SRI VENKATESWARA COLLEGE OF ENGINEERING

KARAKAMBADI ROAD, TIRUPATI-517507

DEPARTMENT OF SCIENCE AND HUMANITIES

LECTURE NOTES

CH23ABS101-CHEMISTRY
Regulation : R23

Academic Year : 2023-2024

Year/Semester : I/I

Prepared by P Ravi Kumar and Dr T Chandraiah

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 SRI VENKATESWARA COLLEGE OF ENGINEERING,TIRUPATI B.Tech–I-I Sem
LTPC
3003
CH23ABS101CHEMISTRY

Unit I
Structure and Bonding Models: Planck's quantum theory, dual nature of matter, Schrodinger
equation, significance of Ψ and Ψ2 , applications to hydrogen, molecular orbital theory –
bonding in homo- and hetero nuclear diatomic molecules – energy level diagrams of O2 and CO,
etc. π-molecular orbital’s of butadiene and benzene, calculation of bond order..
Text Books:
1. Jain and Jain, Engineering Chemistry,16/e,DhanpatRai,2013.
References:
1 .G. V. Subba Reddy, K. N. Jayaveera and C. Ramachandraiah, Engineering
chemistry, Mc Graw Hill, 2020.

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 CONTENTS
1 Unit-I PageNo
1.1 Introduction 4-5
1.2 Unit-I notes 6-22
1.3 PartA-2MarksQuestions and Answers 23
1.4 PartB-10Marks Questions 24

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Introduction:
Atoms are the smallest parts of an element that chemically react. In 1808, John Dalton proposed the
first atomic theory, i.e. an individual particle of matter is known as an atom. At the end of the 19 th
century it was proved experimentally that atoms are divisible and consist of three fundamental
particles like electron, proton, and neutron. This soon leads to the questions about the internal
arrangement of these fundamental particles (Atomic structure).Many atomic model such as J.J.
Thomson’s model, Rutherford’s model Bohr’s model etc.
Electromagnetic Radiations:
In 1864, Clark Maxwell proved that an alternating current of high frequency is capable of radiating
continuous energy in the form of wave that is called electromagnetic wave (or) Electro Magnetic
radiation.
The radiation such as visible, ultraviolet, γ-rays, x-rays etc are called electromagnetic radiations.
The Electro Magnetic radiation has both electric and magnetic properties. It consisting electric
and magnetic field oscillating perpendicular to each other and both are perpendicular to the radiations
of wave functions.
Electromagnetic waves travels with the same speed of Light (3.0x 1010 cm/sec 3.0x 108m/sec)
Characteristics of Electromagnetic radiations:
Wavelength:
The distance between two consecutive crests or troughs of the wave is known as wave
length it is denoted by λ and it is expressed A° 1 A°= 10 -10 m (or) 10-8 cm

Frequency:
The number of times a wave passed through a fixed point for unit time is known as frequency it is
denoted by ʋ and it is expressed Cycles/sec or Hz.
Wavenumber:
The reciprocal of wavelength is called wave number it is denoted by ʋ- and it is expressed cm_1
ʋ- =1/λ

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Amplitude:
The depth of the trough or height of the crest is known as amplitude. It is denoted by a.
Velocity:
The distance travelled by a wave in one second is known as velocity. It is denoted by C and
it is expressed cm/s or m/s.

Electromagnetic Spectrum.
The arrangements of all types of electromagnetic radiations in order of their increasing wavelengths
and decreasing frequencies is known as electromagnetic spectrum.

Black body radiation: When solids are heated they emit radiation over a wide range of
wavelengths.
Blackbody: An ideal body which can emit and absorb radiation of all frequencies is called Black
body.

