STRUCTURE OF ATOM

Bohr’s Model
Neils Bohr proposed his model in 1931. Bohr’s model is applicable only for one electron
system like H, He+, Li2+ etc.
Assumptions of Bohr’s model are
1. Electrons keep revolving around the nucleus in certain fixed permissible orbits where it
doesn’t gain or lose energy. These orbits are known as stationary orbits.
Number of waves in an orbit = circumstances of orbit / wavelength
2. The electrons can move only in those orbits for which the angular momentum is an
integral multiple of h / 2π, i.e.,
mvr = nh / 2π
where, m = mass of electron: v = velocity of electron;
r = radius of orbit
n = number of orbits in which electrons are present
3. Energy is emitted or absorbed only when an electron Jumps from higher energy level to
lower energy level and vice-versa.
ΔE = E2 – E1 = hv = hc / λ
4. The most stable state of an atom is its ground state or normal state.
From Bohr’s model, energy, velocity and radius of an electron in nth Bohr orbit are
(i) Velocity of an electron in nth Bohr orbit
(vn) = 2.165 × 106 Z / n m / s
(ii) Radius of nth Bohr orbit
(rn) = 0.53 × 10-10 n2 / Z m = 0.53 n2 / Z Ao
iii. Energy of the Bohr orbit:

where, n = number of shell; Z = atomic number

As we go away from the nucleus, the energy levels come closer, i.e., with the increase in the
value of n, the difference of energy between successive orbits decreases.
Thus. E2 – E1 > E3 – E2 > E4 – E3 > E5 – E4etc.

Line Spectrum of Hydrogen

When electric discharge is passed through hydrogen gas enclosed in discharge tube under
low pressure and the emitted light is analysed by a spectroscope, the spectrum consists of a
large number of lines which are grouped into different series. The complete spectrum is
known as hydrogen spectrum.
On the basis of experimental observations, Johannes Rydberg noted that all series of lines in
the hydrogen spectrum could be described by the following expression:

Rydberg in 1890, and has given a simple theoretical equation for the calculation of
wavelengths and wave numbers of the spectral lines in different series of hydrogen
spectrum. The equation is known as Rydberg formula (or equation).

This relation is valid for hydrogen atom only. For other species,

where Z is the atomic number of the species.

Here R = constant, called Rydberg constant for hydrogen and n1 , n2 are integers (n2 > n1)
For any particular series, the value of n1 is constant while that of n2 changes. For example,
For Lyman series, n1= 1, n2= 2, 3, 4, 5………..
For Balmer series, n1 = 2, n2 = 3, 4, 5, 6………..
For Paschen series, n1= 3, n2 = 4, 5, 6, 7………..
For Brackett series,n1 = 4, n2 = 5, 6, 7, 8………..
For Pfund series, n1 =5, n2 = 6, 7, 8, 9………..
Thus, by substituting the values of n1 and n2 in the above equation, wavelengths and wave
number of different spectral lines can be calculated. When n1 = 2, the expression given
above is called Balmer’s formula.
Achievements of Bohr’s Theory
1. Bohr’s theory has explained the stability of an atom.
2. Bohr’s theory has helped in calculating the energy of electron in hydrogen
atom and one electron species. The mathematical expression for the energy in
the nth orbit is,
3. Bohr’s theory has explained the atomic spectrum of hydrogen atom.

Limitations of Bohr’s Theory

1. It is unable to explain the spectrum of atom other than hydrogen like doublets or
multielectron atoms.
2. It could not explain the ability of atom to form molecules by chemical bonds. Hence. it
could not predict the shape of molecules.
3. It is not in accordance with the Heisenberg uncertainty principle and could not explain the
concept of dual character of matter.
4. It is unable to explain the splitting of spectral lines in the presence of magnetic field
(Zeeman effect) and electric field (Stark effect)

Dual Behaviour of Matter (de Broglie Equation)

de Broglie in 1924, proposed that matter, like radiation, should also exhibit dual
behaviour i.e., both particle like and wave like properties. This means that like
photons, electrons also have momentum as well as wavelength.
Heisenberg’s Uncertainty Principle
It states that, “It is impossible to determine simultaneously, the exact position
and exact momentum (or velocity) of an electron”.

