CH.

Chapter 2
Alkanes

This chapter is concerned with the chemistry of alkanes. Alkanes are hydrocarbons.
Hydrocarbons are molecules that contain only C and H.

There are two main classes of hydrocarbons: (1) aliphatic and (2) aromatic.

(1) Aliphatic hydrocarbons have three main groups:

a. Alkanes: contain only carbon-carbon single bonds.
b. Alkenes: have carbon-carbon double bonds
c. Alkynes: have carbon-carbon triple bonds

(2) Aromatic hydrocarbons (also called arenes) have conjugated, circular double bonds
that have special properties. These are derivatives of benzene.

H H H
H
H C C H C C H C C H
H H H H
ethyne (alkyne) benzene (aromatic)
ethane (alkane) ethene (alkene)

Electron Waves and Chemical Bonds

Electrons have both particle and wave properties. Chemical bonding between atoms can
be thought of as the interaction of two waves. There are two widely used theories of
chemical bonding: (1) the valence bond model and (2) molecular orbital theory. For
simple molecules the theories are similar.

Consider the bonding between two hydrogen atoms and what happens as the distance
between them begins to decrease. There are three types of interactions: (i) electron-
electron repulsion (minus charge repelling minus charge) (ii) electron-nucleus attraction
(minus charge attracting the positive charge of the nucleus)) and (iii) nucleus-nucleus
repulsion (positive charge repelling positive charge). All of these forces increase as the
distance between the two nuclei decreases. The electrons are mobile and can maximize
their attractive forces while minimizing their repulsive forces. As the nuclei get to
bonding distance the attractive forces are at a maximum and there is a potential energy
minimum. This occurs at 0.74 A°. If the two nuclei approach closer than this the
repulsive forces between the two positively charged nuclei begin to dominate.

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 CH.2

increasing internuclear distance

0.74A°
ΔΕ

H H
H H

104
Kcal/mol H H

There are two ways that waves can add to reinforce each other: constructive interference
in which the two waves add in the same phases and destructive interference in which the
two waves add out-of-phase and cancel each other.

Constructive interference - the waves add to each other

Destructive interference - the waves cancel each other out

Electron waves in atoms are characterized by their wave function, which is a

mathematical description of the shape of the wave. This is called the orbital and defines
where most of the electron density is to be found. The valence bond model constructs the
bond from the overlap of the available orbitals of each bonding atom. These are the
familiar 1s, 2s, 2p orbitals. The molecular orbital theory is more complicated in that it
constructs new orbitals from the available atomic orbitals. These new orbitals are called
molecular orbitals and spread over the entire new molecule.

For bonding in the simple H2 case both theories give a similar picture.

Bonding in Hydrogen: Valence Bond Model

We have an in-phase overlap of a half-filled 1s orbital of one atom with a half-filled 1s
orbital of the other. These combine to form a sigma bond. The

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 CH.2

atomic orbitals molecular orbitals

+ and

1s 1s sigma bond (σ) anti-bonding orbital

(bonding orbital) (σ∗)

The energy of the system is lowered because now each electron is attracted by two
protons, one in each hydrogen nucleus, and each proton is now attract by two electrons.

Molecular Orbital Model

In the molecular orbital model, the two 1s wave functions are combined (in a process
called linear combination of atomic orbitals) to give two new molecular orbitals. There
are two ways that the orbitals (or wave functions) can be combined. They can be added
constructively to give a σ orbital that is bonding. In the bonding
σ orbital most of the electron density of the two bonding electrons is concentrated
between the two nuclei. This bonding orbital will be lower in energy than two separated
hydrogen 1s orbitals. The other way they can be combined is by subtraction. Their signs
will be opposite. This will result in destructive overlap with no electron density between
the two nuclei. This orbital will be anti-bonding and will be higher in energy than two
separated 1s orbitals. This anti-bonding orbital is typically called a σ orbital (sigma star
∗

orbital).

+ -

σ orbital σ∗ orbital

Electrons are then put into the lowest energy orbitals first. The two electrons in H2 go
into the low energy bonding orbital.

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 CH.2

(σ∗) anti-bonding orbital

Energy

1s 1s

(σ) bonding orbital

For a simple molecule like H2, there is not much difference between the valence bond
picture of bonding and the molecular orbital picture but differences do become apparent
when the molecules become larger.

Alkanes: Methane, Ethane Propane

Alkanes have the general formula CnH2n+2.

