Engineering chemistry:

Long answer questions

1.Explain the postulates of Molecular Orbital Theory(MOT)

1. The atomic orbitals combine (overlap) to form a new orbital known as molecular orbital. As a
result, the atomic oritals loose their identity.
2. The molecular orbitals are the energy states of a molecule, in which the electrons of the
molecule are filled just like in case of atomic orbitals.
3. An M.O gives electron probability distribution around a group of nuclei (as M.O always contain
two nuclei)same as the atomic orbitals.
4. Only those A.Os are combined to form M.Os which have comparable energy, and orientations.
For ex: 1s can combine with 1s and not with 2s as they have energy gap. Similarly, s-orbital can
combine with pz but not with px or py as the z-axis is inter nuclear axis and so oriented in line
of s-orbital but others are perpendicular.
5. The no. of M.Os formed are equal to the no. of A.Os combined.
6. When two A.Os combine, they form two M.Os known as bonding molecular
orbital(B.M.O) and antibonding molecular orbital(A.M.O) .
7. The, B.M.O has lower energy and hence greater stability than the corresponding A.M.O.
8. The B.M.Os are represented by σ,π,δ etc. while antibonding M.Os are represented by σ* ,π* ,δ*
etc.
9. The shapes of molecular orbitals depends upon the type of combining atomic orbitals.
10. The filling of M.Os takes place by same rule as for atomic orbitals. like they follow, Aufbau, Pauli
exclusion, and Hund'e rule.

2. Write a note on linear combination of Atomic Orbitals(LCAO)

According to Schrodinger’s wave equation an atomic orbital can be represented in terms of its
wave function which represent the amplitude of the corresponding three dimensional electron
wave.

If two atoms A and B each containing one electron their wave function represented by

The mathematical process of combining atomic orbitals to generate molecular orbitals is

called the linear combination of atomic orbitals (LCAO). The wave function

describes the wavelike properties of an electron. Molecular orbitals are combinations of

atomic orbital wave functions. Combining waves can lead to constructive interference, in

which peaks line up with peaks, or destructive interference, in which peaks line up with

troughs . In orbitals, the waves are three dimensional, and they combine with

in-phase waves producing regions with a higher probability of electron density and out-
 of-phase waves producing nodes, or regions of no electron density.

(a) When in-phase waves combine, constructive interference produces a wave with greater
amplitude. (b) When out-of-phase waves combine, destructive interference produces a wave
with less (or no) amplitude.

Bonding Molecular Orbitals

When addition of wave function takes place, the type of molecular orbitals formed are called
Bonding Molecular orbitals and is represented by ΨMO = ΨA + ΨB.
They have lower energy than atomic orbitals involved. It is similar to constructive
interference occurring in phase because of which electron probability density increases resulting
in formation of bonding orbital.
Molecular orbital formed by addition of overlapping of two s orbitals shown in figure. It is
represented by s.

Anti-Bonding Molecular Orbitals

When molecular orbital is formed by subtraction of wave function, the type of molecular orbitalsformed are called
Antibonding Molecular Orbitals and is represented byΨAMO = ΨA - ΨB

They have higher energy than atomic orbitals. It is similar to destructive interference occurring
out of phase resulting in formation of antibonding orbitals. Molecular Orbital formed by
subtraction of overlapping of two s orbitals are shown in figure.. It is represented by s* (*) is
used to represent antibonding molecular orbital) called Sigma Antibonding.
 Formation of Bonding and Anti-Bonding Orbital

Therefore, Combination of two atomic orbitals results in formation of two molecular orbitals,

bonding molecular orbital (BMO) whereas other is anti-bonding molecular orbital (ABMO).
BMO has lower energy and hence greater stability than ABMO. First BMO are filled then
ABMO starts filling because BMO has lower energy than that of ABMO.

Formation of molecular orbitals occurs by the combination of atomic orbitals of proportional

symmetry and comparable energy. Therefore, a molecular orbital is polycentric and atomic
orbital is monocentric. Number of molecular orbitals formed is equal to the number of atomic
orbitals.

3.)Draw the molecular energy level diagram of N2 molecule and calculate bond order.

Ans)The atomic number of Nitrogen is 7 and

the electronic configuration
is 1s2 2s22px12py12pz1

. N2 molecule is consists of 2 N-atoms, the

total number of electrons in N2 molecule
is 14. In N2molecule's energy level diagram
can be drawn as
BO = [Nb-Na] = [10-4] = 3
Since all the electrons in nitrogen are paired, it is diamagnetic molecule

4.Draw molecular energy diagram of O2 molecule:

The atomic number of oxygen is 8(1s2,2s2,2px2,2py1,2pz1)

O2 molecule has 16 electrons so its MO configuration is σ1s, σ *1s, σ 2s, σ *2s, σ 2pz, [π2px = π2py], [π*2px=
π*2py], σ *2pz
 The bonding electrons are in the σ2s, σ2p, π2px, and π2py MOs, giving 2+2+2+2=8.

the antibonding electrons are in the σ*2s, π*2px, and π*2py MOs, giving 2+1+1=4.

Bond order= 8-4/2 =2

O2 molecule is paramagnetic since it contains two unpaired electrons in

π*2px and π*2py molecular orbitals.

5.Molecular Energ diagram of F2 molecule :

The atomic number of fluorine is 9(1s2, 2s2,2p5)
Electron configuration of F2 is: σ (1s2 ) σ*(1s2 ) σ(2s2 ) σ*(2s2 ) σ(2px 2 ) σ*(2px 2 ) π(2py 2 )
π(2pz 2 )π*(2py 2 ) .