Plank’s quantum theory:

Electromagnetic wave theory could not explain the phenomenon of black
body radiation and photoelectric effect.
 In the year1900 Max planks proposed a theory of radiation which are the emissions and
absorption of the energy by an atom occurs in the form of radiations, is not a continues
process.
 The emission and absorption of the energy by a body occurs in the form of packets of energy
is called photon or quanta.
 The energy of photon is directly proportional to the frequency of radiation is expressed

𝐸α ʋ

ℎ𝑐
𝐸= ℎʋ (𝑜𝑟) − − − − − − −− − −− − − (1)
𝜆
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 Where
E= Energy of the radiation
h= is planks constant (6.623X10-34 j.sec)
ʋ = Frequency of radiation.
λ= wavelength in A0 (or) meters (or) cm
𝐸=ℎ𝑐ʋ−−− − − −− (2)
 The total energy emitted or absorbed by a body is always an integral multiple of hʋ but
never a fraction.
E= nhʋ
n=1,2,3,4

Ex=1hʋ, 2hʋ, 3hʋ, 4hʋ, 5hʋ,

The above Equation says that the wave of higher frequency or lower wavelength will be
more energetic and vice versa.

 Ex: In VIBGYOR the higher frequency of violet is more energetic where as lower
frequency of red is less energetic.

 Niels bohr use this theory to explain the atomic structure

De-Broglie hypothesis (Dual nature of Matter):

Einstein had suggested that light has dual character that is a wave as well as particle nature.
Louis de-Broglie proposed that electron (Matter) also has a dual character as a wave and a
particle nature.

De-Broglie wave equation:

If a particle of mass m moving with velocity V then the wave length
of this moving particle is given by
ℎ
𝜆=
𝑚𝑣
Where
h = planks constant (6.623X10-34 j.sec)

m = Mass of the particle.

v =Velocity of the particle.
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 According to Planks quantum theory
𝐸=ℎʋ − −− − −− −−(1)

According to Einstein-energy-mass relation the energy of E the photon is given b

𝐸=𝑚𝑐2−−−−(2)
From equation1&2 ℎ𝑐
=𝑚𝑐2
𝜆
ℎ
=𝑚𝑐
𝜆
ℎ
𝜆=
𝑚𝑐
ℎ
𝜆= − −− − − − (3)
𝑝

Here P=mc is the momentum of photon having mass ‘m’ and travelling with velocity ‘c’
The above equation (3) is known as the de-Broglie’s wave equation for wavelength of
matter.
De-brogiles concept is significant for small (microscopic) particles like electrons only. For
microscopic particle, the wavelength is so short and wave properties cannot observe. Hence as per
this theory, an electron is not a point mass moving in an orbit but a standing wave extending around
the nucleus in circular fashion.

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Heisenberg Uncertainty principle:
The wave nature of particle is further explained by Heisenberg’s uncertainty principle.
“It is impossible to measure exactly and simultaneously both position and momentum of particle”
If Δx and Δpare the uncertainties in the position and momentum respectively.
When they are simultaneously measured
ℎ ℎ
𝛥𝑥𝛥𝑝≥ 𝑜𝑟𝛥𝑥𝑚𝛥𝑣≥
4𝑀 4𝑀
Δx= Uncertainty in position
Δp= Uncertainty in
momentum
m=Mass of electron
h=Plank’s constant

Case (i):
If the position of the particle known exactly Δx=0
𝛥𝑥𝛥𝑣=ℎ/4𝑀𝑚
𝛥𝑣=ℎ/4𝑀𝑚𝛥𝑥
𝛥𝑣=ℎ/4𝑀𝑚𝑋𝑋0=∞

Case (ii):
If the momentum of the particle known exactly Δv=0
𝛥𝑥𝛥𝑣=ℎ/4𝑀𝑚
𝛥𝑥=ℎ/4𝑀𝑚𝛥𝑣
𝛥𝑥=ℎ/4𝑀𝑚𝑋𝑋0=∞

Uncertainty principle is significant for microscopic level particle like electron only. It provides
the probability of finding an electron in a given space around the nucleus

