STRUCTURE OF ATOM

Electron, proton and neutron; Constitution of nucleus, Properties of alpha, beta and
gamma rays; Rutherford’s scattering experiment; Bohr’s atomic model (mathematical
details excluded); Quantum numbers; Pauli’s exclusion principle; Hund’s rule; Aufbau
principle; Electronic configuration of elements (upto atomic number 36); Shapes of s, p,
and d–orbitals.

CONTENTS INTRODUCTION
 Dalton’s Theory of atom The classical view of atomic structure was
 Subatomic particles constructed with the body of knowledge
accumulated in physics over several
 Various atomic models
centuries. We begin with the focus on
 Photoelectric effect atomic nucleus with its protons and
 Particles & wave nature of electron neutron. This includes obtaining atomic
masses and atomic number. Electrons are
 Heisenberg uncertainty principle
at the heart of our modern view of atomic
 Schrodinger wave equation structure.
 Quantum numbers This chapter, firstly provides experimental
 Rules for filling electrons evidence for the picture of atom. After that
it deals with nature of light and finally
 Shapes and size of orbitals
explains the behaviour of electrons in
 Quantum mechanical treatment of atoms leading to the modern view of atomic
H–atom structure.

1
 Chemistry : Structure of Atom

1. DALTON’S THEORY OF ATOM

In 1807, John Dalton developed his atomic theory. According to this theory :
 An atom cannot be subdivided.
 Atoms are neither created nor destroyed during chemical reactions.
 Atoms of the same element are alike; in particular all atoms of an element have the
same mass.
 Atoms of different elements are not alike; in particular, their masses are different.

1.1 REASON FOR FAILURE OF DALTON’S THEORY

In 1833, Michael Faraday showed that there is a relationship between matter and electricity.
This was the first major break through to suggest that atom was not a simple indivisible
particle of all matter but was made up of small particles. Discovery of electrons, protons and
neutrons discarded the indivisible nature of atom proposed by John Dalton.

2. SUBATOMIC PARTICLES
The researches done by various eminent scientists and the discovery of radioactivity have
established beyond doubt, that atom is not the smallest indivisible particle but had a
complex structure of its own and was made up of still smaller particles like electrons,
protons, neutrons etc. At present about 35 different subatomic particles are known but the
three particles namely electron, proton and neutron are regarded as the fundamental
particles.
We shall now take up the brief study of these fundamental particles.

2.1 CATHODE RAYS (DISCOVERY OF ELECTRON)

Gases are normally poor conductor of electricity at ordinary or high pressure. However
when a tube filled with a gas is evacuated to a pressure of 0.01 mm Hg or lower and an
electric potential is applied across a pair of electrodes into the tube discharge takes place
between the electrodes during which a stream of rays moves from cathode to anode,
William Crookes (1879) called these rays as cathode rays.

2.1a PROPERTIES OF CATHODE RAYS

1. Cathode rays travel in straight lines with a high speed approaching to that of light.
Their linear propagation is shown by the fact that they caste shadows of the solid
objects placed in their path.
2. They produce temperature rise in any object they strike.
3. They pass through thin films of metals but are stopped by thicker foils.
4. Cathode rays can produce mechanical effect e.g. when allowed to fall on a small
paddle wheel they cause rotation of wheel. This experiment shows that cathode rays
consist of material particles.
5. The cathode rays can be deflected by electric and magnetic field. The direction of
deflection is always such that these particles bear a negative charge.
 6. Finally no matter what the nature of the cathode or the gas in the discharge tube, the
negatively charged particles are always the same as reflected by the same e/m ratio by
J.J. Thomson.
These particles constituting cathode rays have been named electron by J.J. Thomson. The
fact that electrons are independent of the nature of source from which they come suggest
that they are constituent of all elements.
Thomson determined e/m ratio of electrons by applying electric and magnetic field

2.1b METHOD OF EXPERIMENTAL DETERMINATION OF E/M

Tube was evacuated
through here and then
sealed off. Anode + Scale pasted on outside of tube
(metal plugs with slits) to measure deflection of cathode ray
–

3 Magnetic only
1 Both or neither
2 Electric only
Cathode – Cathode ray Aluminum plates
(5 cm × 2 cm, 1.5 cm apart)
e
Determination of m ratio of electron

e
of electron = 1.7588 1011 C / kg = 1.7588 108 C / g
m

2.1C DETERMINATION OF CHARGE OF ELECTRON

An American physicist R. A. Millikan determined charge on electron by oil drop experiment
Charge on electron = 1.6022  10–19 coulombs, from the data obtained from the above two
experiments, mass of electron can be calculated.
e
m  9.1  10 –28 g
e
m
Eyepiece of ‘‘telescope’’
with three equally spaced Oil was sprayed in
crosshairs fine drops.
Air
Pinhole with cover

X-rays

‘‘Telescope’’ (low-
power magnifier)
Drop under observation
Brass plates 22 cm in
diameter and 1.6 cm apart
Determination of charge of electron

2.2 POSITIVE RAYS (ANODE RAYS) OR CANAL RAYS

Since electron is an essential constituent of atom and since atom as a whole is electrically
neutral. it follows that an equal magnitude of positive charge must be present in an atom. In
 Chemistry : Structure of Atom

1886 Goldstein discovered that not only cathode rays composed of electrons moving
towards anode are present but positive rays moving in opposite direction are also present.
By perforating the cathode these positive rays can be made to pass through the hole.

2.2a PROPERTIES OF ANODE RAYS

(i) They are deflected in electric and magnetic field just as cathode rays but in the
opposite direction showing that they consist of positively charged particles.
(ii) the charge and mass of the particles constituting anode rays vary and depend upon the
nature of gas contained in the discharge tube.
(iii) Positive rays are not emitted by anode but originate between the electrodes from the
ionization of gas atoms.
The mass of positively charged particle is virtually the same as that of the atoms from which
they are derived, Wein (1898) determined the value of e/m for positive particles and found
that it was different for different gases. When hydrogen gas was taken in the discharge tube,
the lightest positively charge particle was found. It’s mass was nearly the same as that of H
atom (1.673  10 –24 g) and carried a positive charge exactly equal and opposite to that of an
electron. This positively charged particle was named proton.

2.3 DISCOVERY OF NEUTRON

The electrically neutral charge particle, neutron was discovered by James Chadwick by
bombarding boron or beryllium with  -particles.
9
4 Be  42 He 
 12 1
6 C  0n

2.4 CHARACTERISTICS OF THE THREE FUNDAMENTAL PARTICLES ARE

Electron Proton Neutron
Symbol e or e –1 P n
Approximate relative mass 1/1836 1 1
Approximate relative charge –1 +1 No charge
–31 –27
Mass in kg 9.109 10 1.673 10 1.675  10 –27
Mass in amu 5.485 10 –4 1.007 1.008
Actual charge (coulomb) 1.602 10 –19 1.602 10 –19 0
Actual charge (e.s.u.) 4.8 10 –10 4.8 10 –10 0

3. VARIOUS ATOMIC MODELS

3.1 THOMSON’S MODEL
Based on these discoveries J.J. Thomson proposed the Plum Pudding Model. This model
proposed that atoms are blobs of a positively charged jelly like material, with electrons
suspended in it like raisins in a pudding.
3.2 RUTHERFORD’S MODEL
Rutherford allowed a narrow beam of –particles to fall on a very thin gold foil (thickness
= 4 × 10–4 cm) and

he observed
(i) Majority of the  -particles pass straight through the gold strip with little or no
deflection.
(ii) Some -particles are deflected from their path and diverge.
(iii) Very few -particles are deflected backwards through angles greater than 90°.
(iv) Some were even scattered in the opposite direction at an angle of 180° [Rutherford was
very much surprised by it and remarked that "It was as incredible as if you fired a 15
inch shell at a piece of tissue paper and it came back and hit you"].

