INORGANIC CHEMISTRY

I Semester
Unit 1 : Atomic Structure:
Bohr’s Theory – Bohr’s Atomic Model:

Thomson’s atomic model and Rutherford’s atomic model failed to answer any
questions related to the energy of an atom and its stability. In the year 1913, Niels
Bohr proposed an atomic structure model, describing an atom as a small, positively
charged nucleus surrounded by electrons that travel in circular orbits around the
positively charged nucleus like planets around the sun in our solar system, with
attraction provided by electrostatic forces, popularly known as Bohr’s atomic model.
It was basically an improved version of Rutherford’s atomic model overcoming its
limitations.
Postulates:

• Electrons revolve around the nucleus in stable orbits without emission of

radiant energy. Each orbit has a definite energy and is called an energy shell
or energy level.
• An orbit or energy level is designated as K, L, M, N shells. When the electron
is in the lowest energy level, it is said to be in the ground state.
• An electron emits or absorbs energy when it jumps from one orbit or energy
level to another. When it jumps from a higher energy level to lower energy
level it emits energy while it absorbs energy when it jumps from a lower
energy level to a higher energy level.
• The energy absorbed or emitted is equal to the difference between the
energies of the two energy levels (E1, E2) and is determined by Plank’s
equation.
ΔE = E2-E1 = hˠ
Where,
ΔE = energy absorbed or emitted
h= Plank’s constant
ˠ= frequency of electromagnetic radiation emitted or absorbed
 • The angular momentum of an electron revolving in energy shells is given by :
𝒏𝒉
mvr =
𝟐𝝅
Where,
n= number of corresponding energy shell; 1, 2, 3 …..
m= mass of the electron
v= velocity
r=radius
h= Plank’s constant

Limitations of Bohr Atomic Model Theory:

• It is applicable only to hydrogen atom or uni electron system like He+
• The spectra of multielectron systems could not be explained
• The experimental value of ionisation energy and the value of calculated from
Bohr’s theory do not agree
• No proper explanation of chemical bonding is possible
• The uncertainty principle goes against Bohr’s theory.

Need of a new approach to atomic structure

De-Broglie Hypothesis (Dual nature of matter and radiation) :
Earlier, it was thought that light is a stream of particles which are protons
However, this concept failed to explain the phenomena of interference and diffraction
which could be explained only if light is considered to have wave nature. But at the
same time, it was observed that the phenomena of black body radiation and
photoelectric effect could be explained only if light is as well as wave nature, It has a
dual nature
Louis de Broglie, a French physicist in 1924, advanced the idea that like
photons, all material particles such as electron, proton, atom, molecule, a piece of
chalk a piece of stone or an iron ball also possessed dual character. The wave
associated with a particle is called a matter wave or de Broglie wave.

The de-Broglie’s Relation:

The wavelength of the wave associated with any material particle was calculated
by analogy with photon as follows
In case of a photon, if it is assumed to have wave character, its energy is given by

E=hˠ (1) (According to planks quantum theory)

Where ˠ is the frequency of the wave and h is plank’s constant

If the photon is supposed to have particle character its energy is given by

E= mc2 (2) (According to Einstein equation)

Where m is the mass of photon and c is velocity of light

From equation (1) and (2) we get
 hˠ= mc2 (3)
𝒄
ˠ=𝝀
𝒄
h𝝀 = mc2
𝒉
λ= (4)
𝒎𝒄

de Broglie applied equation (4) for any material particle and hence for an electron
also.
In general for any particle of mass m, moving with a velocity u, the de Broglie
equation becomes
𝒉
λ=
𝒎𝒖
𝒉
λ=
𝑷
where mu=P is the momentum of the particle
the above equation is called de-Broglie’s equation.

Heisenberg’s uncertainty principle :

It is impossible to determine to determine the exact momentum as well as exact
position of a moving electron simultaneously. The mathematical form of Heisenberg
uncertainty principle is
ℎ
Δx×Δp≥2𝜋
Where Δx= the error in determination of position
Δp = the error in determination of momentum
h = plank’s constant
significance:
• Δx is small then Δp is large
• Δp is small then Δx is large
• Position and momentum of an moving electron can not be determine
simultaneously
• This principle is applicable only to microscopic moving particles.

