2.

STRUCTURE OF AN ATOM
Bohr’s model:
Bohr’s model for hydrogen atom is based on the following postulates:
1. The electron in the hydrogen atom can move around the
nucleus in a circular path of fixed radius and energy. These
paths are called orbits, stationary states or allowed energy
states. These orbits are arranged concentrically around the
nucleus.

2. The energy of an electron in the orbit does not

change with time. However, the electron will move
from a lower stationary state to a higher stationary
state when required amount of energy is absorbed by
the electron or energy is emitted when electron moves
from higher stationary state to lower stationary state.
3. The frequency of radiation absorbed or emitted
when transition occurs between two stationary states
that differ in energy by ∆E, is given by:
E = E2 - E1
∆E
V=
h
Where E1 and E2 are the energies of the lower and
higher energy states respectively
This expression is commonly known as Bohr’s
frequency rule.

4. The angular momentum of an electron in a given stationary state can be expressed

as
nh
mvr =
2π
Thus an electron can move only in those orbits
for which its angular momentum is
integral multiple of h/2p that is why only certain
fixed orbits are allowed.
According to Bohr’s theory for hydrogen atom:
a) The stationary states for electron are numbered n = 1, 2, 3.......... These numbers are
called as Principal quantum numbers.
b) The radii of the stationary states are expressed as:
rn = n2 a0
Where a0 = 52.9 pm.
Thus the radius of the first stationary state,
called the Bohr orbit, is 52.9 pm.
c) The energy of its stationary state is given by the
expression.
1
En = -RH*
n2
n = 1,2,3…….
Where RH is called Rydberg constant and its value is 2.18×10–18 J.
d) Bohr’s theory can also be applied to the ions containing only one electron. For
example, He+ Li2+, Be3+ etc. The energies of the stationary states of ions (also known as
hydrogen like species) are given by the expression.
and radii by the expression

Where Z is the atomic number and has values 2, 3 for the helium and lithium atoms
respectively. From the above equations, it is evident that the value of energy becomes
more negative and that of radius becomes smaller with increase of Z. This means that
electron will be tightly bound to the nucleus.
Derivation of angular momentum of an electron:
According to de Broglie concept, the electron is not only a particle but has a wave
character also. If the wave is completely in phase, the circumference of the orbit must
be equal to an integral multiple of wave length (λ)
Therefore 2πr = n λ
where ‘n’ is an integer and ‘r’ is the radius of the orbit
But λ = h/mv
Therefore 2πr = nh /mv
(or) mvr = n h/2π
Limitations of Bohr’s theory
i) It does not explain the spectra of atoms having more than one electron.
ii) Bohr’s atomic model failed to account for the effect of magnetic field (Zeeman effect)
or electric field (Stark effect) on the spectra of atoms or ions. It was observed that when
the source of a spectrum is placed in a strong magnetic or electric field, each spectral
line further splits into a number of lines. This observation could not be explained on
the basis of Bohr’s model.
iii) De Broglie suggested that electrons like light have dual character. It has particle and
wave character. Bohr treated the electron only as particle.
iv) Another objection to Bohr’s theory came from Heisenberg’s Uncertainty Principle.
According to this principle “It is impossible to determine simultaneously the exact
position and momentum of a small moving particle like an electron”. The postulate of
Bohr, That electrons revolve in well defined orbits around the nucleus with well defined
velocities is thus not tenable.
e) It is also possible to calculate the velocities of electrons moving in these orbits.
Although the precise equation is not given here, qualitatively the magnitude of velocity
of electron increases with increase of positive charge on the nucleus and decreases with
increase of principal quantum number.

