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Chemical Bondind and Molecular Structure
Chemical Bondind and Molecular Structure
Valence electrons
The electrons in the outermost shell.
Lewis structures.
The structures in which dot represent electrons are called Lewis structures.
Conditions for stability of an atom
Duplet (For atoms with only 1 shell): 2 electrons
Octet (For atoms with more than one shell): 8 electrons in the outermost shell.
Eg:
The electrostatic force of attraction that holds the oppositely charged ions
together is called ionic bond.
Ionic bonds will be formed more easily between elements with comparatively
low ionisation enthalpies and elements with comparatively high negative value
of electron gain enthalpies.
Lattice enthalpy
The energy required to completely separate one mole of a solid ionic compound into
gaseous constituent ions.
COVALENT BONDING
Bonds which are formed by the sharing of an electron pair between two atoms are
known as covalent bonds.
The shared electrons belong to the outermost shells of both the atoms and thus both
the atoms attain octet configuration or stable noble gas configuration.
Covalently bonded molecules have strong bonds within the molecule but
intermolecular forces are weak. Therefore these compounds have low melting and
boiling points.
Electrons are shared between atoms, and charged particles are not formed. Hence
covalent compounds are generally poor conductors of electricity.
Covalent bonding in Oxygen molecule
POLARITY OF BONDS
Covalent bond with partial ionic character
In heteronuclear molecule, when two dissimilar atoms are bonded, the shared electron
pair shifts towards the more electronegative atom. As a result the one of the molecule
having more electronegative atom acquires a partial negative charge while the other
end acquires partial positive charge. Thus positive and negative poles are developed
and this type of bond is called polar covalent bond (ie,covalent bond with partial ionic
character).
Ionic bond with partial covalent character
Fajan’s rule
When a cation approaches an anion, the electron cloud of the anion is attracted
towards the cation and hence get distorted. This is called polarisation of the anion. The
power of the cation to polarise the anion is called its polarising power. The tendency of
the anion to get polarised is called polarisability.
The greater the polarisation produced, more is the neutralisation of the charges, and
hence ionic character decreases and covalent character increases.
Factors favouring the formation of covalent bond(character):
(i) Small size of the cation
The smaller the size of the cation, greater is its polarising power. That is why
LiCl is more covalent than KCl.
(ii) Large size of the anion
Larger the anion, greater is its polarisability.
Thus covalent character of lithium halides is in the order,
LiI > LiBr > LiCl > LiF
(iii) Electronic configuration of the cation
If two cations have the same size and charge , the one with pseudo noble gas
configuration(18 electrons in the outermost shell) has greater polarisability
than the one with noble gas configuration (8 electrons in the outermost
shell).
Eg: CuCl is more covalent than NaCl
DIPOLE MOMENT
The product of the magnitude of the charge and the distance between the
centres of positive and negative charges. Designated by the symbol μ.
In the case of polyatomic molecules, the dipole moment is the vector sum
of the dipole moments of various bonds.
In symmetrical molecules like BF3, CH4 and CCl4 , the molecular dipole moment is found
to be zero. This is because the individual dipole moments cancel out on account of the
symmetry of the molecule.
If all the bonds are not identical, the molecule may have a net dipole moment, eg:
CHCl3.
DIPOLE MOMENTS IN NH3 AND NF3
The net dipole moment of NH3 is greater than that of NF3. This is because in NH3, the
orbital dipole due to lone pair is in the same direction as the resultant dipole moment
of the N-H bonds, whereas in NF3, the orbital dipole is in the direction opposite to the
resultant dipole moment of the three N-F bonds.
The orbital dipole because of lone pair decreases the effect of the resultant N-F bond
moments, which results in the low dipole moment of NF 3.
VSEPR THEORY
VALENCE SHELL ELECTRON PAIR REPULSION THEORY.
Proposed by Sidgwick and Powell in 1940
Further developed and refined by Nyholm and Gillespie in 1957.
Postulates of VSEPR theory
The shape of the molecule depends on the number of valence shell
electron pairs (bonded and nonbonded) around the central atom.
Pairs of electrons in the valence shell repel one another since their
electron clouds are negatively charged.
These pairs of electrons tend to occupy such positions in space that
minimise repulsion and thus maximise distance between them.
The valence shell is taken as a sphere with the electron pairs localising
on the spherical surface at maximum distance from one another.
A multiple bond is treated as a single electron pair and the two or three
electron pairs of a multiple bond are treated as a single super pair.
If there are more structures that can represent a molecule, the VSEPR
model is applicable to any such structure.
The repulsive interaction of electron pairs decreases in the order:
Lone pair - Lone pair > Lone pair – bond pair > bond pair - bond pair
(ii) No. of bond pairs(shared pairs) = number of atoms linked to the central atom
by single bond
(iii) No. of lone pairs = Total number of electron pairs - No. of bond pairs(shared
pairs)
Practice problems:
On the basis of VSEPR theory predict the shape of
(i) ClF3
(ii) BrF5
(iii) NH2-
(iv) H3O+
Pi BONDS
Formed by the sideways overlap of the orbitals of the combining atoms
It can be between
o p and p orbitals
It involves strain in the bonding
Rotation is not possible around the bonds
Less effective and weaker than sigma bonds.