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Schrodinger wave equation:
 Schrödinger wave equation is given by Erwin Schrodinger in1926 based on dual nature of
electron.
 Electron is described as a three-dimensional wave in the electric field of a positively charged
nucleus.
 The probability of finding an electron at any position around the nucleus can be determined by
the help of Schrodinger wave equation.
 In quantum mechanics there is no difference b/w wave and particle in addition it is applicable
for both micro (and) macroscopic particles.
∂2ψ ∂2ψ ∂2ψ 8π2m
+ ∂y2 + ∂z2 + (𝐸 − 𝑉 )ψ = 0
∂x2 ℎ2

Where
m= mass of an electron
E= Total energy of electron
V= Potential energy of electron
h=Plank’s constant
Ψ= Amplitude of the wave function

x, y, z= Cartesian coordinates
Derivation:
The wave equation of stationary wave associated with the particle in terms of coordinate
System is
2
  ASin x ---- (1)

Where
Ψ=Amplitude of the wave function
A= Constant
x= Displacement of wave in the given direction x
λ= Wavelength
Differentiate equation-(1) with respective to x we get
  2  2
 A cos  x
    

 2 2x
 A cos --------------- (2)
  
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Again differentiate equation-(2) with respective to x we get

2 2  2x  2  2 4 2  2x 

A   sin   2   2  A sin    (3)
x 2
     x    

Substitute eq. (1) in eq. (3) then we get

2 4 2
   
x 2 2
4 2
 2   2     (4)
 
x 2
According to de-Broglie wavelength equation

h h2
  v  2 2    (5)
2

mv m

1 2
We know the K .E  mv    (6)
2
1 h2
Put the eq.(5) in eq.(6), we get K .E     (7)
2 m 2

1 h2  h 2   2 
Substitute eq.(4) in eq.(7) K .E    K .E     2  2    (8)
2    8 m  x
 4 2 
m  2 
   
 x 2 

The total energy of the system E is made up of the kinetic energy (K.E) + potential energy(V)
E  K .E  V  K .E  E  V    (9)

 2   8 2 m 
From eq.(8) and (9)    E  V    0    (10)
x 2  h2 

The above eq (10) is called 1-D Schrodinger wave equation

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Significance of Ψ and Ψ2

Significance of Ψ
1. Ψ should be single value

2. Ψ should be continues (There should not be sudden change in its value)

3. Ψ must be finite over the space.

4. Ψ must be normalized (The probability of finding electron in space must be one unity)

5. Ψ must be zero at infinity.

Significance of Ψ2
1. Ψ2 is probability function
2. Ψ2 value is always positive
3. Ψ2 describes the probability of finding an electron around the nucleus and where the
value of Ψ2 is maximum is called an orbital.

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Molecular orbital theory (MOT):
Molecular orbital theory was developed by F.Hund’s and R.S.Milliken in the year 1932.
Postulates:
 Valance bond theory could not explain the paramagnetic nature of oxygen molecule. A new
theory was introduced to explain the paramagnetic nature of oxygen molecule called as MOT.
 This theory is a method for describing the electronic structure of molecules using quantum
mechanics or wave mechanics. Electrons are not assigned to individual bonds b/w atoms. But
are treated as moving under the influence of the nuclei in to the whole molecule.

“The same or individual two atomic orbital’s combine together to form a two new orbital’s called
molecular orbitals”
 The two molecular orbital’s produced by two atomic orbitals, one is bonding molecular
orbital and another one is anti bonding molecular orbital.
 Bonding molecular orbitals has lower energy and more stable whereas anti bonding molecular
orbital’s has higher energy and less stable.
 Bonding molecular orbitals are formed by constructive interference of wave function or
addition of wave function, where as the anti bonding molecular orbital’s are formed by
destructive interference of wave function or subtraction of wave function.
 When two different atomic orbitals combine together forms non bonding molecular orbitals.
 In addition to magnetic nature MOT also explains the bond order, bond stability bond length
and bond energy or bond strength etc.
 The electrons filled in various molecular orbitals just like the electrons filled in various
atomic orbital’s according aufbau principle, Pauli’s exclusion principle and hund’s rule.
 The atomic orbitals are influenced by one nucleus and thus it is mono centric where as the
molecular orbitals are influenced by two or more nuclei and thus it is poly centric.
 The atomic orbital’s are designated as s, p,d,f where as molecular orbital’s are designated as ϭ
, ϭ*, Π, Π*, δ, δ* etc.
 Let us consider electrons as either particle or wave nature. Hence an electron in an atom occupies an
atomic orbital or by a wave function (Ψ). These are the solutions to the Schrödinger wave equation.
Electrons in a molecule occupy molecular orbitals.This can be explained by the linear combination of
atomic orbital’s (LCAO) method.
Linear Combination of Atomic Orbitals (LCAO).
Sailent features of LCAO.
(I)Atomic orbitals consist of atoms; molecular orbital’s consist of molecules.
(ii) Atomic orbital’s are represented as1s,2s,2p--------- etc. whereas molecular orbital’s are represented
as σ/ Π/δ and so on.
(iii) The number of atomic orbital’s are combine to form a number of molecular orbital’s.