Hydrogen atomic spectra:

Spectrum of hydrogen has helped a lot in understanding atomic structure. This
spectrum can be obtained by passing the light obtained from hydrogen gas at low
temperature contained in a discharge tube through the spectrograph.
 The spectrum obtained consists of large number of shapes lens. Each line correspond to
a particular frequency of light emitted by hydrogen atoms. Lines in the emission
spectrum of hydrogen are present in ultraviolet visible and infrared regions.
The lines in the emission spectrum of hydrogen are classified into five series as
possible
• Lyman series ultraviolet region
• Balmer series visible region
• Paschen series
• Bracket series infrared region
• P fund series

1. Transition from higher energy levels with n=2,3,4 etc n=1

These transition involve emission of photons corresponding to ultra violet
region. This results in the formation of Lyman series of hydrogen spectra.
2. Transitions from higher energy levels with n=3,4,5 etc n=2
These transitions result in the formation of balmer series in the visible region.
3. All the transition to the level n=3 from higher levels constitute the paschen
series.
4. Brackett series is obtained because of the transition to level n=4from higher
level.
5. Pfund series is obtained because of the transitions to level n=5 from higher
levels.
Elements of quantum chemistry:
Schrodinger wave equation and meaning of various terms in it:
Considering the above facts schrodinger proposed an equation which describe the
wave motion of electron along any of three axis.

𝐝𝟐 𝛙 𝐝𝟐 𝛙 𝐝𝟐 𝛙 𝟖𝛑𝟐 𝐦
+ 𝐝𝐲 𝟐 + + + [E − V]ψ = 𝟎
𝐝𝐱 𝟐 𝐝𝐳 𝟐 𝐡𝟐

Where ψ is called the wave function and it represents the amplitude of the electron wave at
various points surrounding the nucleus

X,y,z =Cartesian coordinates

m = mass of electron
h = planks constant
E = total energy electron
V = potential energy of the system

Or x , y, z, are the 3 axis (co ordinates )in space.

Application:

• It is used to calculate the energy and wave function of a particle in one dimension or
three dimensions
• It introduces the concept of atomic orbital
• According to above theories and wave mechanics each energy level correspond to an
electron wave enveloping the nucleus. The electron wave will have shape , size , and
orientations hence it is possible to identify region of space around the nucleus.

Significance of ψ and ψ2:

The wave function ψ represent amplitude of electron wave.

Where as ψ2 gives the probability of finding an electron of a given energy E in a given region
around nucleus. Hence probability of finding particle at a particle at a particular point is
proportional to equation of the wave function ψ2 at that point.

Schrodinger equation for hydrogen atom:

Schrodinger wave equation for one electron atomic system (like hydrogen atom )is
𝐝𝟐 𝛙 𝐝𝟐 𝛙 𝐝𝟐 𝛙 𝟖𝛑𝟐 𝐦 Ze2
+ + + + [E + ]ψ = 𝟎
𝐝𝐱 𝟐 𝐝𝐲 𝟐 𝐝𝐳 𝟐 𝐡𝟐 ɤ
For hydrogen atom z=1 schrodinger wave equation for H atom be written as

𝐝𝟐 𝛙 𝐝𝟐 𝛙 𝐝𝟐 𝛙 𝟖𝛑𝟐 𝐦 e2
+ 𝐝𝐲 𝟐 + + + [E + ]ψ = 𝟎
𝐝𝐱 𝟐 𝐝𝐳 𝟐 𝐡𝟐 ɤ

where Ze = charge of the nucleus

Z= atomic number
e = charge on the electron

ψ = wave function
m = mass of electron
E = total energy electron
h = plank’s constant

radial and Angular nodes :

A node is a point where the electron probability is zero for a given orbital there are 2
types of nodes
1. Radial node
2. Angular node
Radial node is called as nodal region. Radial node is a spherical surface where probability of
finding an electron is zero. The number of radial nodes increases with principle quantum
number(n).
Angular node is also called nodal plane. Angular node is a plane that passing through the
nucleus. Angular node is equal to the azimuthal quantum number(l). The number of angular
nodes=1 The number of radial nodes= (n-l-1) total number of nodes=n=1
For atomic orbitals, the wave function can be separated into radial part and an
angular part so that it has the form