Dual Behaviour of Matter: The French physicist, de Broglie in 1924 proposed that the
photon has momentum as well as wavelength, electrons should also have momentum
as well as wavelength, de Broglie, from this analogy, gave the following relation
between wavelength (l) and momentum (p) of a material particle.
h h
λ= =
mv p
Where m is the mass of the particle, v its velocity and p its momentum
De Broglie’s prediction was confirmed experimentally when it was found that an
electron beam undergoes diffraction, a phenomenon characteristic of waves.
Derivation of de-Broglie equation
In case of photon, if it is assumed to have wave character, its energy is given by
E = h𝜗 ------------------ (i) (according to the Planck’s quantum theory)
Where 𝜗 is the frequency of the wave and ‘h’ is Planck’s constant
If the photon is supposed to have particle character, its energy is given by
E = mc2 ------------------ (ii) (according to Einstein’s equation)
Where ‘m’ is the mass of photon, ‘c’ is the velocity of light.
By equating (i) and (ii)
h𝜗 = mc2
hc
λ
= mc2
λ=
h
mc

Heisenberg’s Uncertainty Principle:

It states that it is impossible to determine simultaneously, the exact position and exact
momentum (or velocity) of an electron. Mathematically, it can be given as in Equation.
h
Δx*Δp ≥ 4π
h
Δx*Δ(mv) ≥ 4π
h
Δx*mΔv ≥ 4π
h
Δx*Δv ≥ 4πm
Where h is Planck's
constant, Δx is the
uncertainty in position and Δp or Δvx is the uncertainty in momentum (or velocity) of
the particle.
(i) When ∆x = 0, ∆v = ∞
(ii) When ∆v = 0, ∆x = ∞ So, if the position is known quite accurately, i.e., ∆x is very
small, ∆v becomes large and vice-versa.
If the position ofthe electron is known with high degree of accuracy (Δx is small), then
the velocity of the electron will be uncertain [Δ (vx) is large]. the other hand, if the
velocity of the electron is known precisely (Δ (vx ) is small), then the position of the
electron will be uncertain (Δx will be large).
Significance of Uncertainty Principle:
The effect of Heisenberg Uncertainty Principle is significant only for motion of
microscopic objects and is negligible for that of macroscopic objects. This can be seen
from the following examples. If uncertainty principle is applied to an object of mass, say
about a milligram (10–6 kg), then
h
Δx*Δv ≥ 4πm

The value of Δv*Δx obtained is extremely small and is insignificant. In the case of a
microscopic object like an electron on the other hand, Δv*Δx obtained is much larger
and such uncertainties are of real consequence. For example, for an electron whose
mass is 9.11×10–31 kg., according to
Heisenberg uncertainty principle
h
Δx*Δv ≥ 4πm

It, therefore, means that if one tries to find the exact location of the electron, say to an
uncertainty of only 10–8 m, then the uncertainty Δv in velocity would be

It, therefore, means that the precise statements of the position and momentum of
electrons have to be replaced by the statements of probability.
Quantum mechanical model of an atom:
The atomic model which is based on the particle and wave nature of the electron is
known as wave or quantum mechanical model of the atom. This was developed by Ervin
Schrodinger in 1926. This model describes the electron as a three dimensional wave in
the electronic field of positively charged nucleus. Schrodinger derived an equation
which describes wave motion of an electron. The differential equation is

Where x, y, z are certain coordinates of the electron, m = mass of the electron E = total
energy of the electron. V = potential energy of the electron; h = Planck’s constant and Ψ
(psi) = wave function of the electron.
Significance of Ψ: The wave function may be regarded as the amplitude function
expressed in terms of coordinates x, y and z. When the equation is solved, it is observed
that for some regions of space the value of Ψ is negative. But the probability must be
always positive and cannot be negative, it is thus, proper to use Ψ2 in favour of Ψ.
Significance of Ψ2: Ψ2 is a probability factor. It describes the probability of finding an
electron within a small space. The space in which there is maximum probability of
finding an electron is termed as orbital. The important point of the solution of the wave
equation is that it provides a set of numbers called quantum numbers which describe
energies of the electron in atoms, information about the shapes and orientations of the
most probable distribution of electrons around nucleus.
QUANTUM NUMBERS:
To obtain complete information about an electron in an atom 4 identification numbers
are required and these identification numbers are called as quantum numbers.
(a) Principal quantum number (n)→Shell (Orbit)
(b) Azimuthal quantum number (l) → Sub shell
(c) Magnetic quantum number (m) → Orbital
(d) Spin quantum number (s) → Spin of electron.
(a) Principal Quantum Number (n):
Given By → Bohr
1. It represents the name and energy of the shell and size of orbital.
2. The value of n lies between 1 to ∞
i.e n = 1,2,3,4– – – – –∞ corresponding name of shells are K, L, M, N, O, – – – –
3. Greater the value of n, greater is the distance from the nucleus.
 r1 < r2 < r3 < r4 < r5 – – – – – – – –
4. Greater the value of n, greater is the energy of shell