(iv) The two atomic orbital’s combine and the wave represented as ΨA, ΨB they form constructive
interference and destructive interference.
The constructive interference is called as bonding molecular orbital’s (BMO) and it has lower
energy. The destructive interference is called Anti-Bonding molecular orbital’s (ABMO) and it has
higher energy.

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(v) The combining atomic orbital’s must have same energy or nearly same energy and same shape of
the orbital’s (S-S, Px-Px, Py-Py ----- etc).
S-S Combination of orbital’s.
Let us consider the atoms A and B are hydrogen atoms; then the wave functions ΨA, and ΨB represents
the 1s atomic orbital’s on the two atoms. Two combinations of the wave functions are possible.
(i) The signs of the two wave functions are the same σ1s molecular orbital is formed (BMO)
Ψb = Ψ A + ΨB

(ii) The signs of the two wave functions are different σ*1s molecular orbital is formed (ABMO)
In ABMO the dotted lines b/w the two lobes indicates a node or nodal plane where the probability of
finding electron density is zero.
Ψa = ΨA - ΨB

p-p Combination of orbital’s.

The combination of P-orbital’s which gives the two bonds these are σ and Π the σ bond is formed by
axial combination of P-P orbital’s ,where as incase of side by side or lateral combination Π-orbital’s
are formed.

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 With this it is clear, the interaction of AOs to form the MOs is possible only if the symmetry
considerations are taken care.
i) If s-px combination is allowed then s-py and s-pz combination is not allowed because px lies
along the molecular axis.
ii) Similarly, If x-axis is the molecular axis only Px-Px,Py-Py and Pz-Pz combinations are
Allowed, whereas Px-Py, Px-Pz combinations are not allowed. Py-Py and Pz-Pz combination will
produce Π MOs and Π* MOs. These Π py and Π pz as well as Π *py and Π *pz MOs have the same
energy, i.e. these are degenerate orbital’s.

Order of MOs energy levels: The order of energy levels of the MOs can be determined experimentally
from spectroscopic studies.
Case (i) Increasing order when the molecules containing less than 14electrons (or) 14 electrons
we need to follow the electronic configuration.
σ1s2<σ *1S2<σ2s2<σ *2S2<Π2px2=Π2py2<σ2pz1<Π*2px=Π*2py <σ *2pz
Case (ii) Increasing order when the molecules containing more than14 electrons we need to
follow the electronic configuration.

σ1s <σ*1S<σ 2s<σ*2S<σ2pz<Π2px= Π2py <Π*2px=Π*2py<σ*2pz

Bonding in homo nuclear diatomic molecules:

Homo nuclear diatomic molecules are those molecules which are made up of single nucleus. These
molecules are composed of only two atoms of the chemical elements. The bond in homo nuclear
diatomic molecule is non-polar due to electro negativity difference is zero.
Ex: H2, O2, N2, F2 etc

Energy level diagrams for homo diatomic molecules (N2, O2):

Energy level diagram of N2:
The nitrogen atomic number is 7.
The electronic configuration is1S2,2S2 ,2P3. Each
nitrogen atom has 7 electrons.
N2 molecule has14electrons.
In N2 molecule the total electrons are 14, hence we need to follow the case (i) for fill-up electrons in
molecular orbital.