Methane, with the formula CH4, is the simplest alkane. All four bonds are the same,
oriented in a tetrahedral array. This is the shape that keeps the four substituents as far
apart as possible so as to minimize repulsion between the electrons in the four C-H
bonds. In order to form four equal bonds from we need to use the concept of
hybridization. Look at the electronic structure of carbon.

2p Combine sp3
2s orbitals
4 hybrid orbitals
Energy

1s sp3 orbital

There are three 2p orbitals and one 2s orbitals available for bonding. The 1s orbital is too
low in energy and need not be considered. These four orbitals are combined to give four
sp3 orbitals that are oriented in a tetrahedral fashion.

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 CH.2

sp3 orbital of carbon s orbital of hydrogen

dashed
wedge, bond 109.5 °
going back H
into the paper H C 1.09 A°
H H

solid wedge, bond is

coming out of paper

To form a new C-C single bond as in ethane, C2H6, we need to have the end-to-end
overlap of two sp3 orbital on each carbon. This forms a sigma bond in which the electron
density of the two electrons formed in the bond is largely confined between the two
carbon atoms.

111° ethane, C2H6

H H 1.11 A°

H C C H
H H
1.53 A°
C-C sigma bond

Propane has the formula C3H8 (CH3CH2CH3)

H H 1.53 A°

H C H 1.11 A° propane
C C
112° H
H H H

Ethene, Hybridization and Bonding

Ethene (or ethylene) is trigonal and planar with sp2 hybridized carbons.

1.34 A°
H H
H H H H
117°
C C or C C trigonal, planar C C
1.10 A°
H H H
121° H H
H
sp2 carbon

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 CH.2

To form the three hybrid orbitals that are trigonal planar, combine two 2p orbitals with
one 2s orbital to give three new orbitals that are intermediate in energy between the 2s
and 2p orbitals. These are the sp2 orbitals. They are similar in shape to the sp3 orbitals
but are slightly smaller due to the greater percentage of p character (33.3% p character in
sp2 versus 25% p character in sp3 orbitals). This leave one 2p orbital unchanged. This
will be use to form π−bond.

2p 2p
Combine sp2
3 hybrid orbitals
2s orbitals

Energy Combine two 2p and one 2s orbital to give 3 hybrid orbitals.

1s sp2 orbital

The carbon-carbon double bond is made up of two different types of bonds. There is a
sigma bond made up of end-to-end overlap of two sp2 orbitals, one on each carbon. The
main portion of electron density in this bond is between the two nuclei. The second bond
is the π−bond. It is made up of overlap of the two 2p orbitals, one on each carbon. In the
π−bond the main portion of the electron density is above and below the plane of the
sigma framework. The π−bond is not nearly as strong as the sigma bond and as we will
see in subsequent chapters, it is quite reactive as a nucleophile.

Sideways overlap of the two 2p orbitals creates the π−bond. There is

electron density above and below the plane of the sigma framework.

1s orbital of H overlap of sp2 orbital of

carbon and 1s of
sp2 orbital of carbon hydrogen creates the C-
H bond

end-to-end overlap of two sp2 carbon

orbitals creates the C-C sigma bond

Note that all the six atoms of ethene, the two carbons and four hydrogens, lie in the same
plane and the π−bond, made up of sideways-overlap between the two 2p orbitals, lies
perpendicular to this plane.
H H Another view of ethylene showing only the sigma
framework and the π-portion of the double bond.

H H

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 CH.2

Ethyne, Hybridization and Bonding

Ethyne or acetylene has a triple bond. It is linear with two sp hybridized carbons.

1.2 A°
1.06 A°
H C C H
180 °

To form two identical carbon orbitals that are oriented in a linear fashion, one 2p and one
2s orbital are combined to give two sp hybrid orbitals.

2p 2p
Combine sp
2 hybrid orbitals
2s orbitals

Energy Combine one 2p and one 2s orbital to give 2 hybrid sp orbitals with two 2p
orbitals left over.
1s sp orbital

The sp orbital is similar in shape to the sp3 and sp2 orbitals but it is smaller, with the bulk
of the electron density closer to the nucleus. Therefore an electron in an sp orbital is
more tightly held than an electron in an sp2 orbital, which in turn is more tightly held than
an electron in an sp3 orbital.

