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Fig. 2: The comparison of variation in potential energy of K and F in their neutral and ionic states with
internuclear distance
Valence bond theory and molecular orbital theory - the two theories of bonding.
To understand the energetics of bonding on the basis of the quantum mechanical model of the atom, two
different theories have been used using distinct approaches.
(a) The valence bond theory
Here, to start with, we consider the orbitals of the bonding atoms as one electron wave functions and
then go about combining them before calculating the electronic energy of the resultant 'bonds'. The
essential feature in this approach is that to start with, we distinguish between electrons belonging to
different atoms and correlate them accordingly.
According to quantum theory, the electrons in an atom or a molecule are indistinguishable since they
constantly 'exchange' with each other. The valence bond theory takes care of it by using the concept of
resonance where it implies that the actual "distribution" of electron is a 'resonance hybrid' of all the
different possible "distributions" incorporating all possible types of correlations.
The different "distributions" schemes are referred to as "limiting structures". Thus, for the H2 molecule
we may consider four limiting structures corresponding to the correlations
(i) Atom A - Electron A + Atom B - Electron B (covalent structure)
(ii) Atom A - Electron B + Atom B - Electron A (covalent structure)
(iii) Atom A - Electrons A and B (ionic structure)
(iv) Atom B - Electrons A and B (ionic structure)
We have mentioned this, since the concept of resonance has been used extensively in explaining polar
covalent bonds and bonding in molecules where the electrons are delocalized.
Another special feature about the valence bond approach is that it implies an extra stabilization due to
electron pairing. This is not a general principle.
(b) The molecular orbital theory
Here we consider the orbitals as eigen states in atoms and combine them to form molecular orbitals
before calculating the energies of the latter. Unlike atomic orbitals, the molecular orbitals belong to the
molecule as a whole. After arranging the molecular orbitals in order of increasing energy, we apply Aufbau
principle to fill them up and obtain a description of the electron distribution in the molecule.
(c) Theory and practice - the application of bonding theories for studying chemistry
Both these theories have their advantages and disadvantages and some of the concepts we will be
using are derived from either one or the other of the theories.
Most concepts such as resonance, hybridization of atomic orbitals, orbital box diagrams for electronic
configurations, number of bonds, descriptions of
and
bonds etc. are a direct consequence of the
valence bond theory.
The molecular orbital theory on the other hand has given some approximately parallel concepts such as
bond order instead of the number of bonds;
and
orbitals instead of
and
bonds; bonding,
antibonding and nonbonding electrons instead of bond pairs and lone pairs; delocalised molecular orbitals
instead of resonance, etc.
The electron of hydrogen is represented by a dot. The valence electrons of Fluorine is represented by
crosses 'X'
(b) Expanded octet
Elements belonging to the third and higher period have vacant low lying 'd' orbitals which can be used to
accommodate electrons in excess of eight.
total 17). Then at least one of the atoms will have only seven electrons. Note that none of the atoms
can have nine electrons, i.e. more than an octet (unless in the case of expanded octets as mentioned
above)
But not
Electrons involved in bonding area called bonding electron pairs, where as electrons which are not
participating in bonding are called non bonding electron pairs or lone pairs.
e.g. the oxygen atom in H2O has two lone pairs and two bond pairs.
and
The first is a liquid alcohol and the second a gaseous ether.
2. Some connectivities are ruled out on the basis of octet (or duplet)considerations. For example, H2O
cannot have H-H-O as the connectivity, since it would mean that the middle hydrogen exceeds its duplet.
3. When more than one oxygen atoms are present in a molecule, we normally do not have O-O
connectivity unless and until it is peroxide (or for e.g. ozone, O3). Thus, CH3CO2H cannot have H- -C-OO-H, as the connectivity.
4. For oxoacids, the connectivity should show as many O-H bonds as is the basicity of the acid. For
example H3PO3 (a dibasic acid) should have the connectivity
5. In some cases however, one has to write down the complete Lewis structure, in order to determine
whether it would lead to a stable structure. For example, if you start with N-O-N as the connectivity, the
structure would be
.
Note that in the process, the pair of
lone pair.
Note:
It may also denote the movement of electrons from one molecule to another, but it is never used to
denote the movement of electron deficient species towards electrons, e.g.
(right)
This cannot be shown as
(wrong)
2. In order to show the movement of a single electron, instead of a pair we use a half arrow, e.g.
Structure 1.
Carbon has 1 lone pair and 3 bond pairs.
