Engineering Chemistry

Unit –I
Atomic and molecular structure, Intermolecular forces

1. Define - Bond order.

Bond order is a measurement of the number of electrons involved
in bonds between two atoms in a molecule. It is used as an indicator of the
stability of a chemical bond.

Nb = number of bonding electron

Na = number of anti-bonding electron.

2. What is potential energy surface?

A potential energy surface (PES) describes the potential energy of a system,
especially a collection of atoms, in terms of certain parameters, normally
the positions of the atoms.
3. What is the bond order of N2 molecule?

Nb = 8
Na = 2.
Bond order = ½(8- 2)
= ½(6)
=3

4. How sigma and Pi orbital is formed?

• Sigma bonds (σ bonds) are the strongest type of covalent chemical bond.
 Sigma () is formed by the end to end (head-on) overlap of bonding orbitals
along the internuclear axis. This is called as head on overlap or axial
overlap.

• pi bonds (π bonds) are covalent chemical bonds, formed by the side-to-side

overlap of two atomic orbitals.

5. Define crystal field splitting.

Crystal field splitting is the difference in energy between d orbitals of
ligands. Crystal field splitting number is denoted by the capital Greek letter
Δ. Crystal field splitting explains the difference in color between two
similar metal-ligand complexes.

6. What is dipole-dipole interaction and dipole-induced dipole interaction?

7. dipole-dipole interaction force:
Dipole-dipole forces are attractive forces between the positive end of one polar
molecule and the negative end of another polar molecule. The partially positive end
of a polar molecule is attracted to the partially negative end of another.

dipole – induced dipole interaction force:

A dipole -induced dipole attraction is a weak attraction that results when the
approach of an ion induces a dipole in an atom or in a nonpolar molecule by
disturbing the arrangement of electrons in the nonpolar species.
8. What is spectrochemical series?
A spectrochemical series is a list of ligands ordered on ligand strength and
a list of metal ions based on oxidation number, group and its identity.
F- ˂OH- ˂NH3 ˂H2O ˂SCN ˂NO2- ˂CN- ˂CO
9. What is ligand?
A ligand is an ion or molecule that binds to a central metal atom to form a
complex (alternatively known as a coordination entity). Metals are electron
acceptors. Ligands may be neutral or negatively charged species with
electron pairs available.
10.How the real gases differ from ideal gas?
Real gases have small attractive and repulsive forces between particles
and ideal gases do not. Real gas particles have a volume and ideal
gas particles do not. Real gas particles collide in-elastically (loses energy
with collisions) and ideal gas particles collide elastically.
11.He2+ molecule possible but He2 is not possible why?
The electronic configuration of helium (Z = 2) in the ground state is 1s2
As each helium atom contains two electrons, there will be four electrons in
He2 molecule.
12.What is meant by aromaticity?
Aromaticity is a property of conjugated cycloalkenes in which the
stabilization of the molecule is enhanced due to the ability of the electrons
in the ππ orbitals to delocalize. This act as a framework to create a planar
molecule.

13.What is meant by Hybridization?

Hybridization happens when atomic orbitals mix to form a new atomic
orbital. The new orbital can hold the same total number of electrons as the
old ones.

14.What is the meaning of dia and paramagnetic properties?

If the electronic configuration contain any unpaired or single electron then
this element will give paramagnetic properties, for paired electron system, it
will give diamagnetic properties.
15.What is van Der Waals interactions?
Van der Waals forces are driven by induced electrical interactions between
two or more atoms or molecules that are very close to each other. Van der
Waals interaction is the weakest of all intermolecular attractions between
molecules.
Part-B
1. Draw the energy level diagram for N2 and O2 molecule.
The electronic configuration of nitrogen (Z=7) in the ground state is 1S2
2S2 2p3. Therefore, the total number of electrons present in nitrogen
molecule (N2) is 14.
Oxygen molecule, O2.The electronic configuration of oxygen (Z = 8) in the
ground state is 1s2,2s2,2p4. Each oxygen atom has 8 electrons, hence, in O2
2. Calculate the bond order of F2 and C2 molecule using the energy level
diagram.
MO diagram for F2 Molecule:
MO diagram for C2 Molecule:

The electronic configuration of C atom is 1S2, 2S2, 2P2

The molecular electronic configuration of C2 molecule is,
 3. Explain the Pi-molecular orbitals of butadiene and benzene.
Pi-MOLECULAR ORBITALS OF BUTADIENE