E1 < E2 < E3 < E4 – – – – – – – –

5. Velocity of electron v = 2.18*106*Z/n m/s.
v1 > v2 > v3 --------
6. The angular momentum of a revolving electron is
mvr = nh/2π
Where n = Principal quantum number.
7. The number of electrons in a particular shell is equal to 2n2.
(b) Azimuthal quantum number / Angular quantum number / Secondary quantum
number / Subsidiary quantum number (l)
1. Given by → Sommerfeld
2. It represents the name of the subshell, shape of orbital and orbital angular
momentum
3. Possible values of 'l' are :- i.e l = 0,1,2 – – – – – – – – – (n–1)
l = 0(s Subshell)
l = 1(p Subshell)
l = 2(d Subshell)
l = 3(f Subshell)
4. Value of l lies between 0 to (n – 1) in a particular nth shell:-
Ex: If n = 1 then l = 0 → 1s i.e. in n =1 shell, only one sub-shell's' is present.
If n = 2 then l = 0, 1 → 2s, 2p i.e. in n =2 shell, two sub-shell 's' & 'p' are present.
If n = 3 then l = 0, 1, 2 → 3s, 3p, 3d i.e. in n =3 shell, three sub-shell 's' , 'p' & 'd' are
present.
If n = 4 then l = 0,1,2,3 → 4s,4p, 4d, 4f i.e. in n =4 shell, four subshell 's' , 'p' ,'d' &
'f' are present.
5. If the value of n is same then the order of energy of the various sub-shell will be
s < p < d < f [valid only for multi-electron species]
Ex. 4s < 4p < 4d < 4 f, 3s < 3p< 3d, 2s < 2p
6. If Value of l is same but value of n is different then the order of energy will be.
Ex. 1s < 2s < 3s < 4s < 5s < 6s
3d < 4d < 5d < 6d
4p < 5p <6p
7. The orbital angular momentum = √𝑙(𝑙 + 1) h/2π
Orbital angular momentum: For s subshell = 0
For p subshell = √2 h/2π
8. The number of electrons in a particular subshell is equal to 2(2l +1)
 For s subshell number of electrons = 2 e-
 For p subshell number of electrons = 6 e-
 For d subshell number of electrons = 10 e-
 For f subshell number of electrons = 14 e-
 Shape of the orbital : s → spherical
p → dumb bell shape
d → double dumb bell shape
f → complex shape
(c) Magnetic Quantum Number /Orientation Quantum Number (m):
1. Given by Lande
2. It represents the orientation of electron cloud (orbital)
3. Under the influence of magnetic field each subshell is further subdivided into
orbitals (The electron cloud is known as orbital)
Magnetic quantum number describes these different distributions of electron cloud.
4. Value of m = all integral value from – l to + l including zero. i.e. Value of m = – l to + l
Orbital: 3D space around the nucleus where the probability of finding electrons is
maximum is called an orbital. An orbital can be represented by = Ψn,l,m
Ex. 1: 2px; n=2, l=1, m=–1 or m=+1
Ex. 2: 3dz2; n=3, l=2, m=0
Ex. 3: Ψ3,2,0; n=3, l=2, m=0; 3dz2

Node: It is point /line / plane / surface in which probability of finding electron is zero.
Total numbers of nodes = n-1
They are of 2 types.
(i) Radial nodes / Spherical nodes / Nodal surface
Number of radial nodes =n-l-1
(ii) Angular nodes / Nodal planes
Number of angular nodes /nodal planes=l
* Nucleus and∞ (infinite) are not considered as node.
Types of orbitals:
Case-I: If l = 0 then m = 0, it implies that s sub-shall has only one orbital called as s
orbital.
Shapes of s-orbitals:
The s-orbitals are spherically
symmetrical about the nucleus, i.e.,
the probability of finding electron is
same in all directions from nucleus.

