Professional Documents
Culture Documents
A chemical bond forms if, as a result, the energy of the bonded atoms is substantially lower than that of
separate atoms so that the combination can be detected as a separate unit. If the lowest energy can be
achieved by ion formation, then the bonding will be ionic. If the lowest energy can be achieved by electron
sharing, then the bonding will be covalent. Hence, to come to any conclusion about the type of bonding
present in a compound, we must consider the energy changes that accompany bond formation.
The above description gives a general picture about the energetics of covalent bond formation where both
atoms are electronegative and the resultant bonding involves a sharing of two electrons.
If one atom is electropositive and the other electronegative, even then a potential energy minimum will
be seen corresponding to covalent bond formation. Then why do we have the formation of an ionic bond in
such cases?
If we look at the case of bonding between potassium (K) and fluorine (F), we can further elaborate on the
puzzling situation. The figure 2 sums it up graphically.
At large distance, the potential energy of a neutral (K + F) situation is much lower than the (K+ + F-)
situations. This is because (ionisation energy of K - electron affinity of F) involves an increase in energy
from a system containing isolated gaseous atoms of K and F. However, as the internuclear distance
decreases, the coulombic attraction between K+ and F- gaseous ions starts increasing sharply. The
potential energy curves for the ionic state then crosses the curve for the neutral state to reach a minimum
value, which is much lower than that for the latter.
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.
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.
(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.
Representing Electron Distribution in Covalent Molecules
Lewis, in 1916, used his insight to explain the bonding in covalent molecules by identifying the essential
features of a covalent bond.
"A covalent bond is a pair of electrons shared between two atoms."
He thought that, because the two electrons of a shared pair can attract the nuclei they lie between
and would pull the two atoms together. The brilliance of Lewis lay in conjuring up this figure of 'two'
electrons being shared on the basis of the knowledge about the number of valence electrons in an atom
and about molecular formulas only. He had no idea about orbitals and the quantum mechanical model of
the atom. Today, we know that in covalent bonding, two atoms share an orbital which because of Pauli's
exclusion principle cannot have more than two electrons. Lewis had used an empirical rule called the
octet rule to reach his conclusions.
Octet Rule:
Atoms proceed as far as possible towards completing their octets by sharing electron pairs.
The electron of hydrogen is represented by a dot. The valence electrons of Fluorine is represented by
crosses 'X'
But not
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-O-
O-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 bonding electrons have moved from between C and O on to O as a
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)
(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
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.
Example 2.
HNO3 can be shown as
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
for neutral carbon none 4
for neutral nitrogen 1 3
for neutral oxygen 2 2
for C+ none 3
for N+ none 4
for O+ 1 3
for C- 1 3
for N- 2 2
for O- 3 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
Neutral N and O+ 1 lone pair + 3 bond pairs
Neutral O and N- 2 lone pairs + 2 bond pairs
Writing 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
is only one bond between two atoms, it is a bond. If there are multiple bonds between two atoms, then
one of them is a bond and the others are bonds.
Example 1.
CO
Step 1. (connectivity) C - O
Further, since both C and O have one lone pair and one bond each, the steric number is 1 + 1 = 2 in
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
a pair of its bonding electrons to the corresponding terminal oxygen as shown below.
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
Example 3.
SO2
Here, since S and O belong to the same group and have the same number of valence electrons, one of the
possible structures would be
However, since S belongs to the 3rd period and can undergo valence shell expansion, the octet
restriction need not be applied here and
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.
Final assignment
Steric number for oxygen atoms is 2 lone pairs + 1 =3
Steric number for nitrogen is
zero lone pair + 2 =2
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 Formula after removal
of hetero atom
C 2 H4
C 2 H4 O C 2 H4
C 2 H4
C2H3Cl C2 H4
C 2 H4
C 2 H5 N C2 H4
In the previous section the structure of O3 was written as . It could also be written as
. 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 simple answer is, whenever there is a multiple bond, resonance becomes important. For
example,
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.
Molecules with more than One Lewis Structures: Resonance
and Conjugation
Example 1
Example 2
Example 3
If there is a gap of more than one bond, then there will be no conjugation.
Example 4
If there are no gaps, then too there will be no delocalisation or conjugation.
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.
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 cannot be a
contributing structure.
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
3. Resonance energy
The stabilization of a molecule because of resonance or delocalization is called resonance or delocalisation
energy. This energy becomes large when:
a) The contributing resonance structures are equivalent. For example, as in
Cyclooctatetraene is not aromatic because it has 8 electrons which does not fit the (4n + 2) rule.
The VSEPR or the valence shell electron pair repulsion theory was proposed initially by Sidgwick and
Powell and was later developed by Gilespie.
The electron pairs in the valence shell of a central atom repel to get as far away from each other to
determine the bond angles and ultimately the shapes of molecules.
Predicting shapes:
Electrons around a central atom are two types.
(a) Those involved in bonding with a neighbouring atom called bonding pair or BP.
(b) Those not involved in bonding called lone pair or LP
For applying VSEPR theory, we donot consider the electrons involved in the formation of -bonds which
are always present along with a -bond in a multiple bonding situation and donot move away from each
other due to repulsion. The sum of these i.e. LP + BP = steric number or SN.
The steps involved in applying VSEPR theory to determine shapes of molecules are as follows.
Step 1. Find out the steric number from the lewis structure.
The steric number determines the basic arrangement of electron pairs as follows:
3 Trigonal planar
4 Tetrahedral
5 Trigonal bipyramid
6 Octahedral
7 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.
Note:
In the cases of AB4E, AB3E2 and AB2E3, the lone pair is always assigned to the equatorial site.
Hence, AB3E2 is T-shaped and not trigonal planar.
No such confusion arises in the the case of AB4E2, since in the octahedral distribution, the
axial and equatorial sites are equivalent. The two lone pairs should be trans to each other.
Even if you put them trans to each other on two opposite equatorial sites the shape is still
square planar.
Trigonal planar
AB2E
SO2, , NO2-
Bent
4 Tetrahedral AB4 CH4, CHCl3,
Bond angle 109o 28' NH4+,BH4-, SO42-
,PCl4+
Tetrahedral
AB3E NH3,H3O+,
PCl3,SO32-, XeO3
Trigonal pyramid
AB2E2 H2O,SCl2,OF2,XeO
2
Angular or V-shaped
5 Trigonal bipyramid AB5 PCl5,PF3Cl2
Bond angles 120o,
180o and 90o
Trigonal bipyramid
AB4E SF4, IO2F2-
See-saw or distorted
tetrahedral
AB3E2 BrF3,ClF3
T-shaped
AB2E3 I3-,ICl2-, XeF2
Linear
6 Octahedral AB6 SF6, PF6-
Bond angles 90o, 180o
Octahedral
AB5E BrF5, XeOF4
Square pyramidal
AB4E2 ICl4+, XeF4
Square planar
7 Pentagonal bipyramid AB7 IF7
Bond angles 90o, 180o
and72o
Pentagonal bipyramid
AB6E XeF6
Distorted octahedral
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.