3.2a CONCLUSIONS
1. The fact that most of the  particles passed straight through the metal foil indicates the
most part of the atom is empty.
2. The fact that few  particles are deflected at large angles indicates the presence of a
heavy positively charged body i.e., for such large deflections to occur  -particles must
have come closer to or collided with a massive positively charged body, and he named
it nucleus.
3. The fact that one in 20,000 have deflected at 180° backwards indicates that volume
occupied by this heavy positively charged body is very small in comparison to total
volume of the atom.

3.2b ATOMIC MODEL

Rutherford proposed an atomic model as follows.
(i) All the protons (+ve charge) and the neutrons (neutral charge) i.e. nearly the total mass
of an atom is present in a very small region at the centre of the atom. The atom's
central core is called nucleus.
 Chemistry : Structure of Atom

(ii) The size of the nucleus is very small in comparison to the size of the atom. Diameter of
the nucleus is about 10 –13 while the atom has a diameter of the order 10 –8 of cm. So,
the size of atom is 105 times more than that of nucleus.
(iii) Most of the space outside the nucleus is empty.
(iv) The electrons, equal in number to the net nuclear positive charge, revolve around the
nucleus with high speed in various circular orbits.
(v) The centrifugal force arising due to the high speed of an electron balances the
columbic force of attraction of the nucleus and the electron remains stable in its path.
Thus according to him atom consists of two parts (a) nucleus and (b) extra nuclear part.

3.2C DEFECTS OF RUTHERFORD'S ATOMIC MODEL

1. Position of electrons : The exact positions of the electrons from the nucleus are not
mentioned.
2. Stability of the atom : Neils Bohr pointed out that Rutherford's atom should be highly
unstable. According to the law of electro-dynamics, the electron should therefore,
continuously emit radiation and lose energy. As a result of this a moving electron will
come closer and closer to the nucleus and after passing through a spiral path, it should
ultimately fall into the nucleus.
It was calculated that the electron should fall into the nucleus in less than 10 –8 sec. But it is
known that electrons keep moving outsided the nucleus.
To solve this problem Neils Bohr proposed an improved form of Rutherford's atomic model.
Before going into the details of Neils Bohr model we would like to introduce you some
important atomic terms.

3.3 SOME IMPORTANT CHARACTERISTICS OF A

ELECTROMAGNETIC WAVE
A wave is a sort of disturbance which originates from some vibrating source and travels
outward as a continuous sequence of alternating crests and troughs. Every wave has five
important characteristics, namely, wavelength (), frequency (), velocity (c), wave number
   and amplitude (a).
Magnetic field
component

Direction
of
travel

Electro magnetic wave

Ordinary light rays, X–rays,–rays, etc. are called electromagnetic radiations because
similar waves can be produced by moving a charged body in a magnetic field or a magnet
in an electric field. These radiations have wave characteristics and do not require any
medium for their propagation.
 (i) Wave length () : The distance between two neighbouring troughs or crests is known
as wavelength. It is denoted by  and is expressed in cm, m, nanometers (1nm=10–9m)
or Angstrom (1Å=10–10m).
(ii) Frequency () : The frequency of a wave is the number of times a wave passes
through a given point in a medium in one second. It is denoted by (nu) and is
expressed in cycles per second (cps) or hertz (Hz) 1Hz = 1cps.
The frequency of a wave is inversely proportional to its wave length ()
1 c
 or  =
 
(iii) Velocity : The distance travelled by the wave in one second is called its velocity. It is
denoted by c and is expressed in cm sec–1.
c
c =  or  =

(iv) Wave number    : It is defined as number of wavelengths per cm. It is denoted by
 and is expressed in cm–1.
1 
= (or)  =
 c
(v) Amplitude: It is the height of the crest or depth of the trough of a wave and is denoted
by a. It determines the intensity or brightness of the beam of light.
If all the components of Electromagnetic Radiation (EMR) are arranged in order of
decreasing or increasing wavelengths or frequencies, the pattern obtained is known as
Electromagnetic Spectrum. The following table shows all the components of light.
S.No. Name Wavelength Frequency(Hz) Source
1. Radio wave 14
3 10 – 3 10 7 5
110 –110 9 Alternating current of
high frequency
2. Microwave 3 107 – 6 106 1109 – 5 1011 Klystron tube
3. Infrared (IR) 6  10 6 – 7600 5 1011 – 3.95 1016 Incandescent objects
16 14
4. Visible 7600–3800 3.95 10 – 7.9  10 Electric bulbs, sun rays
5. Ultraviolet(UV) 3800–150 7.9  1014 – 2 1016 Sun rays, arc lamps with
mercury vapours
6. X-Rays 150–0.1 2 1016 – 3  1019 Cathode rays striking
metal plate
7.  -Rays 0.1–0.01 3 1019 – 3 10 20 Secondary effect of
radioactive decay
8. Cosmic Rays 0.01–zero 3 1020 –Infinity Outer space

3.4 ATOMIC SPECTRUM

Electromagnetic spectrum consist of radiations of different wavelength and frequencies. An
instrument used to separate the radiations of different wavelength is called spectroscope or
spectrograph. It consist of a prism or diffraction grating for dispersion of radiations and a
 Chemistry : Structure of Atom

telescope to examine the emergent radiations. In spectroscope the telescope is replaced by

photographic film.
1. Emission Spectrum: When the radiation emitted from some source e.g. from the sun
or by passing electric discharge to high temperature is passed through prism and then
received on photographic plate the spectrum obtained is known as emission spectrum.
Emission spectra are as two types:
(a) Continuous Spectra : When white light from any source such as sun a bulb or hot
glowing body is analysed by passing through the prism. It is observed that it splits up
into seven different wide band of colours. These colours are so continuous that each
merges into the next. Hence spectrum is continuous spectrum.
(b) Line Spectra : When some volatile salt like NaCl is placed in Bunsen Burner or an
electric discharge is passed through a gas. Light is emitted if this light is resolved and
passed in a spectroscope. It is found that no continuous spectrum is obtained but
isolated lines are obtained. This spectrum is called line spectrum. Each line
corresponds to a wavelength.
(2) Absorption Spectra : When white light from any source is first passed through the
solution or vapours of a chemical substance and than analysed by spectroscope. It is
observed that some dark lines are obtained. These dark lines are supposed to result
from the fact that when white light is passed through chemical substance radiations of
certain wavelength are absorbed. Dark lines are obtained at same place where coloured
lines were obtained in emission spectra.

3.4a HYDROGEN SPECTRUM

If an electric discharge is passed through hydrogen gas taken in a discharge tube under low
pressure, and the emitted radiation is analysed with the help of spectrograph, it is found to
consist of a series of sharp lines in the UV, visible and IR regions. This series of lines is
known as line or atomic spectrum of hydrogen. The lines in the visible region can be
directly seen on the photographic film.
Each line of the spectrum corresponds to a light of definite wavelength. The entire spectrum
consists of six series of lines each series, known after their discoverer as the Balmer,
Paschen, Lyman, Brackett, Pfund and Humphrey series. The wavelength of all these series
can be expressed by a single formula.
1 1 1
R 2 – 2
  n1 n1 
 = wave number
 = wave length
R = Rydberg constant (109678 cm –1 )
n1 and n 2 have integral values as follows
Series n1 n2 Main spectral lines
Lyman 1 2, 3, 4, etc Ultra-vio
Balmer 2 3, 4, 5 etc Visible
Paschen 3 4, 5, 6 etc Infra-red
Brackett 4 5, 6, 7 etc Infra-red
 Pfund 5 6, 7, 8, etc Infra-red
Note : All lines in the visible region are of Balmer series but reverse is not true, i.e., all Balmer lines will not fall in
visible region
The pattern of lines in atomic spectrum is characteristic of hydrogen.