Ψ(ɤ, Ɵ, ɸ) = R (ɤ) Y (Ɵ, ɸ )

Where R(ɤ) is the radial component which depends only on the distance from the nucleus.
And Y (Ɵ, ɸ) is the angular component.
Figure various S orbitals All of these orbitals have l=0, but they have different values for n.
the first orbital has n=1 and thus is small and has no nodes. The second orbital has n=2, and
thus is large and has one node. The third orbital has n=3 and thus is even larger and has two
nodes.
Angular nodes:

A radial node will occur where the radial wave function R(ɤ), equals zero of changes sign. At
a node the probability of finding an electron is zero. Which means that will never find an
electron at a node.

Quantum numbers and significance:

Since the electron wave have a certain size, shape and orientation an electron in an atom
is completely described by its quantum number in order to locate the electron in an atom it
is necessary to know about the 4 quantum numbers

1. Principal quantum number (n)

2. Azimuthal quantum number (l)
3. Magnetic quantum number (m)
4. Spin quantum number (S)

Principal quantum number (n):

It is the most quantum number as it determine the energy of an electron and it also
determine the energy of an electron and it also determine the average distance of electron
from the nucleus and represented by ‘n’
The main significance is it gives us the size of the orbital and represents the main
energy level n can have the value 1 , 2, 3, …….n
a. The value of n represent the main energy level in which the electron removes
around the nucleus when n=1 k shell
n =2 l shell
b. n also determine the location of an electron S shell (main energy level)
c. ‘n’ gives the maximum number of electron that a main energy level can hold that is
2n2 where n =1 no. electron=2 k shell
n = 2 no. electron =8 L shell
n = 3 no. electron = 18 M shell
Azimuthal quantum number:
As the portion of energy is associated with orbital m
This orbital motion is described by angular momentum of electron. Thus electron in a atom
are grouped not only into main energy level but also into sub energy levels given by this
quantum numbers and is represented as l = 0,1,2,3…..(n-2)(n-1)
The main significance of this quantum number is it describes the shape of orbital
and represents various sub shells present in the main energy level.

The different values of ‘l’ represent different sub energy level which are
designated by s, p, d, f
Value of ‘l’ 0,1,2,3
Designation S,p,d,f

1. The value of ‘l’ define the shape of sub energy level occupied by the electron for
example where l =0 and sub shell which has a spherical shape
2. L values enables us to calculate the total number of subshell belongs to main energy
level
Example: n = 1 l =0 i.e. 1 subshell ‘s’
n = 2 l =0,1 i.e. 2 subshell ‘s’ ‘p’
the total no. of electron can also be calculated by knowing the L valve 2[2l+1]
example: L=0 2[2(0)+1] =2s
L=1 6p

Magnetic quantum number (m):

Since the electron is an atom is in continuous motion it is associated with the flow of
electric current such a flow of electric current create a magnetic field it interact with
external magnetic or electric field as a result the electrons is given energy subshell orient
themselves in certain specific region of space around the nucleus, these region of space are
called orbitals or space energy levels.
Therefore the main significance of magnetic quantum number is to find the orientation
of the sub energy level in space i.e. along 3 axis there M value depends on value of l
having from -l through +l making a total (2l+1) values.
1. If l=0 M=0 i.e. s orbital since it is spherical it is having only one orientation in space
2. If l =1 M=-1,0,1 hence P orbital has 3 possible orientations P(x) P(y) P(z)

Spin quantum number (s) :

The electron in its motion around the nucleus also spin about its own axis. The
1
electron spin can be either clock wise or anticlockwise, hence 2 values od s are ±2 and is
represented by ↑↓ designated as clock wise or anti clock wise.
Shapes of s , p , and d atomic orbitals:
There are four different kinds of orbitals, denoted s, p, d and f each with a different
shape. Of the four, s and p orbitals are considered because these orbitals are of
most common in organic and biological chemistry. An s-orbital is spherical with the
nucleus at its centre, a p-orbitals is dumbbell-shaped and four of the five d orbitals
are cloverleaf shaped. The fifth d orbital is shaped like an elongated dumbbell with a
doughnut around its middle. The orbitals in an atom are organized into different
layers or electron shells.