Case-II: If l = 1 ( p - subshell) then m = -1(px), 0(py), +1(pz)

It implies that, p subshell have three orbitals called as px, py and pz.
Shape of p-orbitals:
Three p-orbitals possess equivalent energy and therefore, have same relation with the
nucleus. They, however, differ in their direction & distribution of the charge.
These three p-orbitals are situated at right angle to one another and are directed along
x, y and z axis.
Each p orbital has dumb bell shape (2 lobes which are separated from each other by a
point of zero probability called nodal point or node or nucleus).
Case III: When l = 2, 'm' has five values – 2, –1, 0, +1, +2. It implies that d subshell of
any energy shell has five orbitals. All the five orbitals are not identical in shape. Four of
the d orbitals dxy, dyz, dxz, dx2-y2, contain four lobes while fifth orbital dZ2 consists of only
two lobes. Geometry of d orbital is double dumbbell.
Shape of d–orbitals:

Case III: When l = 3, 'm' has seven values -3, – 2, –1, 0, +1, +2,+3. It implies that f
subshell of any energy shell has seven orbitals. Each orbital can accomodate 2
electrons with opposite spin or spin paired. f-subshell have complex shape. Seven
different spatial orientations (ml = 3, 2, 1, 0, 1, 2, 3)

(d) Spin Quantum number (s):

1. Given by Goudsmit and Uhlenbeck
2. It represents the direction of electron spin
around its own axis
1
3. For clockwise spin/spin up(↑ ) electron → ± 2
1
4. For anti-clockwise spin/spin down(↓) electron → ± 2
5. Spin angular momentum of an electron = √𝑠(𝑠 + 1) h/2π

RULES FOR FILLING OF ELECTRONS

(a) Aufbau Principle (b) (n +l) rule
(c) Hund's maximum multiplicity principle (d) Pauli's exclusion principle
(a) Aufbau Principle:
Aufbau is a German word and its meaning is
'Building up'
Principle: The subshell with minimum energy
is filled up first when this subshell obtained
maximum quota of electrons then the next
subshell of higher energy starts filling.
The sequence in which various subshell are
filled are as follows.

1s2, 2s2, 2p6, 3s2, 3p6, 4s2, 3d10, 4p6, 5s2, 4d10, 5p6, 6s2, 4f14, 5d10, 6p6,7s2, 5f14, 6d10....
(b) (n + l) Rule (For multi electron species):
Principle of (n+l) rule:
The subshell with lowest (n+l) value is filled up first. When two or more subshell have
same (n+l) value then the subshell with lowest value of n is filled up first.
Type of Value of n Values of l Values of (n+ l) Relative
orbitals energy
1s 1 0 1+0=1 Lowest energy
2s 2 0 2+0=2 Higher energy
than 1s orbital
2p 2 1 2+1=3 2p orbital (n=2)
have lower
energy than 3s
orbital (n=3)
3s 3 0 3+1=3

Order: 1s2, 2s2, 2p6, 3s2, 3p6, 4s2, 3d10, 4p6, 5s2, 4d10, 5p6, 6s2, 4f14, 5d10, 6p6,7s2, 5f14,
6d10, 6p6,7s2, 5f14, 6d10 ....
(c) Hund's Maximum Multiplicity Rule: (Multiplicity: Many of the same kind)
1. This rule deals with the filling of electrons into the orbitals belonging to the same
subshell (that is, orbitals of equal energy, called degenerate orbitals).

2. It states: pairing of electrons in the orbitals of the same subshell (p, d or f) does not
take place until each orbital of that subshell has got one electron each.

3. Since there are three p, five d and seven f orbitals, therefore, the pairing of electrons
will start in the p, d and f orbitals with the entry of 4th, 6th and 8th electron,
respectively.
(d) Pauli's Exclusion Principle:
In 1925 Pauli stated that no two electron in an atom can have same values of all four
quantum numbers
i.e., an orbital can accommodate maximum 2 electrons with opposite spin.

Exception of Aufbau principle :

In some cases it is seen that
the electronic configuration is
slightly different from the
arrangement given by Aufbau
principle. A simple reason
behind this is that half filled &
full filled subshell have got
extra stability.

PREPARED BY
RAJESH MANDE,
PGT CHEMISTRY,
K V ONGOLE.