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Concept of Resonance

There are certain compounds, which can be represented by more


than one Lewis structures, but none of the structure is able to represent the
molecule in agreement with its experimentally determined parameters. The
phenomenon of resonance is introduced because of the inability of single Lewis
structures to show electron delocalization over the molecule. So Heisenberg
introduced the phenomenon of resonance to explain the properties of certain
molecules.

Take the example of ozone molecule to explain resonance.

In this case, each oxygen atom has an octet of electrons Acc. To


structure (1) there is one single bond (O-O) and one double bond.
The bond lengths for (O-O) and (O=O) are 148pm and 121pm
respectively. So according to the above structures, we expect the
two bond lengths in the ozone molecule will be different, but it is
found that both the bond lengths are equal i.e. 128pm. This bond
length is intermediate between single and double bonds. It means
that above Lewis structures do not account for the observed
experimental facts. It is proposed that the actual structure lies in
between the above two structures and is called resonance hybrid
as shown below.

Resonance hybrid structure of ozone with some electrons delocalized


between the atoms.

Resonance structures have no real existence. These are the only theoretical
based. Also, it does not actual molecule exists as a one form for a certain fraction
of time or in another form. The resonating structures are the only an easiest way
of picturing a molecule to account for its properties.

Thus Resonance can be defined as: when a molecule can’t be represented by a


single structure but its characteristic properties can be described by two or more
than two structures, then the actual structure is said to be a resonance hybrid of
these structures.

Conditions/ Rules for writing the resonating structure:

1) Contributing structure should have same atomic positions. They should


differ only in the electronic arrangement.
2) These structures should have same number of paired and unpaired
electrons.
3) The energy level of contributing structures should be the same.
4) The structure should be written in such a way that the negative charge is
present on the electronegative atom and positive charge is present on the
electropositive atom

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Out of these three structures, 3 one is ruled out because +ve charge is on
more electronegative atom.

5) The like charges should not reside on the adjacent atoms in contributing
structures.
Characteristics of Resonance:

1) Resonating structures are hypothetical and not the real one.


2) The actual molecule has the single structure, which is a resonance
hybrid of various cannonical forms and therefore cannot be presented
by single Lewis structure.
3) The bond lengths in hybrid structure are intermediate of the bond
lengths in various cannonical forms e.g. C – C bind length in benzene
molecule is 139 pm which is intermediate of C – C (154 pm) and C=C
(134pm)
4) Resonance hybrid has lower energy and thus greater stability than any
of its resonating form.
5) The difference of energy between actual bond energy of the molecule
and the most stable resonating form is called resonance energy.
Larger the value of resonance energy more will be the stability of
resonance hybrid.
For example, consider a molecule having three different canonical
structures A, B & C. If C has lower energy and it is more stable. Then the
resonance energy is equal to the difference between the actual bond energy
and the energy of most stable resonating structure. i.e.E3―E

6) Resonating structure are used to calculate the bond order of a


particular bond in a molecule.

For example, take the resonating forms of CO32- ion. For calculating C-O bond
order, consider bonds of C atom with particular O atom in all the resulting
structures.
There are 2 in structure (a),1 in structure (b)and 1 in structure (c)

So the bond order is 2+1+1/3 =1.33

Facts about Resonance:

While studying the concept of resonance we should be very careful about the
following misconceptions

• The sign (↔) present among the resonating structures does not
represent any kind of equilibrium.
• The real molecule cannot be depicted by single Lewis structure.
• The resonating structures (cannonical forms) have no real existence.
• The actual molecule can not be assumed to exist in one cannonical
form at one time and in other cannonical forms at other times.

Resonance Structures and Hybrid:

We can also draw resonance structures from some Lewis


structures. For that the Lewis structure should have multiple bonds
and an adjacent atom with at least one lone pair of electrons. The
general method to draw resonance structures is shown below. The
arrows explain shifting of the electrons from one resonance
structure to another.
Important steps to write resonance structures:

• Transfer one of the lone pairs of electrons on an adjacent


atom down - to form another bond.
• Transfer one of the bonds from either a double or a triple
bond up - to form a lone pair.
• Repeat the same process (above steps) further with the
adjacent atoms to draw additional resonance structures.
• Put double-headed arrows to separate the resonance
structures.