Total electrons in octet = 1
2+3
2 = 8 octet complete
Number of electrons belonging to C = 1
2+3
1=5
which is, 5 - 4 = 1 more than the valence electrons of C (4)
the formal charge is 1-.
Middle nitrogen has 4 bond pairs.
Total electrons in octet = 4
2 = 8 octet complete
Electrons belonging to N = 4 1 = 4
which is, 4 - 5 = -1 or 1 less than valence electrons of N (5)
the formal charge is 1+.
The terminal nitrogen also has one lone pair and three bond pairs as with the carbon. The octet is
complete and 5 electrons belong to this nitrogen. The number is equal to the number of valence electrons
of nitrogen and so there will be no formal charges.
The final assignment will be
Structure 2.
All octets are complete.
Terminal carbon owns 4 electrons and has no charge.
Middle nitrogen owns 4 electrons and has 1+ charge.
Terminal nitrogen owns 6 electrons and has 1- charge.
:
Final assignment is
:
Structure 3.
Octet of terminal carbon is incomplete.
Terminal carbon owns 3 electrons and has 1+ charge
Middle nitrogen owns 5 electrons and has no charge
Terminal nitrogen owns 6 electrons and has 1- charge.
Final assignment is
Identifying Coordinate Covalent Bonds
A coordinate covalent bond is, as the name suggests, a covalent bond. The only difference is, the bond
was not formed by the two atoms contributing one electron each. Instead, one of the atoms has
contributed both the electrons.
While counting the electrons belonging to a bonded atom, however, the history of how the bond was
formed does not matter. There the rules are simple, the two atoms equally share the two electrons of the
bond. The donor atom in a coordinate bond ends up owning one less electron and the acceptor atom
ends up owning one extra electron.
Example 1.
NH3 and BF3 combine to form a coordinate covalent bond, where N is the donor atom and B is the acceptor
atom as shown below.
Thus N owns one electron less and has a positive charge and B owns one extra electron and has
a negative charge. We may identify this situation as a coordinate bond between N and B and depict it as
shown below.
You should also note that, if the acceptor atom carried a positive charge, before coordinate bond
formation, then in the final situation it should become neutral. The only clue for coordinate bond formation
comes from the appearance of a positive charge on the donor atom.
Example 3.
Consider the reaction of NH3 with H+, where N is the donor atom and H+ is the acceptor atom as shown
below.
Though all the four N-H bonds are equivalent (showing why we insist that a coordinate bond is not
different from a covalent bond), the positive charge on N divulges the information that a coordinate bond
has been formed.
Some thumb rules, regarding when C, N and O carry a charge and when are they neutral in the bonded
state.
Lone pairs
Bond pairs
none
1
2
4
3
2
for C+
for N+
for O+
none
none
1
3
4
3
1
2
3
3
2
1
C-, neutral N and O+ are isoelectronic, i.e they own the same number of electrons (which is 5) and they
have identical bonding environment (1 lone pair and 3 bond pairs).
Other similar examples are as follows:
Neutral C and N+
No lone pair + 4 bond pairs
1 lone pair + 3 bond pairs
Neutral N and O+
2 lone pairs + 2 bond pairs
Neutral O and NWriting the complete Lewis structure and finding the steric number of an atom
To write a complete Lewis structure, these five steps are followed:
1. Write down the connectivity.
2. Give each atom its due share of electrons.
3. Pair up all the electrons.
4. Check and correct octets.
5. Assign formal charges.
The steric number (SN) of an atom is given by SN = number of lone pairs + number of
bonds. If there
bond. If there are multiple bonds between two atoms, then
is only one bond between two atoms, it is a
bond and the others are bonds.
one of them is a
Example 1.
CO
Step 1. (connectivity) C - O
Further, since both C and O have one lone pair and one
both the cases.
Example 2.
O3
Step 1. O - O - O
Step 2.
Step 3.
Step 4. Note that the central oxygen has more than an octet (10 electrons). Correct this by transferring
bonding electrons to the corresponding terminal oxygen as shown below.
a pair of its
Step 5. The central oxygen owns only 5 electrons. This implies that there is a positive charge on it.
The right terminal oxygen owns 7 electrons. This implies that there is a negative charge on it.
Final assignment
However, since S belongs to the 3rd period and can undergo valence shell expansion, the octet
restriction need not be applied here and
is also a valid structure.
Example 4.
NO2+
Step 1. O - N - O (not N - O - O, which implies a peroxide)
Step 2.
Since it is
and not NO2, we must remove one electron either from N or from O.
Step 3.
Step 4. Correct the incomplete octet of the right terminal oxygen of the first case.