The Shape of s Orbitals:

• The boundary surface diagram for the s orbital looks like a sphere having the
nucleus as its centre which in two dimensions can be seen as a circle.
• Hence, we can say that s-orbitals are spherically symmetric having the
probability of finding the electron at a given distance equal in all the directions.
• The size of the s orbital is also found to increase with the increase in the value
of the principal quantum number (n), thus, 4s > 3s> 2s > 1s.

The Shape of p Orbitals:

• Each p orbital consists of two sections better known as lobes which lie on
either side of the plane passing through the nucleus.
• The three p orbitals differ in the way the lobes are oriented whereas they are
identical in terms of size shape and energy.
 • As the lobes lie along one of the x, y or z-axis, these three orbitals are given
the designations 2px, 2py, and 2pz. Thus, we can say that there are three p
orbitals whose axes are mutually perpendicular.
• Similar to s orbitals, size, and energy of p orbitals increases with an increase
in the principal quantum number (4p > 3p > 2p).

The Shape of d Orbitals:

• The magnetic orbital quantum number for d orbitals is given as (-2,-1,0, 1,2).
Hence, we can say that there are five d-orbitals.
• These orbitals are designated as dxy, dyz, dxz, dx2–y 2 and dz2.
• Out of these five d orbitals, shapes of the first four d-orbitals are similar to
each other, which is different from the dz2 orbital whereas the energy of all five
d orbitals is the same.

Energy level diagram of multielectron atom:

In a multi electron atom the relative energies of various orbitals in the increasing
order to their energy can be drawn according diagram knows as energy level
diagram in a multielectron atom as there are many number of electrons they are
accommodated from the lower energy levels to higher energy levels as shown in the
diagram.

Rules for filling up of electrons in various orbitals:

Aulbau principle: Aufbau means building up of electronic configuration of atoms
Statement : “ in the ground state of an atom electrons enter the orbitals of the
lowest energy and the orbitals are filled in the order of increasing energy”
The increasing order of energy level can easily remembered with the help
of the following graphical representation. The increasing order of energy is shown by
arrows. Thus the increasing order of energy of orbital are
1s˂2s˂2p˂ 3s˂ 3p˂ 4s˂ 3d˂ 4p˂ 5s˂ 4d˂ 5p˂ 6s˂ 4f˂ 5d˂ 6p˂ 7s˂ 5f˂ 6d˂ 7p

Pauli’s exclusive principle:

Statement: “no two electrons in the same atom can have all the quantum
numbers identical.” Thus in the same atom two electrons may have 3 quantum
numbers identical but the 4th must be different. This principle is very useful in
determining the maximum of electron in any shell.
1
Example: In K shell n=1 l=0 m=0 s=±2

Hence it follows that an orbital can accommodate maximum of two electrons with
opposite spin.
Hund’s rule of maximum multiplicity:
Statement: “ electron pairing in orbitals of same energy level will not take
place unless when all the available orbitals of same energy contain 1 electron each’”.
Example: There are 3 orbitals Px Py and Pz in ‘P’ subshell according to this rule each
of the P orbital must get one electron each and then the pairing of electron takes
place with opposite spin. This means pairing of electrons begins with the repulsion
of 2 electron in s orbital 4th electron in p orbital 6th electron in d and 8th in f orbitals.
Example: N =7 E.C. 1s2 2s2 2p3

(n+ l) rule: To find the order of increasing energy levels (n + l) rule may also be used

Rule 1: when 2 orbitals have different values for lower value of n + l is of lower energy
Example: 3d orbital n + l = 3+2=5
4s orbital n + l = 4+0=4

Therefore 4s is having lower energy than 3d as (n + l) value is lower for 4s

Rule 2: when 2 orbitals have same value foe (n + l) the orbital with lower value of ‘n’
is lower energy.
Example: 3d = n + l = 3+2=5

4p = n + l = 4+1=5
3d has lower value for ‘n’ than 4p, therefore 3d is lower energy than 4p.