Alkanes and Cycloalkanes

Bonding in H2 : The Valence Bond Model

The characteristic feature of valence bond theory is that it pictures a covalent bond
between two atoms in terms of an in-phase overlap of a half-filled orbital of one atom
with a half-filled orbital of the other, illustrated for the case of H2.

Electrostatic potential maps to show this build-up of

electron density in the region between two hydrogen
atoms as they approach each other closely enough for
their orbitals to overlap.

A bond in which the orbitals overlap along a line

connecting the atoms (the internuclearaxis ) is
called a sigma ( σ) bond. The electron distribution
in a bond is cylindrically
symmetrical; were we to slice through a σ bond
perpendicular to the internuclear axis, its cross
section would appear as a circle.
 In molecules, the problem of understanding the
interactions of electrons with the nuclei is more
Molecular Orbital Theory complicated because there are more nuclei and more
electrons that interact.

Imagine, however, the situation that occurs when two nuclei approach one another. If
the two atoms come close enough together, an AO of one atom which contains a single
electron will occupy to some extent the same region of space as an AO of the second
atom which contains a single electron.

When those AOs overlap, an electron from

one atom shares a region of space with the
electron from the other atom. When such an
event occurs, each electron is no longer
influenced by just one nucleus but by two.

This new fact define a new region of space where there is a high probability of finding
both electrons. Furthermore, only two electrons can occupy any particular region of space.
This new region of space is called a molecular orbital (MO), the electrons in the MO are of
lower energy than when they were in their separate AOs, and the lowered energy gives
rise to a chemical bond between the atoms.

Chemical bonds result from the overlap of singly occupied Aos to

give a doubly occupied MO (called a bonding MO) in which each
electron of the pair interacts with both nuclei.
In order to simplify things, we’ll consider the interaction of the orbitals containing
valence electrons to create molecular orbitals. The wave functions of hydrogen atom
A and hydrogen atom B can interact either constructively or destructively.
Constructively:
Ψ(σ) or Ψ+ = (1/√2 ) [φ(1sa) + φ(1sb) ]
Destructively:
Ψ(σ*) or Ψ- = (1/√2 ) [φ(1sa) - φ(1sb) ]

The bonding orbital results in The antibonding orbital results in a

increased electron density between node between the two nuclei, and is of
the two nuclei, and is of lower energy greater energy than the two separate
than the two separate atomic orbitals. atomic orbitals.
 The result is an energy level
diagram with the bonding orbital
occupied by a pair of electrons. The
filling of the lower molecular orbital
indicates that the molecule is stable
compared to the two individual
atoms.

The bonding orbital is sometimes

given the notation σg, where the g
stands for gerade, or symmetric with
respect to a center of inversion.

The anti-bonding orbital is sometimes

given the notation σu, where the u
stands for ungerade, or asymmetric
with respect to a center of inversion.

The signs on the molecular orbitals indicate the sign of the wave function, not ionic
charge!!!
 Introduction to Alkanes: Methane, Ethane, and
Propane

Methane is the lowest boiling alkane, followed by ethane, then propane.

It is generally true that as the number of carbon atoms

increases, so does the boiling point. All the alkanes with four
carbons or fewer are gases at room temperature and
atmospheric pressure.

All of the carbon atoms have four bonds, all of the bonds are single bonds, and
the bond angles are close to tetrahedral.
The methane molecule is CH4 and the four bonds to
carbon are directed toward the corners of a
tetrahedron. Valence bond theory is based on the in-
sp3 Hybridization and Bonding in Methane
phase overlap of half-filled orbitals of the connected
atoms. But with an electron configuration of 1s2 2 s2
2px 1 2 py1 carbon has only two half-filled orbitals
In the 1930s Linus Pauling offered an ingenious
solution to this puzzle !!!!

The electron configuration of a carbon bonded to other atoms need not be the same as a
free carbon atom. By mixing (“hybridizing”) the 2 s 2px 2 py , and 2 pz orbitals, four new
orbitals are obtained. These four new orbitals are called sp 3 hybrid orbitals because they
come from one s orbital and three p orbitals.

1. All four sp 3 orbitals are of equal energy .

2. The axes of the sp 3 orbitals point toward
the corners of a tetrahedron .
3. Bonds involving sp 3 hybrid orbitals of
carbon are stronger than those involving
unhybridized 2s or 2p orbitals .
Isomeric Alkanes: The Butanes

Methane is the only alkane of molecular formula CH4 , ethane the only one that is C2H6
,and propane the only one that is C3H8 . Beginning with C4H10 , however, constitutional
isomers are possible; two alkanes have this particular molecular formula. In one, called n
- butane, four carbons are joined in a continuous chain. The n in n –butane stands for
“normal” and means that the carbon chain is unbranched. The second isomer has a
branched carbon chain and is called isobutane.