Since there is electron charge cloud above and below the orbitals, it is a reactive
site for the incoming electrophiles.
A single bond will always be a sigma bond.
A double bond consists of one sigma bond and one pi bond.
A triple bond consist of one sigma bond and two pi bonds.
HYBRIDISATION
The process of intermixing of atomic orbitals of slightly different energies so as to
redistribute their energies, resulting in the formation of new set of orbitals of
equivalent energies and shape is called hybridisation.
Salient feaures of hybridisation
The number of hybrid orbitals is equal to the number of atomic orbitals that get
hybridised.
The hybridised orbitals are always equivalent in energy and shape.
The hybrid orbitals are more effective in forming stable bonds than the pure
atomic orbitlas.
These hybrid orbitals are directed in space in some preferred direction to have
mimimum repulsion between electron pairs and thus a stable arrangement.
Therefore the type of hybridisation indicates the geometry of the molecules.
Important conditions for hybridisation
The orbitlas present in the valence shell of the atom are hybridised.
The orbitals undergoing hybridisation should have almost equal energy.
Promotion of electron is not essential condition prior to hybridisation.
It is not necessary that only half filled orbitals participate in hybridisation. In
some cases, even filled orbitals of valence shell take part in hybridisation.
TYPES OF HYBRIDISATION
(1) sp hybridisation or diagonal hybridisation.
Invoves mixing of one s and one p orbital resulting in the formation of
two equivalent sp hybrid orbitals. (s and pz).
Each sp hybrid orbitals have 50% s character and 50% p character.
Has linear geometry.
Eg: BeCl2.
o So the triple bond between two carbon atoms is made up of one sigma bond
and two pi bonds.
Eg: BF3.
HW: Explain the structures of BH3 and C2H4
Eg: CH4.
AMMONIA : NH3
The force of repulsion between a lone pair and a bond pair is more than the the force
of repulsion between two bond pairs of electrons. The molecule thus gets distorted
and the bond angle gets reduced to 1070 from 109.50.
Thus the geometry of the molecule is pyramidal (trigonal pyramidal).
Hybridisation is sp3.
WATER : H2O
Hybridisation : sp3
Bond angle and geometry: The four sp3 hybrid orbitals acquire a tetrahedral geometry,
with two corners occupied by hydrogen atoms while the other two by the lone pairs.
The bond angle is thus reduced to 104.50 from 109.50 and the molecule acquires a
V- shape or bent shape.
o In PCl5, the five sp3d hybrid orbitals of phosphorus overlap with the singly
occupied p orbitals of chlorine atoms to form five P-Cl sigma bonds.
o Three P-Cl bonds lie in one plane and make an angle of 1200 with each other.
These bonds are termed as equatorial bonds.
o The remaining two P-Cl bonds- one lying above and the other lying below the
equatorial plane, make an angle 900 with the plane. These bonds are called axial
bonds.
o As the axial bonds suffer more repulsive interaction from the equatorial bond
pairs, therefore axial bonds have been found to be slightly longer and weaker
than the equatorial bonds. As a result of which PCl5 molecule is more reactive.
(5) sp3d2 hybridisation
In SF6 the central sulphur atom has the ground state configuration, 3s23p4 . One electron each
from 3s and 3p orbitals is promoted to 3d orbitals. These six orbitals get hybridised to form
six sp3d2 hybrid orbitals. Each of these sp3d2 hybrid orbitals overlaps with 2p orbital of
fluorine to form S−F bond. Thus, SF6 molecule has octahedral structure.
MOLECULAR ORBITAL THEORY
Developed by F Hund and RS Mulliken in 1932.
Salient features:
The electrons in a molecule are present in the various molecular orbitals
as the electrons of atoms are present in the various atomic orbitals.
The atomic orbitals of comparable energies and proper symmentry
combine to form molecular orbitals.
While an electron in an atomic orbital is influenced by one nucleus
(monocentric), in a molecular orbital it is influenced by two or more nuclei
(polycentric) depending upon the number of atoms in the molecule.
The number of molecular orbitals formed is equal to the number of
combining atomic orbitals.
o One is known as bonding molecular orbital
o The other is known as anti antibonding molecular orbital
The wave functions formed by the addition of atomic orbitals is called the
bonding molecular orbital.
The wave functions formed by the subtraction of atomic orbitals is called the
antibonding molecular orbital.
The bonding molecular orbital always possesses lower energy than either of the
atomic orbitals that have combined to form it.
The energy of the antibonding molecular orbital is raised above the energy of
the parent atomic orbitals.
For O2 and F2
σ1s < σ*1s < σ2s < σ*2s < σ2pz < (π2px = π2py) < (π*2px = π*2py) < σ*2pz
ENERGY LEVEL DIAGRAM FOR MOLECULAR ORBITALS
BO = 1 : Single bond
BO = 2 : Double bond
BO = 3 :Triple bond
BOND LENGTH
MAGNETIC NATURE
H2:
Practice time
Q: Compare the relative stability of the following molecules and indicate their magnetic
properties.
a) O2, O2+, O2-, O22-
Q: Predict the magnetic property of the following molecules.
a) H2
b) Cl2
c) Be2
d) C2
e) N2
f) O2-
g) F2