=3
The general formula for a open chain hydrocarbon with no bond (saturated hydrocarbon) is CnH2n + 2.
The number of hydrogen atoms decreases in units of two for every - bond. Thus the general formula for
an alkene is CnH2n and for an alkyne it is CnH2n-2. In case of cyclic compounds, each ring means a decrease
of two hydrogen atoms from the formula of open chain saturated hydrocarbon)
Thus an index is formulated called hydrogen deficiency index (HDI) of a hydrocarbon having formula
CxHy as
HDI =
where HDI = (number of bonds) + (number of rings)
For example in C6H6 (benzene)
HDI =
In benzene we have 3 bonds and 1 ring.
In case hetero atoms are present, simply remove the atoms to get back to the parent hydrocarbon
formula
(i) Remove halogen and replace by a hydrogen atom.
(ii) Remove oxygen of sulphur - no further adjustment is necessary.
(iii) Remove nitrogen or phosphorus and remove a hydrogen atom along with it.
(In the same manner if you decrease one carbon atom to step down in the homologous series, remove
one CH2)
For example,
Structural formula
Molecular formula
C 2 H4 O
C 2 H4
C 2 H4
C2H3Cl
C2 H4
C 2 H5 N
C2 H4
C 2 H4
. The natural question that comes to our mind is, which one is correct? Ozone is not any
unique case. The concept of resonance is a very important component of the valence bond theory of
bonding and is actually related to the more general phenomenon of delocalization of electrons in a
molecule.
The concept of resonance:
Let us look at the actual electron distribution in ozone. Both the oxygen-oxygen bonds are exactly
equivalent and each of the terminal oxygen atoms carries 1/2 unit of negative formal charge. Using the
concept of resonance, therefore, each of the structures is a hypothetical limiting structure and the actual
electron distribution is considered as a resonance hybrid of all possible limiting structures.
Conventionally double headed arrows are used to show resonance involving limiting structures.
Thus for O3 we write
For SO2 we write
, etc.
Each description is used to explain the various aspects of reactivities of carbonyl compounds.
A more significant use of resonance is to describe the long range delocalization of electrons (as we have
observed in ozone) leading to an extra stability in molecules. Such a delocalization can take place when
there is 'conjugation' in the molecule.
Example 2
Example 3
If there is a gap of more than one bond, then there will be no conjugation.
The
Example 4
If there are no gaps, then too there will be no delocalisation or conjugation.
But since there is no gap of any bond, we cannot write resonance structures (as suggested below). There
is no conjugation possible here.
Which one of the limiting structures, I or II, is more significant? The general rule is that if a limiting
structure denotes an unstable (hypothetical) molecule, it is not significant. On these grounds we may say
that structure I showing a positive charge on an electronegative oxygen atom is not significant.
Let us study some of the rules which will tell us how to distinguish between possible and impossible
resonance structures, and also between those that are significant and there which are not.
Applying rules of resonance
1. Possible and impossible structures
a) The number of paired and unpaired electrons must be the same in all the limiting structures.
b) Resonance involves only the movement of electrons for a given nuclear arrangement, i.e., the relative
position of the nuclei cannot differ from one limiting structure to another (distinction from tautomerism)
c) Resonance implies the delocalization of electrons which is possible when the molecule is planar. For
example, benzene is planar and there is electron delocalization because of resonance.
But there may be no resonance involved, though all the conditions required for conjugation may
'apparently' exist. For example:
does not show resonance since it is not planar, but tub shaped as shown below.
d) Structures should not imply the expansion of octets for elements of the second period (or duplets for
elements of the first period). For example, we have already seen that
contributing structure.
cannot be a
b) Generation of isolated charges in a structure reduces its significance. This is another reason why the
second structure shown for butadiene above becomes so insignificant. Structures with more than two
isolated charges have insignificant contribution.
c) Heterovalent resonance may give rise to significant structures if it increases the negative charge
(electron density) on the more electronegative atom. We have already seen an example of this in the
example of resonance in but-2-enal.
d) Structures where like charges are present close to each other are normally not significant.
For example, in
etc. For n = 1, we have the well known case of benzene where the extra resonance stabilization is related
to aromaticity.
Aromaticity and aromatic stabilization may be present in compounds other than benzene and also for
other values of n. Some other such examples of molecules and ions showing aromatic stabilization are
given below.
Step 1. Find out the steric number from the lewis structure.