Relative sizes oof the hybrid orbitals.

sp2 sp
sp3

The sigma framework of ethyne is linear. The C-C single bond is made up of end-to-end
overlap of two carbon sp bonds and the two C-H sigma bonds are made up of overlap of a
carbon sp bond and a 1s orbital of hydrogen. The sp hybridization leaves two 2p orbitals
on each carbon. These 2p orbitals are mutually perpendicular. They overlap to form two
mutually perpendicular π−bonds.

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 CH.2

π−bond formed from overlap of two 2p orbitals

Second π−bond formed from overlaps of the

other pair of 2p orbitals.
The two π−bonds are mutually perpendicular.

Sigma C-H bond formed from overlaps of

carbon sp orbital and 1s orbital of hydrogen.

Sigma C-C bond from end-to-

end overlap of two carbon sp
orbitals.

Another picture, showing the sigma framework and the two mutually
H C C H perpendicular π−bonds. One π−bond is in the plane of hte page
and the other π−bond is coming out of the page, perpendicular to
the first one.

Butane has the formula C4H10. Butane can exist in two different forms called isomers.
Isomers are molecules that have the same formula but have one or more properties that
are different. There are several types of isomers possible. Isomers in which the atoms are
connected together in different ways are called constitutional isomers.
H H H H CH3
H C C C C H CH3 C CH3
H H H H H
This is sometimes called n-butane isobutane
where n = normal or unbranched.

Methane, ethane, propane and butane are all gases are room temperature.

CH4 CH3CH3 CH3CH2CH3 CH3CH2CH2CH3 (CH3)3CH

methane ethane propane n-butane isobutane
b.p. -160 °C b.p. -89°C b.p. -42 °C b. p. -0.4 °C b.p. -10.2 °C

Note the regular increase in boiling point as the number of carbons increases.

Note also:

CH3 CH2 C
H
methyl group methylene group methine group

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 CH.2

Pentane, C5H12, has three possible constitutional isomers. Note the zigzag shape for n-
pentane.

n-pentane CH3CH2CH2CH2CH3 or CH3(CH2)3CH3 or

isopentane CH3CHCH2CH3 or (CH3)2CHCH2CH3 or

CH3

CH3
neopentane or (CH3)4C or
CH3 C CH3
CH3

The number of isomers increases rapidly as the number of carbon atoms increases. For
example, C6H14 has 5 isomers, C7H16 has 9 isomers and C40H82 has 62,491,178,805,831
isomers!!! There is no simple way to tell how many isomers are possible for a given
number of carbons. The best way to find all the isomers is to draw out the straight chain
isomer first and then systematically branch the carbon atoms. The key thing is the way
the carbons are connected (the connectivity). For example, all of the following molecules
are actually the same.

CH3 CH3 CH3

CH3CHCH2CH3 CH3CHCH2CH3 CH3CH2CHCH3 CH3CH2CHCH3 CHCH2CH3
CH3 CH3 CH3

Types of Carbons

Carbons are classified according to the number of other carbons attached to the carbon in
question.
- Primary (1°) carbons have one other carbon attached.
- Secondary (2°) carbons have two other carbons attached.
- Tertiary (3°) carbons have three other carbons attached.
-Quaternary carbons have four other carbons attached.

secondary carbon
CH3 CH3 primary carbon
CH3 C CH2 C CH2 CH3
CH3 H
tertiary carbon
quaternary carbon

IUPAC Nomenclature

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 CH.2

The International Union of Pure and Applied Chemistry has devised a systematic set of
rules for naming compounds. The rules are somewhat arbitrary but they are internally
consistent and each compound has its own unique name. We need to learn these rules,
first for alkanes, and then for other functional groups as we proceed through the course.
The rules for alkanes provide the foundation for the rules to follow.

Number of carbons formula alkane alkyl group representation

C1 CH4 methane methyl CH3

C2 CH3CH3 ethane CH2CH3

ethyl

C3 CH3CH2CH3 propane propyl CH2CH2CH3

isopropyl CH3 CH CH3

C4 CH3(CH2)2CH3 butane butyl CH2CH2CH2CH3

CH3
isobutyl CH2CH
CH3
sec-butyl CH3 CH CH2CH3

CH3
tertiary-butyl C CH3
CH3

C5 CH3(CH2)3CH3 pentane pentyl CH2CH2CH2CH2CH3

CH3
isopentyl
CH2CH2CH
CH3
CH3
neopentyl CH2 C CH3
CH3
C6 CH3(CH2)4CH3 hexane hexyl