The C5H12 Isomers

Three isomeric alkanes have the molecular formula C 5 H 12 . The unbranched isomer
is n -pentane. The isomer with a single methyl branch is called isopentane . The third
isomer has a three-carbon chain with two methyl branches. It is called neopentane .
 Physical Properties of Alkanes and Cycloalkanes
Boiling Point. Methane, ethane, propane, and butane are gases at room temperature.
The unbranched alkanes pentane (C5H12 ) through heptadecane (C17H36 ) are liquids,
whereas higher homologs are solids.

The boiling points of unbranched alkanes increase

with the number of carbon atoms.

that the boiling points for 2-methyl-branched alkanes

are lower than those of the unbranched isomer.

By exploring at the molecular level the reasons for the

increase in boiling point with the number of carbons and
the difference in boiling point between branched and
unbranched alkanes, we can continue to connect structure
with properties.

A substance exists as a liquid rather than a gas because attractive forces between molecules
(intermolecular attractive forces) are greater in the liquid than in the gas phase. Attractive forces
between neutral species (atoms or molecules, but not ions) are referred to as van der Waals forces and
may be of three types:

1. dipole–dipole (including hydrogen bonding)

2. dipole/induced-dipole
3. induced-dipole/induced-dipole
It might seem that two nearby molecules A and
B of the same nonpolar substance would be
unaffected by each other.

In fact, the electric fields of both A and B are

dynamic and fluctuate in a complementary
way that results in a temporary dipole moment
and a weak attraction between them.

An alkane with a higher molecular weight has more atoms and electrons and,
therefore, more opportunities for intermolecular attractions and a higher boiling point
than one with a lower molecular weight.
Branched alkanes have lower boiling
points than their unbranched isomers.
Isomers have, of course, the same
number of atoms and electrons,
but a molecule of a branched alkane
has a smaller surface area than an
unbranched one.
sp 2 Hybridization and Bonding in Ethylene

Ethylene is planar with bond angles

close to 120°; therefore, some
hybridization state other than sp3 is
required. The hybridization scheme is
determined by the number of atoms to
which carbon is directly attached.

In ethylene, three atoms are attached to each carbon, so three equivalent hybrid orbitals
are needed. These three orbitals are generated by mixing the carbon 2s orbital with two of
the 2p orbitals and are called sp2 hybrid orbitals.

The three sp2 orbitals are of equal

energy; each has one-third s character
and two-thirds p character. Their axes
are coplanar, and each has a shape
much like that of an sp3 orbital. The
three sp2 orbitals and the unhybridized p
orbital each contain one electron.
Each carbon of ethylene uses two of its sp2 hybrid orbitals to form bonds to two
hydrogen atoms. The remaining sp2 orbitals, one on each carbon, overlap
along the internuclear axis to give a bond connecting the two carbons.

Each carbon atom still has, at this point, an

unhybridized 2p orbital available for
bonding. These two half-fi lled 2 p orbitals
have their axes perpendicular to the
framework of σbonds of the molecule and
overlap in a side-by-side manner to give a
pi (π) bond.

Electrons in a bond are called π electrons.

The probability of finding a electron is
highest in the region above and below the
plane of the molecule. The plane of the
molecule corresponds to a nodal plane,
where the probability of finding a electron is
zero.
sp Hybridization and Bonding in Acetylene

The structure of acetylene with its bond

distances and bond angles. Its most
prominent feature is its linear geometry.

Because each carbon in acetylene is bonded to two other atoms, the orbital
hybridization model requires each carbon to have two equivalent orbitals available for
σ bonds.

According to this model the

carbon 2 s orbital and one of its 2
p orbitals combine to generate
two sp hybrid orbitals, each of
which has 50% s character and
50% character p.
The two carbons of acetylene are connected to each other by a 2 sp –2 sp
σ bond, and each is attached to a hydrogen substituent by a 2 sp –1 s σ
bond.

The unhybridized 2 p orbitals on

one carbon overlap with their
counterparts on the other to form
two π bonds. The carbon–carbon
triple bond in acetylene is viewed
as a multiple bond of the σ + π + π
type.