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 Electronic configuration of N2 is:
σ1s2<σ *1S2<σ2s2<σ *2S2<Π2px2=Π2py2<σ2pz2<Π*2px=Π*2py <σ *2pz

Number of electrons in BMO−Number of electrons in ABMO

Bond order =
2
10− 4
Bond order= =3
2

Bond order indicates nitrogen molecule contains a triple bond. Since all the electrons in bonding as
well as anti-bonding molecular orbital’s are paired ,hence it is diamagnetic.

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 Energy level diagram of O2:
The oxygen atomic number is 8.
The electronic configuration is1S2,2S2,2P4.

Each oxygen atom has 8 electrons.

O2 molecule has16electron
In O2 molecule the total electrons are 16, hence we need to follow the case (ii) for fill-up electrons in
molecular orbital.

Electronic configuration of O2 is:

σ1s <σ*1S<σ 2s<σ*2S<σ2pz<Π2px= Π2py <Π*2px=Π*2py<σ*2pz

Number of electrons in BMO−Number of electrons in ABMO

Bondorder=
2

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 10− 6
Bond order = =2
2

Bond order indicates oxygen molecule contains a double bond. The O 2 molecule exhibits
paramagnetic behavior, due the presence of two unpaired electrons in Π *2py and Π *2px molecular
orbitals.

Bonding in hetero nuclear diatomic molecules:

In hetero nuclear diatomic molecule the electron distribution between the two atoms is not
symmetrical due to the difference in their energy levels. This leads to polar bonds, in which electron
pairs is shared unequally by two atoms
Ex: CO, NO, HF etc
Energy level diagram of CO:
The carbon atomic number is 6; Electronic configuration is 1S 2, 2S2, 2P2.
The oxygen atomic number is 8; Electronic configuration is1S 2,2S2,2P4.
The CO has total number of electrons are 14; hence we need to follow the case (i) for fill-up the
electrons in molecular orbital’s.
In CO oxygen has more electro negative than carbon, hence the oxygen contains less energy levels
compared to carbon.
Electronic configuration of CO is:
σ1s2<σ *1S2<σ2s2<σ *2S2<Π2py2=Π2px2<σ2pz2<Π*2py=Π*2px <σ *2pz

Number of electrons in BMO−Number of electrons in ABMO

Bond order =
2
10− 4
Bond order= =3
2
Bond order indicates the presence of a triple bond in the molecule. Further the molecular orbital
configuration of CO is similar to the (isoelectronic) N2.
Since all the electrons in bonding as well as anti-bonding molecular orbitals are paired it exhibits
diamagnetic behavior.

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π -Molecularorbitalsof1, 3-butadiene:
CH2=CH-CH=CH2
The structure of 1,3-butadiene consists of two conjugated double bonds. The structure has four sp2
hybridized carbon atoms. Each carbon atom contributes a ‘p’ atomic orbital which is not involved in
hybridization consisting of one electron, resulting in the arrangement of four π electrons from four p-
orbital’s which combine in four different ways and form four molecular orbital’s designated by Ψ1,
Ψ2, Ψ3, and Ψ4.
The π -orbital can be interacted with another π -orbital of a same molecule with the same plane or
same symmetry.
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Another interaction of the π –orbital’s in opposite direction is called as out of plane or symmetry.

The energy level diagram of butadiene is represented below.