3.5 PLANCK’S QUANTUM THEORY OF RADIATION

In order to explain the spectral distribution of energy radiated by a back body. Max Planck
(1901) put forward quantum theory of radiation. According to this theory.
(i) Radiant energy is emitted or absorbed discontinuously in the form of tiny bundles or
packets known as quanta or photon.
(ii) The energy of a quantum is directly proportional to the frequency of the radiation
Ev
E = hv
v = frequency of radiation
h = planck’s constant
(iii) A body can emit or absorb energy only in whole number multiples of quantum i.e 1hv,
2hv, etc.
Energy in fractions of a quantum cannot be lost or absorbed. this is known as quantization
of energy.
Illustration 1: Calculate the frequency and wave number of radiation with wavelength
480 nm.
Solution : Given
 = 480 nm = 480 × 10–9 m [1 nm = 10–9 m]
c = 3 × 108 m/s
c 3 108 ms 1
Frequency, v   6.25 1014 s 1 = 6.25 × 1014 Hz.
 48  109
Illustration 2: Find the quantum numbers of the excited state of electrons in He+ ion which
on transition to ground state and first excited state emit two photons of
wavelengths. 30.4 nm and 108.5 nm respectively. (RH = 1.09678 × 107 m–1).
1 1 1
Solution :  R H Z2  2  2 
  n1 n 2 
n1 = 1, n2 = ?
1 1 1 
9
 1.09678  10 7  4  2  2  n2 = 2
30.4  10  11 n 2 
n1= 2 (first excited state), n2 = ?
1 1 1
9
 1.09678  107  4  2  2  n2 = 5
108.5 10 2 n2 
 Chemistry : Structure of Atom

Illustration 3: In the measurement of the quantum efficiency of photosynthesis in green

plants, it was found that 8 quanta of red light at 6850 Å were needed to
release one molecule of O2. The average energy storage in the
photosynthesis process is 112 kcal/mol O2 released. What is the energy
conversion efficiency in the photosynthetic process ?
hc
Solution : Energy possessed by one quanta, E1 

6.625  1034  3  108
= 10
 2.9  1019 J / molecule
6850  10
Average energy storage in photosynthesis = 112 kcal/mol
112  103  4.2
=  7.81  10 19 J / molecule
6.023  10 23
Average energy storage
Energy conversion efficiency =  100
Energy of 8 quanta

7.81 10 19

=  100  33.66%
8  2.9  10 19

EXERCISE – 1
1. Calculate the energy associated with photon of light having a wavelength 6000 Å.
2. How many photons of light having a wavelength 4000 Å are necessary to provide 1.00
J of energy?
3. How many moles of photon would contain sufficient energy to raise the temperature of
225 g of water 21°C to 96°C? Specific heat of water is 4.18 J g–1 K–1 and frequency of
light radiation used is 2.45 × 109 s–1.

3.6 BOHR’S ATOMIC MODEL

Bohr developed a model for hydrogen and hydrogen like atoms one-electron species
(hydrogenic species). He applied quantum theory in considering the energy of an electron
bond to the nucleus.

3.6a IMPORTANT POSTULATES

An atom consists of a dense nucleus situated at the center with the electron revolving around
it in circular orbits without emitting any energy. The force of attraction between the nucleus
and an electron is equal to the centrifugal force of the moving electron.
Of the finite number of circular orbits possible around the nucleus, and electron can revolve
only in those orbits whose angular momentum (mvr) is an integral multiple of factor h/ 2 .
 nh
mvr 
2
where, m = mass of the electron
v = velocity of the electron
n = orbit number in which electron is present
r = radius of the orbit
As long as an electron is revolving in an orbit it neither loses nor gains energy. Hence these
orbits are called stationary states. Each stationary state is associated with a definite amount
of energy and it is also known as energy levels. The greater the distance of the energy level
from the nucleus, the more is the energy associated with it. The different energy levels are
numbered as 1, 2, 3, 4, (from nucleus onwards) or K, L, M,N etc.
Ordinarily an electron continues to move in a particular stationary state without losing
energy. Such a stable state of the atom is called as ground state or normal state.
If energy is supplied to an electron, it may jump (excite) instantaneously from lower energy
(say 1) to higher energy level (say 2, 3, 4, etc) by absorbing one quantum of energy. This
new state of electron is called as excited state. The quantum of energy absorbed is equal to
the difference in energies of the two concerned levels.
Since the excited state is less stable, atom will lose it’s energy and come back to the ground
state.
Energy absorbed or released in an electron jump, (E) is given by
E  E 2 – E1  hv
Where E 2 and E1 are the energies of the electron in the first and second energy levels, and
v is the frequency of radiation absorbed or emitted.

Note: If the energy supplied to hydrogen atom is less than 13.6 eV, it will accept or absorb only those
quanta which can take it to a certain higher energy level i.e., all those photons having energy less
than or more than a particular energy level will not be absorbed by hydrogen atom. But if energy
supplied to hydrogen atom is more than 13.6 eV then all photons are absorbed and excess
energy appear as kinetic energy of emitted photo electron.

3.6b MERITS OF BOHR’S THEORY

(i) The experimental value of radii and energies in hydrogen atom are in good agreement
with that calculated on the basis of Bohr’s theory.
(ii) Bohr’s concept of stationary state of electron explains the emission and absorption
spectra of hydrogen like atoms.
(iii) The experimental values of the spectral lines of the hydrogen spectrum are in close
agreement with the calculated by Bohr’s theory.

3.6C LIMITATIONS OF BOHR’S THEORY

(i) It does not explain the spectra of atoms or ions having more than one electron.
 Chemistry : Structure of Atom

(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 attainable.

3.6d BY BOHR’S THEORY

(i) Radius and Energy levels of hydrogen atom: Consider an electron of mass `m’ and
charge `e’ revolving around a nucleus of charge Ze (where, Z = atomic number and e is
the charge of the proton) with a tangential velocity v.r is the radius of the orbit in
which electron is revolving.
By Coulomb’s Law, the electrostatic force of attraction between the moving electron
KZe2
and nucleus is Coulombic force  2
r
1
K (where 0 is permitivity of free space)
4 0
K  9  109 Nm 2 C –2
In C.G.S. units, value of K = 1 dyne cm 2 (esu) –2
mv 2
The centrifugal force acting on the electron is
r
Since the electrostatic force balance the centrifugal force, for the stable electron orbit.
mv2 KZe 2
 2 … (i)
r r
KZe2
(or) v2  … (ii)
mr
According to Bohr’s postulate of angular momentum quantization, we have
nh
mvr 
2
nh
v
2mr
n 2h 2
v2  … (iii)
4 2 m 2 r 2
Equating (2) and (3)
 KZe 2 n 2h 2
 2 2 2
mr 4 m r
n 2h 2
Solving for r we get r 
42 mKZe 2
where n = 1, 2, 3, … 
Hence only certain orbits whose radii are given by the above equation are available for
the electron. The greater the value of n, i.e., farther the level from the nucleus the
greater is the radius.
The radius of the smallest orbit (n = 1) for hydrogen atom (Z = 1) is r0 .
n2h 2 12  (6.626 10 –34 ) 2
r0    5.29 10 –11 m
42 me 2K 4  (3.14)2  9 10 –31  (1.6 10 –19 )2  9 109
r0  0.5629Å
Radius of nth orbit for an atom with atomic number Z is simply written as
n2 n2
rn  r0  0.529  Å
z z
(ii) Energy level of Hydrogen atom: The total energy, E of the electron is the sum of
kinetic energy and potential energy. Kinetic energy of the electron = 1 2 mv 2
–KZe 2
Potential energy 
r
KZe2
Total energy  1 2 mv 2 – … (iv)
r
From equation (1) we know that
mv2 KZe 2
 2
r r
KZe2
 1
2 mv2 
2r
Substituting this in equation (iv)
KZe 2 KZe2 KZe 2
Total energy (e)  – –
2r r 2r
1
KE  – PE, KE  –TE
2
Substituting for r, gives us
22 mZe2e4 K 2
E where n = 1, 2, 3, …
n 2h2
This expression shows that only certain energies are allowed to the electron. Since this
energy expression consists so many fundamental constant, we are giving you the
following simplified expressions.
 Chemistry : Structure of Atom