C7 CH3(CH2)5CH3 heptane heptyl

octane octyl
C8 CH3(CH2)6CH3

C9 nonane nonyl
CH3(CH2)7CH3

decyl
C10 CH3(CH2)8CH3 decane

Rules for Naming:

1. Pick out the longest continuous chain. This is the parent chain.

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 CH.2

2. Identify the substituent groups.

3. Number the longest continuous chain so that the substituent at the first point of
branching gets the lowest number.

1 2 3 4 5 2 3 4 5
CH3 CH CH2CH2CH3 or CH3 CH CH2CH2CH3 pentane
CH3 1 CH3

4. Write the name designating the position of the substituent by number.

1 2 1 2 3 4 5
3 4 5
CH3 CH CH2CH2CH3 CH3CH2 CH CH2CH3
CH3 CH3
2-methylpentane 3-methylpentane

5. If a substituent occurs more than once, use di-, tri-, tetra-, etc. and repeat the number.
CH3
1 3 4 5
CH3 C CH2CH2CH3 2,2-dimethylpentane
2
CH3

6. If there is more than one substituent, list them in alphabetical order, ignoring any
prefix such as di-, tri-, etc.

CH2CH3
1 2 3 6
CH3 CH2 CH CH CH2CHCH2CH3 4-ethyl-3,6-dimethyloctane
CH3 4 5 CH 7 8
3

7. Number the chain so as to give the lowest number at the “first point of difference” in
the two possible numbering schemes.

8 4 2 1 3 5 7
6 2 4 6 8
7 5 3 1
B
A 2,2,6,6,7-pentamethyloctane 2,3,3,7,7-pentamethyloctane
CORRECT INCORRECT
A is the correct numbering since there is a '2' at the second number
whereas B has a '3' at the second number position.

Cycloalkanes

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 CH.2

CH2 CH2 CH2 CH2 CH2 CH2

CH2 CH2 CH2
CH2 CH2 C
cyclopropane H2
cyclobutane cyclopentane
H2
C
CH2 CH2
CH2 CH2
C
H2 cyclohexane

Number the ring so that the lowest number is given to the substituent at the first point of
difference between the two possible numbering schemes.

CH3 CH3 CH3 CH3

CH2CH3
1 2 3 2
ethylcyclopentane 3 B
A
CH2CH3 1 CH2CH3
CORRECT INCORRECT

3-ethyl-1,1-dimethycyclohexane 1-ethyl-3,3-dimethylcyclohexane

Numbering scheme A is correct because the lowest number at the first point of difference
is 1,1,3 and not 1,3,3- as in numbering scheme B.

When the ring itself has fewer carbons than the alkyl that is attached, the ring is
considered as a substituent.

1 2 3 4 5
CH3 CH CH2CH2CH3 2-cyclobutylpentane

Physical Properties of Alkanes

There is a regular increase in the boiling point as the number of carbons increases. The
boiling points are lowered for 2-methyl branched alkanes. This is due to a decrease in the
weak intermolecular attractive forces. A branched alkane has a smaller surface area than
a linear molecule. Therefore there is less surface area for the induced dipole-induced
dipole interactions. (See below)

CH3
CH3CH2CH2CH2CH3 CH3CHCH2CH3 CH3 C CH3
CH3 CH3
pentane
2-methylbutane 2,2-dimethylpropane
b.p. 36 °C
b.p. 28 °C b.p. 9 °C

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 CH.2

In general there are three types of attractive forces between molecules:

(1) dipole-dipole interactions, including hydrogen-bonding.

(2) dipole-induced dipole interactions
(3) induced dipole-induced dipole interactions

The intermolecular attractive forces in alkanes are due to the induced dipole-induced
dipole interactions called van der Waal’s forces. These are very weak. Alkanes are
essentially non-polar so the only attractive forces are these weak van der Waal’s forces.
In small alkanes (four carbons or less) the overall effect is weak and the compounds are
gases at room temperature. As the molecules become larger the cumulative effect of the
forces increase and we see the increase in boiling points as the number of carbons
increases until finally large hydrocarbons can be solids at room temperature.

The induced dipoles are caused by the moment of the electrons in the C-H bonds. At any
given instant, as the electron moves in its wave pattern in the molecular orbital, it may
create a slight excess of (-) charge in one localized region. This tiny, transient excess of
(-) charge will in turn induce an excess of (+) charge in a neighboring molecule.