Ψ1 has bonding interactions between C1-C2, C2-C3 and C3-C4 Therefore; there exist 3 bonding
interactions (BI)
Ψ2 has bonding interactions between C1-C2 and C3-C4 and anti-bonding interactions (ABI) betweenC2-
C3. Therefore, they have single anti-bonding interaction. It is the highest occupied molecular orbital
(HOMO).
Ψ3 has bonding interactions between C2-C3 but anti-bonding interactions between C1-C2 and C3-C4.
Therefore, they have two anti-bonding interaction. It is the lowest unoccupied molecular orbital
(LUMO).
Ψ4 has anti-bonding interactions between C1-C2,C2-C3 and C3-C4.Therefore, they have 3anti- bonding
interactions.
With this information it is clear out of the four orbitals available, the molecular orbitals Ψ1 and Ψ2 are

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Bonding molecular orbitals whereas the molecular orbitals Ψ3 and Ψ4 are anti-bonding molecular
orbitals. The energy in molecular orbitals increases with the rise in the number of nodes.
Π-MolecularorbitalsofBenzene:
Benzene is a conjugated cyclic structure it has six carbon atoms, each carbon atom undergoes sp2
hybridization. But each carbon atom has one un hybridized Pz orbital. Now the six un hybridized Pz
orbital’s are combine to form 6 molecular orbital’s namely Ψ1,Ψ2, Ψ3,Ψ4, Ψ5, Ψ6.out of which 3 are
bonding molecular orbital’s ,the other is anti bonding molecular orbitals.Eachmoleculeorbitalcan
accommodate two electrons having opposite spins. It gives the no of orbital’s present with respect to
the Π electron cloud. Π electron cloud depends on the no of nodes.
The energy level diagram of Benzene is represented below.

Ψ2, Ψ3 - HOMO Ψ4, Ψ5 - LUMO

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 PartA-Question &Answers
1. What is Wave Length?
Ans: The distance between two consecutive crests or troughs of the wave is known as wave length
it is denoted by λ and it is expressed A° 1 A°= 10-10 m (or) 10-8 cm.
2. Define the term Frequency.
Ans: The number of times a wave passed through a fixed point for unit time is known as frequency
it is denoted by ʋ and it is expressed Cycles/sec or Hz.
3. What is Electromagnetic Spectrum?
Ans: The arrangements of all types of electromagnetic radiations in order of their increasing
wavelengths and decreasing frequencies is known as electromagnetic spectrum.
4. What is Schrodinger wave equation and explain terms in it.
Ans:
2 2 2 2
∂ ψ ∂ ψ ∂ ψ 8π m
+ + + (𝐸 − 𝑉)ψ = 0
∂x2 ∂y2 ∂z2 ℎ2

Here,

m= mass of an electron; E= Total energy of electron; V= Potential energy of electron; h=Plank’s

constant; Ψ = Amplitude of the wave function; x,y,z= Cartesian coordinates
5. Write briefly Significance of Ψ
Ans:1. Ψ should be single value; 2. Ψ should be continues (There should not be sudden change in
its value); 3. Ψ must be finite over the space; 4. Ψ must be normalized (The probability of finding
electron in space must be one unity); 5. Ψ must be zero at infinity.
6. Significance of Ψ2
Ans:1. Ψ2 is probability function; 2. Ψ2 value is always positive; 3. Ψ2 describes the probability of
finding an electron around the nucleus and where the value of Ψ 2 is maximum is called an orbital.
7. Define the term Bond order.
Ans: Bond order= Number of electrons in BMO−Number of electrons in ABMO
2

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 PartB-10MarksQuestions
1. Derive Schrodinger wave equation Significance of Ψ and Ψ2
2. Construct molecular energy level diagram for CO molecule
3. Explain the dual nature of matter.
4. Draw the Π-molecular orbital energy level diagrams of butadiene and benzene.
5. Write brief note on Heisenberg’s uncertainty principle
6. Discuss the molecular orbital diagram of CO and find out its bond order
7. Write brief notes on LCAO or Salient features of Molecular Orbital Theory.
8. Explain the Planck’s quantum theory.
9. Illustrate the energy level diagrams of O2,C2 and N2

Assignment questions
1. Write Plank’s quantum theory and de-Broglie’s wave equation
2. Describe Schrodinger wave equation?
3. Write the postulates of MOT?
4. Write the energy level diagram of O2 and CO molecule
5. Write the pi molecular orbital of benzene

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