Number of electrons in bonding molecular orbital=10

Number of electrons in Anti bonding molecular orbital=8
 Bond Order = 1/2 [10-8] = 1 Number of covalent bond in Fluoride is 1.
The presence of all paired electrons shows that fluorine molecule is diamagnetic.

6.ΠMolecular Orbital diagram of 1,3 Butadiene

1. HOMO: HOMO is 𝜋2.it is the valence electrons of the 𝜋 system.they will be

lostreadily.if butadiene participate in a reaction ,where it is a
electrondonar(nucleophile).its electrons are going to come from that orbital.
2. LUMO:Lumo is𝜋3* itislowest
Energy unoccupied orbital.if butadiene participate in a reation ,whre it is
electron acceptor(electrprophile)the elcetrons will be donated to that orbital.
1)1,3 Butadiene contains alternative double bond and it is a conjugated diene.

2)All the carbon atoms in 1,3 butadiene are sp2 hybridized and each sp2 hybridized carbon atom contains
one unhybridized p-orbital.

3)so in 1,3 butadiene there are four unhybridized p orbitals on four sp2 hybridized corbon atom.Each
unhybridized p orbital contains one electron.These atomic orbitals combine to form molecular orbitals.

4)In π system,number of molecular orbitals formed is equal to the number of contributing p orbitals.so in
the case of 1,3 butadiene,as there are four contributing p orbitals,there will be formation of four molecular
orbitals.

5.The atomic orbitals of 1,3 Butadiene can combine to give two bonding molecular orbitals (π1,π2) andtwo
anti bonding molecular orbitals(π3*,π4*).
6.Formation of the molecular orbitals of 1,3 Butadiene can be visualized in this manner.

π1is the bonding molecular orbital with lowest energy.it contains paired up electrons.It has no nodal planes
and no anti bonding interactions.There are three bonding interactions.

Π2 bonding orbital is the next higher energy molecular orbital.It is the highest occupied molecular
orbital(HOMO).in this molecular orbital also the electrons are paired up.it has one nodal plane and one pi
anti bonding interaction.There are two bonding interactions.
π3* antibonding moecualr orbital is the next higher energy molecular orbital.it has the lowest unoccupied
molecular orbital(LUMO).This molecular orbital has no electrons and has two nodal planes,two anti bonding
and one bonding interaction.
π4* Anti bonding molecular is the highest energy moelcualr orbital.this moelcualr orbital also empty, it has
three nodal planes,three anti bonding interactions and bonding interactions are absent

6.Salient features of crystal field theory:

This theory was put forwarded by Brethe and Van V lack in the year 1932.

Valence bond theory failed to explain the stability,colour and magnetic properties of co-
ordination compounds and difference between strong and weak ligands. Crystal field theory
could explain these properties.

The following are the salient features of crystal field theory.

A complex is considered as a combination of central metal ion surroundedby ligands.

1.The metal-ligand bond arises due to electrostatic interaction between metalion and ligands.
2.Crystal field theory considerers anions like Cl-,Br-,CN- (ligands as point chargers and neutral
molecules as diploes(H2o,NH3ect).
3.When transition metals are not bonded to any ligand, their d orbitals are degenerate.(having
same energy).
4.When they start bonding with ligands due to different symmetryof d
Orbitals and inductive effect of ligands ,the d orbitals split apart and become non-degenerate.
5.The pattern of splitting of d orbitals depends upon the nature of the ligand and metal ion.
6.The five d orbitals are classified in to two sets. three dxy, dyzand dzxwhich are oriented in
between co-ordinate axis and are called t2g set orbitals and other two orbitals dx2-y2 and
dz2(donut shaped)oriented along axis are designated as egsetorbitals.
.7The energy difference between t2g and eg level is designated by ∆ and is called crystal field
splitting energy.

Crystal field splitting in octahedral complexes :

 1. In an octahedral complex like[COF6]3- ,the central metal ion is surrounded bysix
ligands which contain lone pair ofelectrons.

2. When they approach the dorbitals of metal ion during complex formation there
will be repulsion between the electrons of the ligands and electrons of d orbitals
asa result the d orbitals lose their degeneracy and split in to two sets ofd-orbitals.
3. inoctahedralcomplexestheligandsapproachthecentralmetalionthroughlobes present
along the axis, the energy of eg orbitals (dx2-y2 and dz2) is raised and the energy of
t2g orbitals isreduced.

4.The energy of eg orbitals is raised by +3/5 Δ0 and the energy of t2g orbital is
decreased by -2/5 Δ0

7.Crystal field splitting in Tetrhedral complexes

 1. In tetrahedral complexes there are four ligands attached to the central metal ion[Nicl4]2-.

2. in the case of tetrahedral complexes the ligand approach the central metal ion between the
axis(dxy, dyzand dzx) as a result the energy tg orbitlas is raised and the energy of 2tg orbitlas is
reduced.

3.The energy of t2orbitals is raised by +2/5 Δtand the energy of eorbitals is decreased by
-3/5 Δt

4. Thesplittingofd-orbitlasexplains1)colourofthe complex2)spectraof the complex3)

magnetic properties of co-ordinatecomplexes.

8.Crystal field splitting in Square planar complexes:

Thee crystal field splitting diagram for square planar geometry can be derived from the octahedral diagram.

Example:

1.The splitting diagram of square planar can be derived from the splitting diagram of Octahedral
complexes.

2.Square planar coordination can be imagined to result when two ligands on the z-axis of an
octahedral are removed from the complex, leaving only the ligands in the x-y plane.
3.As ligands move away along the z-axis, d-orbitals with a z-component will fall in energy. The
dz2 orbital falls the most, as its electrons are concentrated in lobes along the z-axis. The dxz and
dyz orbitals also drop in energy.

On the other hand, the dx2-y2 and the dxy orbitals increase in energy.