Significance of Uncertainty Principle

(i) It rules out existence of definite paths or trajectories of electrons and other
similar particles.
(ii) The effect of Heisenberg’s uncertainty principle is significant only for
microscopic objects and is negligible for macroscopic objects.

Quantum Mechanical Model of Atom

It is the branch of chemistry which deals with dual behaviour of matter. It IS given by
Werner Heisenberg and Erwin Schrodinger
Schrodinger wave equation is

where. x, y, z = cartesian coordinates

m = mass of electron, E = total energy of electron
U =potential energy of electron, h =Planck’s constant
Ψ (Psi) = wave function which gives the amplitude of wave
Ψ2 = probability function
For H-atom. the equation is solved as
HΨ = EΨ
where, H is the total energy operator, called Hamiltonian. If the sum of kinetic energy
operator (T) and potential energy operator (U) is the total energy. E of the system,
H=T+U
(T + U)Ψ = EΨ
[The atomic orbitals can be represented by the product of two wave functions (i) radial
wave function (ii) angular wave function.
The orbital wave function, Ψ has no significance, but Ψ2 has significance, it measures the
electron probability density at a point In an atom. Ψ can he positive or negative but ‘I’: is
always positive.
Probability Diagrams
The graph plotted between Ψ2 and distance from nucleus is called probability diagrams.
Node
A region or space, where probability of finding an electron is maximum called a peak, while
zero probability space is called node. Nodes are of two types:
(a) Radial nodes
(b) Angular nodes
(i) (n – I – 1) = radial node
(ii) (l) = angular node
(iii) (n – 1) = total + node
Number of Peaks and Nodes for Various Orbitals
S. No. Type of orbital Number of peaks

1 s n

2 p n–1

3 d n–2

4 f n–3

Quantum Numbers
Each electron in an atom is identified in terms of four quantum numbers.
Principal Quantum Number (Niels Bohr)
It is denoted by n . It tells us about the main shell in which electron resides. It also gives an
idea about the energy of shell and average distance of the electron from the nucleus. Value
of n = any integer.
It gives the average distance of the electron from the nucleus.
(ii) It completely determines the energy of the electron in hydrogen atom and
hydrogen like particles.
(iii) The maximum number of electrons present in any principal shell is given by
2n2 where n is the number of the principal shell.

Azimuthal Quantum Number (Sommerfeld)

It is denoted by I. It tells about the number of subshells (s. p, d, f) in any main shell. It also
represents the angular momentum of an electron and shapes of subshells. The orbital
angular momentum of an
electron = √l (l + 1) h / 2π
Value of l = 0 to n – 1.
I = 0 for s, I = 2 for d
I = 1 for P. l = 3 for f
Number of subshells in main energy level = n.

Magnetic Quantum Number

is denoted by m. It tells about the number of orbitals and orientation of each subshell. Value
of m = – l to + 1 including zero.
Number of orbitals in each subshell = ( 2l + 1)

S.No. Subshell Orbital

1 s 1
2 p 3
3 d 5
4 f 7

Number of orbitals in main energy level = n2

Spin Quantum Number

“It is denoted by m, or s. It indicates the direction of spinning of electron, i.e., clockwise or
anti- clockwise.
Maximum number of electrons in main energy level = 2n2

Shapes of s-orbitals
s-orbital is present in the s-subshell. For this subshell, l = 0 and m = 0. Thus, s-
orbital with only one orientation has a spherical shape with uniform electron
density along all the three axes.
The probability of Is electron is found to be maximum near the nucleus and
decreases with the increase in the distance from the nucleus. In 2s electron, the
probability is also maximum near the nucleus and decreases to zero probability.
The spherical empty shell for 2s electron is called nodal surface or simply node.
• Shapes of p-orbitals
p-orbitals are present in the p-subshell for which l = 1 and m 1 can have three
possible orientations – 1, 0, + 1.
Thus, there are three orbitals in the p-subshell which are designated as p x, py and
pz orbitals depending upon the axis along which they are directed. The general
shape of a p-orbital is dumb-bell consisting of two portions known as lobes.
Moreover, there is a plane passing through the nucleus along which finding of
the electron density is almost nil. This is known as nodal plane as shown in the
fig.