A temporary excess of negative charge induces a

corresponding excess of (+) charge in a
neighboring molecule.

Reactions of Alkanes

Alkanes are relatively unreactive. One important reaction that they do undergo is
combustion.

CH4 + 2O2 CO2 + 2H2O ΔH = -890 KJ/mol

The heat of combustion, ΔΗ, is defined as the heat of the products at standard pressure
minus the heat of the reactants. ΔΗ is the enthalpy or heat given off.

ΔΗ = ΔΗ°products - ΔΗ°reactants

The heat of combustion is a measure of the stability and potential energy of the molecule.
The smaller the heat of combustion, the more stable the molecule.

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 CH.2

ΔΗ = −5471 ΚJ/mol

ΔΗ = −5466 ΚJ/mol

ΔΗ = −5458ΚJ/mol

ΔΗ = −5452ΚJ/mol lowest in energy, most stable

In general the heat of combustion decreases with increased branching. The attractive
intramolecular forces increase more than the repulsive forces as the molecule becomes
more compact.

Oxidation/Reduction

Calculation of oxidation state for carbon:

For CH4, assume that H has an oxidation state of +1; therefore carbon is -4.

For CO2, oxygen has an oxidation state of -2; therefore carbon is +2.

Look at the following carbon oxidation states.

H OH O O O
H C H H C H H C H H C OH HO C OH O C O
H H
+2 +4 +4
-4 -2 0
fully oxidized
fully reduced

In general, when carbon is oxidized there is an increase in the number of bonds between
C and O and there is a decrease in the number of hydrogens attached to the carbon.

In general when carbon is reduced, there is an increase in the number of C-H bonds and a
decrease in the number of C-O bonds.

To calculate the oxidation number of carbon:

(1) Write a Lewis structure with the electron pair. (2) Assign the electrons in a covalent
bond to the more electronegative partner. (3) For the bond between two atoms that are the
same, give one electron to each atom. (4) Count the electrons assigned to each atom and
subtract this from the number of valence electrons in the neutral atom (carbon has 4
valence electrons). For ethanol:

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 CH.2

H H H H

H C C O H (2) H C C (3) C2 C1 O H
O H
2 1 2 1
H H H H
step 1 step 3
step 2

C1 has 5 electrons – 4 valence electrons = -1 oxidation state.

C2 has 7 electrons – 4 valence electrons = -3 oxidation state.
Oxygen has oxidation state -2 and hydrogen has oxidation state +1.

A carbon is oxidized if a hydrogen atom is replaced by a more electronegative atom. For

the hydrocarbons:

increasing oxidation of carbon, decreasing hydrogen content

H H H
H
H C C H C C H C C H

H H H H

ethane, fully reduced ethene, partially oxidized ethyne, more oxidized

(contains 14 electrons) contains 12 electrons contains 10 electrons

For CH3Cl and CH3OH both carbons have the same oxidation state of -2. The reaction of
chlorine with methane, to be discussed in CH. 4, involves an oxidation of the carbon.

CH4 + Cl2 CH3Cl + HCl

And, a carbon is reduced if a hydrogen atom is replaced by a less electronegative atom.

Here the carbon goes from oxidation state -2 to oxidation states -4, the same as in CH4.

CH3Cl + 2Li CH3Li + LiCl

Bonding in Ammonia and Water

We can use the same valence bond theory to describe the bonding in ammonia, NH3, and
water, H2O, which we have used for the hydrocarbons. It is useful to view the central
atom in both these molecules as sp3 hybridized and therefore tetrahedral in shape.

In ammonia, we have an sp3 hybridized nitrogen and three hydrogen atoms and one lone
pair. The lone pair occupies one of the four equivalent sp3 orbitals and the three
hydrogens occupy the other three sp3 orbitals. There is a slight deviation from the ideal
109.5° tetrahedral angles. The H-N-H angles is 107° because the lone pair takes up a bit
more space since the two electrons are not bonded to another atom.

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 CH.2

In water, we have an sp3 hybridized oxygen and two hydrogens occupying sp3 orbitals and
two lone pair in similar orbitals. In water the H-O-H angle is 105°, smaller than the
tetrahedral 109.5° due to the larger space occupied by the lone pair.

C N O
H H H
H 107°
H H 109.5° H H 105°

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