Z2
E  –21.8 10 –12  erg per atom.
n2
Z2 Z2
 – 21.8  10 –19  J per atom = – 13.6  eV per atom
n2 n2
z2
E n  –13.6 eV per atom
n2
(1eV = 3.83 10 –23 Kcal)
(1eV = 1.602 10 –12 erg)
(1eV = 1.602 10 –19 J)
Z2
E  –313.6  kcal/mole (1 cal = 4.18 J)
n2
The energies are negative since the energy of the electron in the atom is less than the
energy of a free electron (i.e., the electron is at infinite distance from the nucleus)
which is taken as zero. The lowest energy level of the atom corresponds to n = 1, and
as the quantum number increases, E become less negative.
When n =  , E = 0 which corresponds to an ionized atom i.e., the electron and nucleus
are infinitely separated.
 H   e – (ionization).
H 
(iii) Velocity of electron
nh nh
We know that, mvr  ;v
2 2mr
By substituting for r we are getting
2 KZe 2
v
nh
Z
Where excepting n and z all are constant, v = 2.18 108 cm / sec.
n
Further application of Bohr’s work was made, to other one electron species
(Hydrogenic ion) such as He and Li 2 . In each case of this kind, Bohr’s prediction of
the spectrum was correct.
(iv) Explanation for hydrogen spectrum by Bohr’s theory: According to the Bohr’s
theory electron neither emits nor absorbs energy as long as it stays in a particular orbit.
However, when an atom is subjected to electric discharge or high temperature, and
electron in the atom may jump from the normal energy level, i.e., ground state to some
higher energy level i.e., excited state. Since the life time of the electron in excited state
is short, it returns to the ground state in one or more jumps.
During each jumps, energy is emitted in the form of a photon of light of definite
wavelength or frequency. The frequency of the photon of light thus emitted depends
upon the energy difference of the two energy levels concerned ( n1 , n 2 ) and is given by
 –22 mZ e4 K 2 1 1
hv  E 2 – E1   2 – 2
h2  n 2 n1 
22 mZ 2 e4 K 2  1 1
v 3  2 – 2
h  n1 n 2 
The frequencies of the spectral lines calculated with the help of above equation are
found to be in good agreement with the experimental values. Thus, Bohr’s theory
elegantly explains the line spectrum of hydrogen and hydrogenic species.
Bohr had calculated Rydberg constant from the above equation.
C 22 mZ2e4 K 2  1 1
  3  2 – 2
 h  n1 n 2 
1 22 mZ 2 e 4 K 2 1 1
  2 – 2
 h 3c  n1 n 2 
22 me4 K 2
where 3
 1.097  10 –7 m –1 or 109678 cm –1
hc
1 1 1
i.e. Rydberg constant (R)    RZ 2  2 – 2
  n1 n 2 
  wave number.
Illustration 4: Calculate the ratio of the radius of Li+2 ion in 3rd energy level to that of He+
ion in 2nd energy level.
n2
Solution: r
z
2
r1  n1   z 2 
   
r2  n 2   z1 
n1  3
n2  2
z1  3 (for Li 2 )
z2  2 (for He )
2
r1  3   2  3
    
r2  2   3  2
Illustration 5: How far from the nucleus is the electron in a hydrogen atom if it has energy
of –0.850 eV.
Z2
Solution: En  –  21.69 10 –19
n2
 Chemistry : Structure of Atom

Z2
– 2
 21.69 10 –19  –0.85 1.6 10 –19
n
Illustration 6: Find the wavelengths of the first line of He+ ion spectral series whose
1 1
interval between extreme lines is –  2.7451104 cm –1
1 2
Solution: Extreme lines means first and last.
1 1 1 1  1 1  RZ2
–  RZ2  2 – 2–R
2
 2– 2   2
 2  n1    n1 (n1  n)  (n1  1)
109677.76  2 2
2.7451104 
(n1  1)2
(n1  1)  4
n1  3
Wavelength of first line,
1 1 1
 109677.76  22   2 – 2 
 3 4 
  4689 10–8 cm  4689Å

Illustration 7 : The velocity of electron in a certain Bohr's orbit of hydrogen atom bears the
ratio of 1 : 275 to the velocity of light
(a) What is the quantum number (n) of orbit?
(b) Calculate the wave number of radiations emitted when electron jumps
from (n+1) state to ground state
1 3 108 m/sec
Solution : Velocity of electron = velocity light  = = 1.09  106 m/sec
275 275
2 ZKe 2 2.18  106  Z
Vn = = m/sec
nh n
2.18  106
For hydrogen Vn = m/sec
n
2.18  106
 1.09  106 = n=2
n
When electron jumps from (n+1) i.e., 3 to ground state
1 1 1
 = RH =  2  2 
 1 3 
1 1 1 
 = 1.09678  107    = 9.75  102 m–1
 1 9 
Illustration 8: Two hydrogen atoms collide head on and end up with zero kinetic energy.
Each then emits a photon of wave length 121.6 nm which transition leads to
this wavelength? How fast were the hydrogen atoms travelling before
collision?
RH = 1.09678  107 m–1
MH = 1.672  10–27 Kg
Solution: As wavelength of emitted radiation is 121.6 nm, which falls in UV region of
spectrum
Therefore, n1 = 1
1 1 1 
For hydrogen atom  RH  2  2 
 1 n 
1 1 1 
 = 1.09678  107   2 
121.6  10 9 1 n 
n=2
Energy released is due to collision and all the kinetic energy released in form
of radiant energy
1 hc
mv2 =
2 
1 6.625  1034  3 108
 1.67  10–27  V2 =
2 121.6 109
 V = 4.42  104 m/sec

EXERCISE –2
1. Calculate the radii of the first two Bohr orbits of Li2+.
2. Ionisation energy of H-atom is 13.6 eV. Calculate ionization energy of He+, Li2+ and
Be3+ (all isoelectronic of H).
3. If the electron in a hydrogen atom were in the energy level with n = 3, how much
energy would be required to ionize the atom ?

4. PHOTOELECTRIC EFFECT
Emission of electrons from a metal surface when exposed to light radiations of appropriate
wavelength is called photoelectric effect. The emitted electrons are called photoelectrons.
Work function or threshold energy may be defined as the minimum amount of energy
required to eject electrons from a metal surface.
According to Einstien,
Maximum kinetic energy of the ejected electron = absorbed energy – work function

1 2 1 1 
2 mv max  hv  hv0  hc   
  0 
 Chemistry : Structure of Atom

where v0 and 0 are threshold frequency and threshold wavelength.