From the dumb-bell pictures, it is quite obvious that unlike s-orbital, a p-orbital is
directional in nature and hence it influences the shapes of the molecules in the
formation of which it participates.
• Shapes of d-orbitals
d-orbitals are present in d-subshell for which l = 2 and m[ = -2, -1, 0, +1 and +2.
This means that there are five orientations leading to five different orbitals.
Difference between Orbit and Orbital

Electronic Configuration
Arrangement of electrons in the space around nucleus in an atom known as electronic
configuration

Pauli’s Exclusion Principle

It states, no two electrons in an atom can have identical set of four quantum numbers.
The maximum number of electrons in s subshell is 2, p subshell is 6, d subshell is 10 and f
subshell is 14.

Aufbau Principle
According to this principle, in the ground state of an atom, the electrons occupy the lowest
energy orbitals available to them, i.e., the orbitals are filled in order of increasing value of n
+ l. For the orbitals having the same value of n + 1, the orbital having lower value of n is
filled up first.
The general order of increasing energies of the orbital is

The energy of atomic orbitals for H-atom varies as

Is < 2s = 2P < 3s 3p = 3d < 4s = 4P = 4d = 4f
Half-filled and completely filled electronic configurations are more stable Hence. outer
configuration of Cr is 3d5 4s1 and Cu is 3d10 4s1.
The order may be remembered by using the method given in fig. 2.11.

Hund’s Rule of Maximum Multiplicity

It states
(i) In an atom no electron pairing takes place in the p, d and f orbital until each orbital of the
given subshell contains one electron.
(ii) The unpaired electrons present in the various orbitals of the same subshell should have
parallel spins.

Methods of Writing Electronic Configuration

(i) Orbital method: In this, the electrons present in respective orbitals are denoted. e.g Cl
(17) = 1s2, 2s2, 2 p6, 3s2, 3p5.
(ii) Shell method: In this, the number of electrons in each shell is continuously written. e.g.,
Cl (17) =

(iii) Box method: In this method, each orbital is denoted by a box and electrons are
represented by half-headed (↑) or full-headed (↑) arrows. An orbital can occupy a
maximum of two electrons.
e.g.,
Electronic Configuration of Ions
To write the electronic configuration of ions. first write the electronic configuration of
neutral atom and then add (for negative charge) or remove (for positive charge) electrons in
outer shell according to the nature and magnitude of charge present on the ion. e.g:
O (Z= 8) : 1s2, 2s2 2 p4
O-2 (10) = 1s2, 2s2 2 p6

Causes of Stability of Completely Filled and Half Filled Subshells

The completely filled and half filled subshells are stable due to the following
reasons:

1. Symmetrical distribution of electrons: The completely filled or half filled

subshells have symmetrical distribution of electrons in them and are therefore
more stable.
2. The stabilizing effect arises whenever two or more electrons with same spin
are present in the degenerate orbitals of a subshell. These electrons tend to
exchange their positions
and the energy released due to their exchange is called exchange energy. The
number of exchanges that can takes place is maximum when the subshell is
either half filled or completely filled.
-As a result the exchange energy is maximum and so is the stability.

Different Types of Atomic Species

(a) Isotopes Species with same atomic number but different mass number are called
isotopes, e.g. , 1H1, 1H2.
(b) Isobars Species with same mass number but different atomic number are called isobars.
e.g., 18Ar40, 19K40.
(c) Isotones Species having same number of neutrons are called isotones,
e.g., 1H3 and 2He4 are isotones.
(d) Isodiaphers Species with same isotopic number are called Isodiaphers, e.g., 19K39, 9F19
Isotopic number = mass number – 2 * atomic number .
(e) Isoelectronic Species with same number of electrons are called isoelectronic species,
e.g., Na+, Mg2+.
(f) Isostere Species having same number of atoms and same number of electrons, are called
isostere, e.g., N2 and CO.