Butadiene

Pi Molecular Orbitals of Benzene

Benzene:
4. How will you explain the aromaticity of benzene molecule?
• The aromatic compounds contain alternate double and single bonds in a
cyclic structure and resemble benzene in chemical behaviour. They undergo
substitution rather than addition reactions. This characteristic behaviour is
called Aromatic character or Aromaticity. *
o Aromaticity is, in fact, a property of the sp2 hybridized planar rings in which
the p orbitals (one on each atom) allow cyclic delocalization of  electrons.
o An aromatic compound is cyclic and planar
o Each atom in an aromatic ring has a p orbital. These p orbitals must be
parallel so that a continuous overlap is possible around the ring.
o The cyclic  molecular orbital (electron cloud) formed by overlap of p
orbitals must contain (4n+2)  electrons, where n= integer 0,1,2,3 etc. This
is known as Huckel rule
Example: Benzene

5. Write the assumption of molecular orbital theory.

i. The atomic orbitals combine (overlap) to form a new orbital known as molecular
orbital. As a result, the atomic oritals loose their identity.
ii. 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.
iii. An M.O gives electron probability distribution around a group of nuclei (as M.O always
contain two nuclei)same as the atomic orbitals.
iv. 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.
v. The no. of M.Os formed are equal to the no. of A.Os combined.
vi. 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) .
vii. The, B.M.O has lower energy and hence greater stability than the corresponding A.M.O.
viii. The B.M.Os are represented by σ,π,δ etc. while antibonding M.Os are represented by
σ* ,π* ,δ* etc.
ix. The shapes of molecular orbitals depends upon the type of combining atomic orbitals.
The filling of M.Os takes place by same rule as for atomic orbitals. like they follow,
Aufbau, Pauli exclusion, and Hund'e rule.

6. Write the assumption of Crystal field theory.

The assumptions and features of crystal field theory are,
• VBT (valence bond theory) considers the metal ligand bond to be covalent, CFT
considers electrostatic interaction between the metal ions and the ligands.
• Since these interactions are similar to this present in Crystals, hence the theory is
called as crystal field theory.
• If the ligand is anion (negatively charged) then the metal ion has to be a cation
(positively charged)and the force of attraction is due to opposite charges.
• It considers the effect of ligands on the relative energies of d-orbitals of the central
metal ion
 • In all free transition metal ion, all the five d-orbitals have equal energies
• The d-orbitals split into two parts (named as t2g and eg orbitals) depending on the
number of ligands approaching the metal ion.
• t2g : The 3 d-orbitals (dxy, dyz and dzx ) which orient in the regions between the
axes . These are non-axial orbitals . t2g are three fold degenerate.
• eg : the other two orbitals (dz2 and d(x2 -y2) ) which orient along the axis . These
are two fold degenerate and also known as axial orbitals.

7. Discuss the various factors affecting the crystal field Stabilization

energy.

i) Ligand effect on o :

If the metal connected with strong field ligand, then this complex
will have more o , this is due to the pairing of unpaired electron in the

d-orbital, whereas, weak field ligand complex has low o value.

ii) Effect of Metal Oxidation state on o:

In This case, Fe3+ complexes has more o value compared with Fe2+
complex, this may be due to absence of electron in eg energy level in
the complex of Fe2+.
Examples :
Fe2+ << Fe3+

II 2+ cm-1 4
[Fe (H O) ]  = 10,400 3d
2 6 o
III 3+ cm-1 3
[Fe (H2O)6] o = 13,700 3d
 iii) Different charges on the different
metals:
In this category, CFSE (crystal field stabilization energy)
is based on the size of metal ion that means, more oxidation
state element will have smallest size, so the smallest size
metal ion will have more o value.
Examples:
II 2+ cm-1 3
[V (H O) ]  = 12,400 3d
2 6 o
III 3+ cm-1 3
[Cr (H O) ]  = 17,400 3d
2 6 o

iv) Same charges with different metals

In this case, Co2+ has lowest CFSE value compared with Ni2+
complex, this is due to the lowest electron count in eg energy level in
Co 2+ complex.