4.1 LAWS OF PHOTOELECTRIC EFFECT

(i) Rate of emission of photoelectrons from a metal surface is directly proportional to the
intensity of incident light.
(ii) The maximum kinetic energy of photoelectrons is directly proportional to the
frequency of incident radiation; moreover, it is independent of the intensity of light
used.
(iii) There is no time lag between incidence of light and emission of photoelectrons.
(iv) For emission of photoelectrons, the frequency of incident light must be equal to or
greater than the threshold frequency.
Illustration 9 : Photo - electrons are liberated by ultraviolet light of wavelength 3000Å from
a metallic surface for which the photoelectric threshold is 4000Å. Calculate
de-Broglie wavelength of electrons emitted with maximum kinetic energy
hc hc
Solution: As,  = h° + KE    K.E
 o
1 1  hc(   o )
 .E. = hc   o   =
   
6.625  10 34  3  108 (4000  10 10  3000  10 10 )

3000  10 10  4000  10 10
6565  10–19 Joule
1
Also m2 = 1.6565  10–19
2
 m2v2 = 2  1.65665  10–19  m
 v2 = 2  1.6565  10–19  9.109  10–31  m = 5.49  10–25
h 6.625  10 34
=  = 1.2  10–9 m
mv 5.49  1025
Illustration 10 : Photo - electrons are liberated by ultraviolet light of wavelength 3000Å from
a metallic surface for which the photoelectric threshold is 4000Å. Calculate
de-Broglie wavelength of electrons emitted with maximum kinetic energy
hc hc
Solution: As, h = h° + KE    K.E
 o
1 1  hc(   o )
 K.E. = hc   o   =
   
6.625 1034  3  108 (4000  10 10  3000  10 10 )
=
3000  10 10  4000  1010
=1.6565  10–19 Joule
1
Also m2 = 1.6565  10–19
2
  m2v2 = 2  1.65665  10–19  m
 m2v2 = 2  1.6565  10–19  9.109  10–31
 m = 5.49  10–25
h 6.625  10 34
=  = 1.2  10–9 m
mv 5.49 1025

5. PARTICLE AND WAVE NATURE OF ELECTRON

In 1924, de Broglie proposed that an electron, like light, behaves both as a material particle
and as a wave. This proposal gave birth to a new theory known as wave mechanical theory
of matter. According to this theory, the electrons, protons and even atoms, when in motion,
possess wave properties.
de Broglie derived an expression for calculating the wavelength of the wave associated with
the electron.
According to Planck’s equation
c
E  hv  h  …(i)

The energy of a photon on the basis of Einstein’s mass–energy relationship is
E = mc2 …(ii)
where c is the velocity of the electron.
Equating both the equations, we get
c
h  mc2

h h
 
mc p
Momentum of the moving electron is inversely proportional to its wavelength.
Let kinetic energy of the particle of mass ‘m’ is E.
E = ½ mv2
2Em = m2v2
2Em = mv = p (momentum)
h h
 
p 2Em

5.1 DAVISSON AND GERMER MADE THE FOLLOWING MODIFICATION IN DE

BROGLIE EQUATION
Let a charged particle say an electron be accelerated with a potential of V; then the kinetic
energy may be given as :
½mv2 = eV
 Chemistry : Structure of Atom

m2v2 = 2eVm
mv  2eVm  p
h

2eVm
de Broglie waves are not radiated into space, i.e. they are always associated with electron.
The wavelength decreases if the value of mass (m) increases, i.e., in the case of heavier
particles, the wavelength is too small to be measured. de Broglie equation is applicable in
the case of smaller particles like electron and has no significance for larger particles.

5.2 BOHR’S THEORY VERSUS DE BROGLIE EQUATION

One of the postulates of Bohr’s theory is that angular momentum of an electron is an
h
integral multiple of . This postulate can be derived with the help of de Broglie concept
2
of wave nature of electron.
Consider an electron moving in a circular orbit around nucleus. The wave train would be
associated with the circular orbit as shown in figure.

(a) (b)
(a) The number of waves around the orbit
is a whole number (6) times the wavelength.
(b) The number of waves around the orbit is not
a whole number multiple of the wavelength.
When the wave goes around the orbit many times,
it cancles itself out.
If the two ends of the electron wave meet to give a regular series of crests and troughs, the
electron wave is said to be in phase, i.e., the circumference of Bohr’s orbit is equal to whole
number multiple of the wavelength of the electron wave.
So, 2r = n 
2 r
or 
n
From de Broglie equation,
h

mv
h 2r
Thus, 
mv n
h
or mvr  n 
2
 [v = velocity of electron and r = radii of the orbit]
h
i.e., Angular momentum = n 
2
This proves that the de Broglie and Bohr–concepts are in perfect agreement with each other.
Illustration 11 : What is the mass of a photon of sodium light with a wavelength of 5890 Å.
h
Solution: 
mc
h
or m
c
6.63 1027
So, m = 3.752 × 10–33 g
5890 10 8  3 1010
Illustration 12 : An electron beam can undergo diffraction by crystals. Through what
potential should a beam of electrons be accelerated so that its wavelength
becomes equal to 1.54 Å
Solution : If an electron accelerated by potential V, has velocity 'u' and associated de
Broglie's wavelength .
1/2 m2 = eV … (i)
h
= … (ii)
mu
h
From equation (ii)  
m
2
 h  h2
 1/2 m   =eVV=
 m  2m 2 c
(6.625  10 34 ) 2
= = 63.3 volt
2  9.108  10 31  (1.54  1010 ) 2 1.602  10 19
Illustration 13 : As the speed of a particle of mass m increases, its de Borglie wavelength
 decreases. What is the rate of change of  with the kinetic energy, E for an
electron with  = 1 A ?
Solution: According to de Broglie.
h h
Matter wavelength,   
mv p
We have, kinetic energy
1 p2 h2
E  mv 2   2
2 2m  (2m)
h
 
2mE
 Chemistry : Structure of Atom

The rate of change of de Broglie wavelength  with the kinetic energy E,

d h d(E) 1/ 2 1 h 3 m
= =   2
dE 2m dE 2 2mE  E h

 d  (1  10 10 )3  9.1  1031

 dE   34 2
 2.07×106 m J -1
 at  14 (6.62  10 )

EXERCISE – 3
1. What accelerating potential must be imparted to a proton beam to give it an effective
wavelength of 0.050Å ?
2. A 1.0 g projectile is shot from a gun with velocity of 100 m s–1. What is the de Broglie
wavelength ?
3. Two particles A and B are in motion; if wavelength of A is 5 × 10–8 m, calculate
wavelength of B so that its momentum is double of A.

6. HEISENBERG UNCERTAINTY PRINCIPLE

For heavier objects, the velocity and their position can be measured accurately at any instant
of time but same is not the case for subatomic particles. As a consequence of dual nature of
matter, Heisenberg in 1927 gave a principle about the uncertainties in simultaneous
measurement of position and momentum of small particles.
This principle states that
“It is impossible to measure simultaneously the position and momentum of a small
microscopic moving particle with absolute accuracy or certainty i.e. if an attempt is made to
measure any one of these two quantities with higher accuracy the other becomes less
accurate”
Mathematical expression for the Heisenberg uncertainty principle is simply written as
x . p  h / 4

where p  mv

Explaination of Heisenberg uncertainty Principle : Suppose we attempt to measure both

the position and momentum of an electron, to pinpoint the position of the electron we have
to use light so that the photon of light strikes the electron and the reflected photon is seen in
the microscope. As a result of the hitting, the position as well as the velocity of the electron
are disturbed. The accuracy with which the position of the particle can be measured depends
upon the wavelength of light used the uncertainty in position is  . The shorter the
wavelength, the greater is the accuracy. But shorter wavelength means higher frequency and
hence higher energy. So if position is fixed velocity will not be fixed.
Illustration 14 : Why electron cannot exist inside the nucleus according to Heisenberg’s
uncertainty principle?
Solution : Diameter of the atomic nucleus is of the order of 10–15m
The maximum uncertainty in the position of electron is 10–15 m.
 Mass of electron = 9.1 10–31 kg.
h
x. p =
4

x  (m.v) = h/4
h 1 6.63  10 34 1
v =  =  15
4  x.m 22 10  9.1  10 31
4
7

v = 5.80  1010 ms–1

This value is much higher than the velocity of light and hence not possible.