The steric number determines the basic arrangement of electron pairs as follows:
Steric number
Shape
Linear
Trigonal planar
Tetrahedral
Trigonal bipyramid
Octahedral
Pentagonal bipyramid
Step 2. Write down the VSEPR formula for the given molecule as ABmEn where m is the
number of BP = number of connected neighbouring atoms (B) and n is the number of LP or
non bonding electron pairs (E).
Writing VSEPR formulas for molecules and identifying molecules having
identical VSEPR formulas
Write down the Lewis structure. then number of LP = m and number of
bonds or
connected neighbours = n for the central atom.
Example 1
ClF3
Lewis structure
Number of LP for Cl = 2 = n
Number of nearest neighbours of Cl = 3 = m
VSEPR formula AB3E2
Note:
m + 2n = 3 + 4 = 7 = number of valence electrons in Cl.
Example 2
SO2
Lewis structure
Number of LP for s = 1 = n
Number of nearest neighbours of s = 2 = m
VSEPR formula AB2E
Note:
2m + 2n = 4 + 2 = 6 number of valence electrons in S.
In the first case we have calculated the number of valence electrons as m + 2n but in the
second case we have calculated it as 2m + 2n.
This is because in ClF3 all the bonds are single bonds but in SO2 all the bonds are double
bonds.
If we remember that oxygen forms double bonds whereas halogens (e.g. F) forms single
bonds we can identify different molecules having same VSEPR formula.
The table above gives us an idea regarding the group number of the central atom
corresponding to different VSEPR formulas and also tell us how the sets.
(i) AB2, AB2E, AB2E2, AB2E3
(ii) AB3, AB3E, AB3E2
(iii) AB4, AB4E, AB4E2
(iv)AB5, AB5E and
(v) AB6, AB6E will show variation of shapes within each set.
Step 3.
Determine the shapes of the molecule with respect to ABm on the basis of the table.
Since the lone pairs cannot be seen, the shape of molecule, will be different from the
"arrangement of valence shell electrons", if lone pairs are present on the central atom.
Determining the shapes of molecules on the basis of VSEPR formula ABm En
Let us consider an example:
XeF2 has VSEPR formula AB2 E3 with steric number 5. The arrangement of electrons will be
trigonal bipyramid. But the shape will only be with respect to the bonded atoms since the
lone pairs cannot be seen. The difference should become clear from the figure below.
Steric
number
2
Arrangement
Linear
Bond angle 180o
VSEPR
formula
Shape
AB2
Linear
Trigonal planar
Bond angle 120o
Example
CO2, NO2+, N2O,
HgCl2, OCS
BF3, NO3-, CO32-,
SO3
AB3
Trigonal planar
AB2E
SO2,
, NO2-
Bent
4
Tetrahedral
Bond angle 109o 28'
AB4
CH4, CHCl3,
NH4+,BH4-, SO42,PCl4+
Tetrahedral
NH3,H3O+,
PCl3,SO32-, XeO3
AB3E
Trigonal pyramid
AB2E2
H2O,SCl2,OF2,XeO
2
Angular or V-shaped
5
Trigonal bipyramid
Bond angles 120o,
180o and 90o
AB5
PCl5,PF3Cl2
Trigonal bipyramid
SF4, IO2F2-
AB4E
See-saw or distorted
tetrahedral
AB3E2
BrF3,ClF3
T-shaped
I3-,ICl2-, XeF2
AB2E3
Linear
6
SF6, PF6-
Octahedral
AB6
Bond angles 90o, 180o
Octahedral
BrF5, XeOF4
AB5E
Square pyramidal
ICl4+, XeF4
AB4E2
Square planar
IF7
Pentagonal bipyramid
AB6E
XeF6
Distorted octahedral
Predicting bond angles and explaining variations:
It is clear that if the steric number of two molecules are the same, their bond angles should have similar
values. For example, CH4, NH3 and H2O all have central atoms with SN = 4. The bond angles are as
follows:
H - C - H in CH4 109o28' (AB4 molecule)
H - N - H in NH3 107o (AB3E molecule)
H - O - H in H2O 104.5o (AB2E2 molecule)
We can also explain the direction of variation using VSEPR theory (one being greater or less than the
other). Lone pairs repel more than bond pairs. Hence, lone pairs will try to push the bond pairs together
and reduce the angle between the bond pairs. The greater the number of lone pairs, the greater will be
the reduction in bond angles. Thus we have the bond angles in the example above in the order.
AB2E2 < AB3E < AB4
Note:
The VSEPR theory cosiders only the number of BP and LP. It has no consideration for the size or
electronegativity of the atoms concerned. Hence it cannot explain the difference in the bond angles of
molecules having the same VSEPR formula.