II 2+ cm-1 7
[Co (H2O)6] o = 9,300 3d
II 2+ cm-1 8
[Ni (H2O)6] o = 8,500 3d

8. Draw the energy level diagrams for any two transition metal ions and find
their magnetic properties using crystal field theory.
EXAMPLE FOR CRYSTAL FIELD SPLITTING OF OCTAHEDRAL
TETRAHEDRAL COMPLEX
CFSE = -0.4 (t2g electron) + 0.6 (eg electron)
= -0.4 (5) + 0.6 (0)
= -2.0 
o
 CFSE = + 0.6 (eg electron) + (-0.4 (t2g electron))
= 0.6 (4) + (-0.4 (3))
= 1.2 
t

9. Write a short note on the types of interaction force.

vander waals interaction force:
• Attractive intermolecular forces are known as van der Waals forces
• Van der Waals forces vary considerably in magnitude and include dispersion forces or
London forces, dipole-dipole forces, and dipole-induced dipole forces.
i. ionic interaction force:
Ionic bonding is the complete transfer of valence electron(s) between atoms. It is a
type of chemical bond that generates two oppositely charged ions. In ionic bonds, the
metal loses electrons to become a positively charged cation, whereas the nonmetal
accepts those electrons to become a negatively charged anion.
For example: Na+ Cl-

ii. dipole-dipole interaction force:

Dipole-dipole forces are attractive forces between the positive end of one polar
molecule and the negative end of another polar molecule. The partially positive end
of a polar molecule is attracted to the partially negative end of another.

iii. dipole – induced dipole interaction force:

A dipole -induced dipole attraction is a weak attraction that results when the
approach of an ion induces a dipole in an atom or in a nonpolar molecule by
disturbing the arrangement of electrons in the nonpolar species.
10.Explain the Potential energy surfaces of H3, H2F and HCN molecules.
 11.Write equations of state of real gases.
EQUATIONS OF STATE OF REAL GASES

• Real gases show deviations from ideal gas law because molecules
interact with each other.
• At high pressures molecules of gases are very close to each other.
Molecular interactions start operating. At high pressure, molecules do
not strike the walls of the container with full impact because these are
dragged back by other molecules due to molecular attractive forces.
• This affects the pressure exerted by the molecules on the walls of the
container. Thus,
the pressure exerted by the real gas is lower than the pressure
exerted by the ideal gas.

-----------------------(1)
• Repulsive interactions are short-range interactions and are significant
when molecules are almost in contact. This is the situation at high
pressure. The repulsive forces cause the molecules to behave as
small but impenetrable spheres.
• The volume occupied by the molecules also becomes significant
because instead of moving in volume V, these are now restricted to
volume (V–nb) where nb is approximately the total volume occupied
by the molecules themselves. Here, b is a constant.
Having taken into account the corrections for pressure and volume, we can
rewrite the equation (1).

---------------------------(2)
Equation (2) is known as van der Waals equation.
n is number of moles of the gas. Constants a and b are called vander
Waals constants and their value depends on the characteristic of a gas.
Value of ‘a’ is measure of magnitude of intermolecular attractive forces
within the gas and is independent of temperature and pressure.
• Redlich–Kwong equation of state is an empirical, algebraic
equation that relates temperature, pressure, and volume of
gases. It is generally more accurate than the van der Waals
equation and the ideal gas equation at temperatures above
the critical temperature.

The Redlich–Kwong equation is formulated as

where:
• p is the gas pressure
• R is the gas constant,
• T is temperature,
• Vm is the molar volume (V/n),
• a is a constant that corrects for attractive potential of molecules, and
• b is a constant that corrects for volume.

DEVIATIONS FROM IDEAL BEHAVIOUR

• An ideal gas is one which obeys the gas laws or the gas
equation PV = RT at all pressures and temperatures.
• However no gas is ideal. Almost all gases show significant
deviations from the ideal
behaviour. Thus the gases H2, N2 and CO2 which fail to obey the
ideal-gas equation are termed nonideal or real gases.
Compressibility Factor
 • The extent to which a real gas departs from the ideal behaviour
may be depicted in terms of a new
function called the Compressibility factor, denoted by Z. It is
defined as Z =PV /RT.
• For an ideal gas, Z = 1
• The deviations from ideal behaviour of a real gas will be
determined by the value of Z being greater or less than 1. The
difference between unity and the value of the
compressibility factor of a gas is a measure of the degree
of non ideality of the gas.

Z versus P plots for H2, N2 and CO2 at 300 K

CRITICAL TEMPERATURE

The critical temperature of a substance is the temperature at and

above which vapor of the substance cannot be liquefied, no matter
how much pressure is applied.

CRITICAL PRESSURE.
The critical pressure of a substance is the pressure required to
liquefy a gas at its critical temperature