EXERCISE – 4
1. Calculate the wavelength of a soft ball of mass of 100 g traveling at a velocity of
35 ms–1.
2. If uncertainties in the measurement of position and momentum are equal, calculate
uncertainty in the measurement of velocity.
3. Calculate the uncertainty in the velocity of wagon of mass 2000 kg whose position is
known to an accuracy of ± 10 m.

7. SCHRODINGER WAVE EQUATION

8 2 m
 2  (E  U)  0
h2
This equation implies in essence that a body of mass m, velocity v, potential energy U and
total energy E has a wave associated with it of an amplitude given by wave function . The
schrodinger equation has an infinite many solution. For any physical situation  must be
finite, single valued and continuous. The particular values of  which yield satisfactory
solution of above equation are called wave functions. Wave function for an electron is
called an atomic orbital. Each solution is identified by three quantum numbers. A set of
three quantum numbers is needed to describe an electron because electrons in atoms are
moving in three dimensional space.

Schrodinger Solve Wave function 2

Probability of finding electron
equation 
for electron this wave
function is known as
atomic orbital

The wave function  has got no meaning but the square of the wave function 2 is a
mathematical expression of how the probability of finding an electron in a small volume
varies from place to place. Square of wave function is like the square of amplitude of an
electromagnetic wave. The intensity of electromagnetic radiation is proportional to square
of amplitude.
 Chemistry : Structure of Atom

8. QUANTUM NUMBERS
To understand the concept of Quantum Numbers, we must know the meaning of some terms
clearly so as to avoid any confusion.
Energy Level: The non-radiating energy paths around the nucleus are called as Energy
Levels of Shells. These are specified by numbers having values 1, 2, 3, 4, ... or K, L, M, N,
... in order of increasing energies. The energy of a particular energy level is fixed.
Sub-Energy Level: The phenomenon of splitting of spectral lines in electric and magnetic
fields reveals that there must be extra energy levels within a definite energy level. These
were called as Sub-Energy Levels or Sub-Shells. There are four types of sub-shells namely;
s, p, d, f.
First energy level (K or ) has one sub-shell designated as 1s, the second energy level
(L or 2) has two sub-shell as 2s & 2p, the third energy level (M or 3) has three sub shell as
3s, 3p and 3d, and the fourth energy level (N or 4) has four sub-shells as 4s, 4p, 4d and 4f.
The energy of sub-shell increases roughly in the order: s < p < d <f.
Orbital: Each sub-energy level (sub-shell) is composed of one or more orbitals. These
orbitals belonging to a particular sub-shell have equal energies and are called as degenerate
orbitals. s-sub-shell has one orbital, p has three orbitals, d have five orbitals and f has seven
orbitals.
To describe or to characterize the electrons around the nucleus in an atom, a set of four
numbers is used, called as Quantum Numbers. These are specified such that the states
available to the electrons should follows the laws of quantum mechanics or wave
mechanics.

8.1 PRINCIPAL QUANTUM NUMBER: (n)

This quantum number represents the main energy levels (principal energy levels) designated
as n = 1, 2, 3, ... or the corresponding shells are named as K, L, M, N, ... respectively. It
gives an idea of position and energy of an electron. The energy level n = 1 corresponds to
minimum energy and subsequently n = 2, 3, 4, ..., are arranged in order of increasing
energy.
Higher is the value of n, greater is its distance from the nucleus, greater is its size and also
greater is its energy.
It also gives the total electrons that may be accommodated in each shell, the capacity of
each shell is given by the formula 2n 2 , where n : principal quantum number.

8.2 AZIMUTHAL QUANTUM NUMBER: (l)

This number determines the energy associated with the angular momentum of the electron
about the nucleus. It is also called as the angular momentum quantum number. It accounts
for the appearance of groups of closely packed spectral lines in electric field.
It can assume all integral values from 0 to n–1. The possible values of l are :
0, 1, 2, 3, ..., n–1.
Each value of l describes a particular sub-shell in the main energy level and determines the
shape of the electron cloud.
 When n = 1, l = 0, i.e., its energy level contains one sub-shell which is called as a s-sub-
shell. So for l = 0, the corresponding sub-shell is a s-sub-shell. Similarly when l = 1, 2, 3,
the sub-shells are called p, d, f sub-shells respectively.
As you known for n = 1, l = 0, there is only one sub-shell. It is represented by 1s. Now for n
= 2, l can take two values (the total number of values taken by l is equal to the value of n in
a particular energy level). The possible values of l are 0, 1. The two sub-shell representing
the IInd energy level are 2s, 2p. In the same manner, for n = 3, three sub-shells are
designated as 3s, 3p, 3d corresponding to l = 0, 1, 2, and for n = 4, four sub-shells are
designated as 4s, 4p, 4d, 4f corresponding to l = 0, 1, 2, 3.
h
The orbital Angular momentum of electron =  (  1) .
2
Note that its value does not depend upon value of n.

8.3 MAGNETIC QUANTUM NUMBER (m)

An electron with angular momentum can be thought as an electric current circulating in a
loop. A magnetic field due to this current is observed. This induced magnetism is
determined by the magnetic quantum number. Under the influence of magnetic field, the
electrons in a given sub-energy level prefer to orient themselves in certain specific regions
in space around the nucleus. The number of possible orientations for a sub-energy level is
determined by possible values of m corresponds to the number of orbitals in a given sub-
energy level).
m can have any integral values between –l to +l including 0, i.e., m = –l, 0 +, l, …, 0, 1, 2,
3, 4, . . ., l–1 + l. We can say that a total of (2l + 1) values of m are there for a given value of
l– 2, –1, 0, 1, 2, 3.
In s sub-shell there is only one orbital [l = 0,  m = (2l +1) = 1].
In p sub-shell there are three orbitals corresponding to three values of m : –1, 0 +1. [l = 1
 m = (2l +1) = 3]. These three orbitals are represented as p x , p y , p z along X, Y, Z axes
perpendicular to each other.
In d sub-shell, there are five orbitals corresponding to –2, –1, 0 +1, +2, [l = 2
 m = ( 2  2  1)  5] . These five orbitals are represented as d xy , d yz , d zx , d x 2 – y2 , dz 2 .
In f sub-shell there are seven orbitals corresponding to –3, –2, –1, 0, +1, +2, +3 [l = 3
 m = (2  3  1)  7] .