Resonating Structures of some Molecules:

a) Resonance structures of carbonate ions:

b) Resonating structure of bisulfate ion (conjugate base of sulfuric acid)


c) Resonating structure of Carbon monoxide

d) Resonating structure of phosphate ion


Explanation of some structures:

1) Sulfur dioxide

Let’s consider the sulfur dioxide, SO2, molecule. Structural studies explain that
both the bonds in SO2 are of equal length and strength. This electronic
distribution is unexplained by either single Lewis structure, but is clearly
illustrated when both Lewis formulae are taken into consideration.
In resonance hybrid structure, pi electron pair is delocalized or spread
over both S-O bonds and not localized in a single S-O bond.

2) Nitrate ion

Lewis structure for the nitrate ion, NO3-, is drawn below.


Two different types of bonds are shown by Lewis structure in nitrate ion - single
and double. A double bond is stronger than a single bond as it requires more
energy to break a double bond than a single bond.

Bond length of a double bond is always shorter than single bond because the
distance between the nuclei of two atoms in a bond is less than the single bond.
But, experimentally it is found that all the 3 bonds in nitrate ion are of same
strength and same length.

It has been observed that these bonds are longer than double bond but shorter
than single bond. These are also stronger than single bonds but not as strong as
double bonds. This can be explained for the nitrate ion and polyatomic ions like it
with the help of valence-bond model.
Resonating Structure of Nitrate ion:

These resonating structures help the chemists to develop better descriptions of


the nitrate ion, which cannot be explained by a Lewis structures.

The resonance hybrid of nitrate ion (polyatomic):

The actual geometry of the nitrate ion is trigonal planar with bond angles of 120º
3) Formate ion

Resonance structures for the formate ion (HCO2-) are

Second resonance structure can be made from the first by shifting one
lone pair of electron down to form another bond and transferring an
adjacent bond up to form a lone pair. The arrows show the hypothetical
shift of electrons. These resonance structures lead to the resonance
hybrid as drawn below.

Exceptions:

Sometimes general method of drawing resonance structures fails


to draw a reasonable resonance structure. For example:

Fluorine atoms do not participate in resonance. For a fluorine atom to


form two bonds and two lone pairs, it has to lose an electron which is not
possible because of its high electronegativity. Thus any resonance
structure is not considered a reasonable resonance structure that has a
double bond with fluorine atom.
a) But in case of fluoroethene (CH2CHF), it has a double bond and an
adjacent atom with a lone pair of electrons (the factors required for
resonance structure). Out of two hypothetical resonance structures only
one is reasonable:

So fluoroethene does not show resonance and only the first structure is
best described for CH2CHF molecule.

b) Taking the case of formic acid, HCO2H, which has a double bond and
an adjacent atom with a lone pair of electrons? By appearance it gives an
impression of forming a resonance structures.

Similar is the situation with oxygen atoms present in formic acid. Although
it is possible for oxygen atoms to have three bonds and one lone pair yet
it’s not possible for the oxygen atom which is the second most
electronegative element to lose the electron to form the resonance
structure of formic acid.

Thus, we will do away with resonance structures that have three bonds
and a lone pair for an oxygen atom.
The first Lewis structure is reasonable while the second one having three
bonds and a lone pair on an oxygen atom is not a reasonable resonance
structure. So formic acid does not show resonance and only the first
structure is best described for formic acid.

Resonance and the Benzene Molecule:

Resonance structures can also be drawn without the participation of lone


pairs. The examples for this type of resonance structures are benzene,
C6H6, and compounds that contain the benzene ring. All the six carbon
atoms of benzene are linked to each other in a six-membered ring. Lewis
structure of benzene is often represented with three double bonds as
shown below. Its simplest and easiest representation is also shown below.
(1) (2)

(1) With symbols of the elements


(2) Simplest one

It appears from the Lewis structures that benzene molecule it


contains two types of C-C bonds, double and single. But actually all
of C-C bonds of benzene are same, and can be explained why, in
terms of resonance. It is as if the benzene ring were resonating
between the two structures below.

The resonance hybrid of benzene is shown below.


Implications of resonance are

(1) the actual electron distribution is different than would be expected based on a
single Lewis structure, and

(2) the energy of the actual molecule is lower than expected from a single Lewis
structure. This energy lowering is due to electron delocalization and is called
resonance stabilization. The degree of energy lowering or molecular stabilization
is related to the number of resonance structures and the relative stabilities of the
resonance structures.

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