bonding in benzene - sp2 hybridisation and delocalisation

Page 1 of 5

BONDING IN BENZENE
Important! This article builds on knowledge about the bonding in
methane, and the bonding in ethene.
You will find the current page much easier to understand if you read
these other ones first.
You may also find it useful to read the article on orbitals if you aren't sure
about simple orbital theory.
You can also read about the evidence which leads to the structure
described in this article. That page includes the Kekul structure for
benzene and the reasons that it isn't very satisfactory.

An orbital model for the benzene structure

Building the orbital model
Benzene is built from hydrogen atoms (1s1) and carbon atoms
(1s22s22px12py1).
Each carbon atom has to join to three other atoms (one
hydrogen and two carbons) and doesn't have enough unpaired
electrons to form the required number of bonds, so it needs to
promote one of the 2s2 pair into the empty 2pz orbital.
So the first thing that happens is . . .
Promotion of an electron

There is only a small energy gap between the 2s and 2p orbitals,

and an electron is promoted from the 2s to the empty 2p to give
4 unpaired electrons. The extra energy released when these
electrons are used for bonding more than compensates for the
initial input.
The carbon atom is now said to be in an excited state.
Hybridisation
Because each carbon is only joining to three other atoms, when
the carbon atoms hybridise their outer orbitals before forming
bonds, they only need to hybridise three of the orbitals rather

file:///C:/Users/NAJAMU~1/AppData/Local/Temp/Low/B6AFMXHA.htm

24-Jul-14

bonding in benzene - sp2 hybridisation and delocalisation

Page 2 of 5

than all four. They use the 2s electron and two of the 2p
electrons, but leave the other 2p electron unchanged.

Important! If you have any doubts about this then you should follow the
links at the top of the page.

The new orbitals formed are called

sp2 hybrids, because they are
made by an s orbital and two p
orbitals reorganising themselves.
The three sp2 hybrid orbitals
arrange themselves as far apart as
possible - which is at 120 to each
other in a plane. The remaining p
orbital is at right angles to them.
Each carbon atom now looks like
the diagram on the right. This is all
exactly the same as happens in
ethene.
The difference in benzene is that
each carbon atom is joined to two
other similar carbon atoms instead
of just one. Each carbon atom uses the sp2 hybrids to form
sigma bonds with two other carbons and one hydrogen atom.
The next diagram shows the sigma bonds formed, but for the
moment leaves the p orbitals alone.
Remember: A sigma bond is formed by the end-to-end overlap
between atomic orbitals.

Only a part of the ring is shown because the diagram gets

extremely cluttered if you try to draw any more.

file:///C:/Users/NAJAMU~1/AppData/Local/Temp/Low/B6AFMXHA.htm

24-Jul-14

bonding in benzene - sp2 hybridisation and delocalisation

Page 3 of 5

Notice that the p electron on each carbon atom is overlapping

with those on both sides of it. This extensive sideways overlap
produces a system of pi bonds which are spread out over the
whole carbon ring. Because the electrons are no longer held
between just two carbon atoms, but are spread over the whole
ring, the electrons are said to be delocalised. The six
delocalised electrons go into three molecular orbitals - two in
each.
Remember: A molecular orbital is the region of space which contains a
bonding pair of electrons.
Warning! Be very careful how you phrase this in exams. You must
never talk about the p orbitals on the carbons overlapping sideways to
produce a delocalised pi bond. This upsets examiners because a pi
bond can only hold 2 electrons - whereas in benzene there are 6
delocalised electrons. Talk instead about a "pi system" - or just about the
delocalised electrons.

In common with the great majority of descriptions of the bonding

in benzene, we are only going to show one of these delocalised
molecular orbitals for simplicity.
In the diagram, the sigma
bonds have been shown as
simple lines to make the
diagram less confusing. The
two rings above and below the
plane of the molecule represent
one molecular orbital. The two
delocalised electrons can be found anywhere within those rings.
The other four delocalised electrons live in two similar (but not
identical) molecular orbitals.
Relating the orbital model to the properties of benzene
Note: To get the best out of this section you ought to read the article on
the Kekul structure for benzene.

The shape of benzene

Benzene is a planar regular hexagon, with bond angles of 120.
This is easily explained. It is a regular hexagon because all the
bonds are identical. The delocalisation of the electrons means
that there aren't alternating double and single bonds. It is planar
because that is the only way that the p orbitals can overlap
sideways to give the delocalised pi system.
The energetic stability of benzene

file:///C:/Users/NAJAMU~1/AppData/Local/Temp/Low/B6AFMXHA.htm

24-Jul-14

bonding in benzene - sp2 hybridisation and delocalisation

Page 4 of 5

This is accounted for by the delocalisation. As a general

principle, the more you can spread electrons around - in other
words, the more they are delocalised - the more stable the
molecule becomes. The extra stability of benzene is often
referred to as "delocalisation energy".
The reluctance of benzene to undergo addition reactions
With the delocalised electrons in place, benzene is about 150 kJ
mol-1 more stable than it would otherwise be. If you added other
atoms to a benzene ring you would have to use some of the
delocalised electrons to join the new atoms to the ring. That
would disrupt the delocalisation and the system would become
less stable.
Since about 150 kJ per mole of benzene would have to be
supplied to break up the delocalisation, this isn't going to be an
easy thing to do.
The symbol for benzene
Although you will still come across the Kekul
structure for benzene, for most purposes we use
the structure on the right.
The hexagon shows the ring of six carbon atoms,
each of which has one hydrogen attached. (You
have to know that - counting bonds to find out how many
hydrogens to add doesn't work in this particular case.)
The circle represents the delocalised electrons. It is essential
that you include the circle. If you miss it out, you are drawing
cyclohexane and not benzene.
Questions to test your understanding
If this is the first set of questions you have done, please read the
introductory page before you start. You will need to use the BACK
BUTTON on your browser to come back here afterwards.
questions on the bonding in benzene
answers

Where would you like to go now?

To read about the Kekul structure for benzene. . .
To the organic bonding menu. . .
To menu of basic organic chemistry. . .
To Main Menu . . .

file:///C:/Users/NAJAMU~1/AppData/Local/Temp/Low/B6AFMXHA.htm

24-Jul-14

bonding in benzene - sp2 hybridisation and delocalisation

Page 5 of 5

Jim Clark 2000 (last modified March 2013)

file:///C:/Users/NAJAMU~1/AppData/Local/Temp/Low/B6AFMXHA.htm

24-Jul-14