8.4 SPIN QUANTUM NUMBER (s)

When an electron rotates around a nucleus it also spins about its axis. If the spin is
clockwise, its spin quantum number is +1/2 and is represented as  . If the spin is anti-
clockwise, its value is –1/2 and is represented as  . If the value of s is +1/2, then by
convention, we take that electron as the first electron in that orbital and if the value of s is –
1/2, it is taken as second electron.
Illustration 15: Write down the values of quantum numbers of all the electrons present in
the outermost orbit of argon (At. No. 18)
Solution: The electronic configuration of argon is 1s 2 , 2s 2 2p 6 ,3s 2 3p 2x 3p 2y 3p 2z
 Chemistry : Structure of Atom

Values of quantum numbers are:

n 1 m s
2 3 0 0 +1/2, –1/2
3s
3p 2x 3 1 1 +1/2, –1/2

3p 2y 3 1 1 +1/2, –1/2

3p 2z 3 1 0 +1/2, –1/2

Illustration 16: (a) An electron is in 5f-orbital. What possible values of quantum numbers n,
l, m and s can it have?
(b) What designation is given to an orbital having (i) n = 2, l =1, and (ii)
n = 3, l = 0?
Solution: (a) For an electron in 5f-orbital, quantum number are:
1 1
n = 5, l = 3; m = –3, –2, –1, 0, +1, +2, +3 and s = either + or –
2 2
(b) (i) 2p, (ii)3s

EXERCISE – 5
1. Give the possible values for the missing quantum numbers :
(a) n = 3, l = 0, ml = ? (b) n = 3, l = ?, ml = –1
(c) n = ?, l = 1, m1 = + 1 (d) n = ?, l = 2, ml = ?
2. Write appropriate values of n, l and ml quantum numbers for each of the following
orbital designations :
(a) 4s (b) 3p
(c) 5f (d) 6g
(e) 3d (f) 7s
Also arrange them in increasing energy.
3. Which of the following sets of quantum numbers is/are not allowable ? Why not ?
(a) n = 2, l = 1, ml = 0 (b) n = 2, l = 2, ml = –1
(c) n = 3, l = 0, ml = 0 (d) n = 3, l = 1, ml = 1
(e) n = 2, l = 0, ml = –1 (f) n = 2, l = 2, ml = –1
4. What type of electron orbital is designated for :
(a) n = 2, l = 1, ml = –1 (b) n = 2, l = 2, ml = –1
(c) n = 5, l = 0, ml = 0

9. RULES FOR FILLING ELECTRONS

9.1 AUFBAU PRINCIPLE
The aufbau principle states that
in the ground state of an atom, the orbital with a lower energy is filled up first before the
filling for the orbital with a higher energy commences.
 In other words :
The electrons enter the various orbitals in the order of increasing energy.
1s

2s 2p

3s 3p 3d

4s 4p 4d 4f

5s 5p 5d

6s 6p

7s

This order of orbitals is only a guidance and exceptions are known in few cases
of atoms.

9.2 PAULI'S EXCLUSION PRINCIPLE

This an important generalisation given by Wolfgang Pauli, in 1925, which determines the
maximum number of electrons that an energy level can accommodate.
Pauli's exclusion principle states that
It is impossible for any two electrons in the same atom to have all the four quantum numbers
identical.
Thus, in the same atom, any two electrons may have three quantum numbers identical but the
fourth must be different. This principle is very useful in determining the maximum number of
electrons that can occur in any shell/sub shell. For K-shell, for instance, since n=1,  can have
only one value (viz., 0) and m can also have only one value (viz., 0). Hence s can be either
+1/2 or -1/2. Thus, there are two combinations of the quantum number, as shown below:
n =1  = o m = 0 s = +1/2
n =1  = o m = 0 s = -1/2
This shows that in the K-shell, there is only one subshell  = 0 and there are only two
electrons of opposite spins.
For L-shell, since n = 2,  can have two values ( 0 and 1,) m can have one value of  = 0 and
three values of  =1 (-1,0 and +1) and s can have two values (=+1/2 and-1/2) for each value of
m. These possibilities would give rise to eight combinations of the four quantum numbers,
keeping in view the exclusion principle . The maximum number of electrons in a shell is
given by 2n2.

9.3 HUND'S RULE OF MAXIMUM MULTIPLICITY

This rule states that
Electron pairing in orbitals of same energy (degenerate orbitals) will not take place unless
all the available orbitals of a given subshell contain one electron each with parallel spin.
For example, we know that there are three p orbitals (px, py and pz) of the p-subshell in a
principle energy level. According to Hund's rule, each of the three p orbitals must get one
 Chemistry : Structure of Atom

electron each of parallel spin before any one of them gets the second electron of opposite spin
as shown below

9.4 RULE OF EXTRA STABILITY OF COMPLETELY HALF FILLED OR

COMPLETELY FILLED ORBITAL
When the energy of a wave function is evaluated by using the appropriate Schrodinger
equation, two types of energies, viz., Colulomb and exchange energies, are involved. The
coulomb energy is a measure of the mean repulsion of two electrons occupying different
orbitals, the exchange energy is the lowering of energy for a set of two electrons of parallel
spin which arises as a result of in distinguish ability of the electron coordinates. For a system
containing more than two electrons of parallel spin, the lowering of energy due to exchange of
electrons is given by
E = N × K
where N is the total number of possible exchanges of coordinates between sets of two
electrons of parallel spin and K is the average exchange energy per set of electrons of parallel
spin. For a system containing n electrons of parallel spin. For a system containing n electrons
of parallel spin, N is given by
n!
N
2(n  2)!
The exchange energies for the two possible configurations of Cr are as follows:
3d4, 4s2 n = 5 E = 10K
1
3d5, 4s n = 6 E = 15K
that is, the exchange energy stabilization of 3d5, 4s1 configuration is larger than 3d4, 4s2
configuration. Besides this, since the two electrons with parallel spins remain farther apart
than two electrons with opposed spins, the Columbic repulsion energy is also smaller in case
of two parallel spins. Thus the configuration 3d54s1, which contains more number of parallel
spins, is more stable than 3d54s2. The stability of the 3d104s1 configuration for the copper atom
may be explained in the same way.
Thus, it may be concluded that the unusual stability of electronic configurations involving
half-filled and completely filled orbitals is due to the larger exchange energy and lesser
columbic repulsion.
The simplified explanation of the above illustration is given below :
Exchange Energy : This stabilizing effect arises whenever two or more electrons with the
same spin are present in the degenerate orbitals of a subshell. These electrons tend to
exchange their positions and the energy released due to this exchange is called exchange
energy. The number of exchanges that can take place is maximum when the subshell is either
half filled or completely filled (Figure given below). As a result the exchange energy is
maximum and so is the stability.
 1 2 3

4 exchange by 3 exchange by 2 exchange by

electron 1 electron 2 electron 3

1 exchange by
electron 4
Fig. Possible exchanges for a d5 configuration.

9.5 ELECTRONIC CONFIGURATIONS OF ELEMENTS

Based on the rules, we can easily determine the electronic configurations of most elements.
We just need to know the atomic number of an element, the order in which orbitals are to be
filled and the maximum number of electrons in a shell, sub-shell or orbital. The configuration
so obtained can be represented in two ways. As an illustration, let us consider fluorine (Z = 9):
F (Z = 9) 1s2 2s2 2p 2x 2p 2y 2p 1z or         
1s 2s 2px 2py 2pz
Importance of knowing the exact electronic configuration of an element lies in the fact that
the chemical properties of an element are dependent on the behaviour and relative
arrangement of its electrons.
Electronic configurations of heavier elements (beyond Z = 56) deviate a little from the order
mentioned previously. These are brief listed below
a) Lanthanides La (Z = 57) : [Xe] 6s25d1 (not 4f1)
Ce (Z = 58) : [Xe] 6s25d14f1
Pr (Z = 59) : [Xe] 6s25d14f2
b) Actinides Ac (Z = 89) : [Rn] 7s26d1 (not 5f1)
Th (Z = 90) : [Rn] 7s26d15f1
Pa (Z = 91) : [Rn] 7s26d15f2
c) Beyond Z = 103 Z = 104 : [Rn] 5f146d27s2
Z = 105 : [Rn] 5f146d37s2
Z = 106 : [Rn] 5f146d47s2
Z = 112 : [Rn] 5f146d107s2

EXERCISE – 6
1. State the basic ideas that are violated by each of the following electronic configuration
and replace each by the correct configuration :
(a) B5 – 1s2 2s2 (b) Na11 – 1s2 2p6 2p6 2d1
(c) K19 – [Ar] 3d1 (d) Ti22 – [Ar] 4s2 4p2
(e) Hg80 – [Xe] 4f10 5d10 6s2 6p2
2. Which of the following will be coloured ion ?
 Chemistry : Structure of Atom

(a) Fe2+ (b) Cu+

(c) Sc3+ (d) Mn2+
Which has the maximum magnetic moment ?
3. Magnetic moment of X3+ ion of 3d series is 35 B.M. What is atomic number of X3+ ?

10. SHAPES AND SIZES OF ORBITALS

By shape of an orbital we mean the shape of the region in space in which there is probability
of finding an electron. It is basically determined by the azimuthal quantum number (  ),
while the orientation of an orbital depends on the magnetic quantum number (m). The size
of an orbital increases with the value of the principal quantum number (n). Shapes of
orbitals in the various sub-shells are as discussed below:
The place where probability of finding an electron is 0 ( = 0) is known as node and a
plane passing through node is known as nodal plane.
Total number of nodal planes = 
There are two types of nodes:
(i) Radial node: These are the points at some distance from the nucleus where there is
zero probability of finding the electrons. S-orbital being spherically symmetric and
hence non-directional, can’t have angular node. (i.e. points where 4r 2  2  0 )
(ii) Angular nodes: These are directional in nature so these are associated with p and d
orbitals.
For a particular quantum number n
Total nodes = n – 1
Radial nodes = n –  – 1
Angular nodes = 

10.1 s – ORBITALS
s - orbitals (  = 0) : The orbitals are spherical and y

symmetrical about the nucleus. There is vacant

space between two successive s-orbitals, known
1s 2s
as ‘radial node’. Due to nucleus symmetricity, nucleus x
these are non-directional.
Z radial node
10.2 p – ORBITALS
p - orbitals (  = 1): These have a dumb - bell shape, having three possible mutually
perpendicular orientations. As they are not symmetrical, they have a directional character.
The two lobes of p-orbitals are separated by a nodal plane, where the probability of finding
electron is zero.
z z
z yz plane
y y y
xy plane
xz plane
x x x

px orbital py orbital pz orbital

The three 2p orbitals and Nodal Planes
10.3 d – ORBITALS
d - orbitals (  = 2): They have relatively complex geometry. Out of the five d-orbitals, the
 
first two d z2 & d x 2  y2 lie along the axes, while the other three (dxy, dzx, dyz) project in
between the axis.
z z z

y y y

x x x

dxy orbital dxz orbital dyz orbital

z z

y y

x x

dx2 – y 2 orbital dz2 orbital

The five d orbitals

10.4 NODES AND NODAL PLANES FOR d-ORBITALS
 Chemistry : Structure of Atom

z
z
Nodal cone

y
y

x x

Two nodal surface forming two nodal cones about z axis for d Z2 orbital.
z z
xz - nodal plane

y xy - nodal
plane y

z x

Two nodal planes xy and xz for dyz orbital

yz - nodal plane z
z

y y

xy - nodal
plane

x
x

Two nodal planes yz and xy for dxz orbital

z yz - nodal plane
z

y y

xz - nodal
plane

x x

Two nodal planes xz and yz for dxy orbital

 z z

y
y

x x

Nodal planes for d x2  y2 at angle 45° to x and y axis

Illustration 17 : Name the orbitals corresponding to given set of quantum numbers

(a) n = 3,  = 2, m =  2 (b) n = 4,  = 0, m = 0
(c) n = 3,  = 1, m  1 (d) n = 2,  = 1, m = 1
Solution: (a) 3d x2  y2 (b) 4s

(c) 3p x or 3p y (d) 2px or 2py

 Chemistry : Structure of Atom

Illustration 18 : (a) Find the orbital angular momentum of an electron in the following
orbital
(i) 3p (ii) 3d (iii) 3s
(b) Arrange the electrons represented by the following sets of quantum
number in decreasing order of energy
(i) n = 4, l = 0, m = 0, ms = 1/2
(ii) n = 3, l = 2, m = 0, ms = 1/2
(iii) n = 3, l = 1, m = 1,ms = –1/2
(iv) n = 3, l = 0, m = 0,ms = –1/2
h
Solution : (a)  =  (  1) = (  1) 
2
(i) For 3p,  = 1  = 1(1  1)  2 
h
(ii) For 3d ,  = 2  = 2(2  1)  6 
2
(iii) For 3s,  = 0, l = 0
(b) For the same value of n, higher the value of (n + ), higher is the energy.
(c) For the same value of n + , higher the value of n, higher will be the
energy.
For (i) ( n + ) = 4 for 4s orbital
For (ii), (n+) = 4, for 3d orbital
For (iii) ( n + ) = 4 for 3p orbital
For (iv), (n+) = 3 3s orbital
Decreasing order of energy = (ii)  (i)  (iii)  (iv)

11. QUANTUM MECHANICAL TREATMENT OF HYDROGEN ATOM

Hydrogen atom is the simplest system consisting of one electron and one proton.
Schrodinger equation is written in terms of Cartesian coordinates (x, y, z). If electron moves
at a distance from the stationary nucleus and atom is spherical in shape. If the position of
electron is expressed in polar coordinates (r, , ), the schrodinger equation can be solved
easily.
The Cartesian coordinates can be converted to polar coordinates by following relation.
x = r sin  cos 
y = r sin  sin 
z = r cos 
and also, x2 + y2 + z2 = r2
 When Schrodinger equation is solved in polar coordinates, for hydrogen atom. It gives the
possible energy states and corresponding wave function [ (r, , )], called atomic orbitals.
The schrodinger equation cannot be exactly solved for a multi electron atom.
Atomic Orbitals and their Pictorial Representation : An atomic orbital is an electron wave
function,  (r, , ) obtained from the solution of the schrodinger equation. Wave function
 is a mathematical function of the three coordinates of electron (r, , ). This wave
function can be written into three separate parts each of which is a function of only one
coordinate.
 = f(r, , )
 (r, , ) = R(r), (), ()
R is function of r,  is function of  and  is function of .
Where, R is radial function and  and  are angular function. The radial function depends
on quantum numbers n and . The angular function depends on  and m.
Significance of Wave Function  : The orbital wave function  has no physical
significance. It is the square of the absolute value of wave function ||2, which has a
physical significance. It measure the electron probability density at a point in an atom.
If the variations of  or ||2 with r, ,  are to be observed graphically. It would need a four
dimensional graph in space but on the plane of paper we can draw only two dimensional
graph to overcome this difficult.
We draw separate diagrams for
(i) Variation of radial function
(ii) Variation of Angular function
R is known as radial wave function
R2 is known as radial probability density and 42r2R2 is known as radial probability.

11.1 FUNCTION VARIATION OF RADIAL FUNCTION

(i) Plot of Radial Wave Function (R) vs r: In all cases R approaches zero as r
approaches infinity. There is a node (where the probability of finding electron is zero)
in 2s orbital radial function. At the node the value of radial function changes from
positive to negative for 2s orbital. In general ns orbitals have (n – 1) nodes.

Node

The plots of the radial wave function R Vs. distance r

(ii) Radial Probability Density (R2)vs r: The square of radial wave function R2 for an
orbital gives the radial density. The radial density gives the probability density of
finding the electron at a point along a particular line.
 Chemistry : Structure of Atom

Node

2
The plots of the radial probability density R Vs. distance r

(iii) Radial Probability Functions (42r2R2) vs r: Radial probability function gives the
probability of finding the electron at a distance r from the nucleus regardless of
direction.

2 2
The plots of the radial density function 4 r R Vs. distance r