CHAPTER 2 STRUCTURE OF ATOM (JEE-NEET)

Dalton’s Atomic Theory

In 1809 John Dalton regarded the atom as a hard dense and smallest indivisible particle of matter. The
main postulates of Dalton’s atomic theory are
(i) Atoms of a particular element are alike but differ from atoms of another element. This accounted for
identical behaviour of different samples of the same element and different behaviour of different
elements.
(ii) Atoms of each element have a characteristic mass. This explained the fact that macroscopic samples
at material substances have mass.
(iii) Atoms are indestructible, i.e. they can neither be created nor destroyed.
(iv) Atoms combine to form molecules, which accounts for the observation that elements combine to
form compounds.
Dalton’s atomic theory was successful in explaining the following facts.
(i) It gave satisfactory explanation for the chemical combination.
(ii) It explained most of the properties of gases and liquids known at that time.
However, Dalton’s atomic theory failed to explain the following facts
(i) It did not explain why atoms of different elements should differ in their masses, valencies, etc.
(ii) It did not explain the existence of isotopes and isobars.
(iii) It did not explain why there should not be some material difference in the “make up of atoms of
different element.
Various experiments convinced the scientists that atom is not indivisible but consists of smaller
fundamental particles. It is now established that atom consists of three major fundamental particles
called electrons, protons and neutrons.

DISCOVERY OF ELECTRON: CATHODE RAYS

During the latter half of the nineteenth century, it was found that while normally dry gases do not
conduct an electric current, they do so under very low pressure and then patches of light are seen. The
passage of electricity through gases as studied by a number of physicists, particularly by Faraday, Davy,
Crookes and J.J. Thomson.
When a current of high voltage (10,000 volts) is passed through a gas of air kept at a very low pressure
(0.01 – 0.03 mm) blue rays are seen emerging from the case. These rays are called “Cathode Rays”.
-4
V >100,000 volts Gas at low pressure (10 atm)

– +
Cathode Anode
(Invisible rays )
vaccum pump (Cathode rays)

Some of the important properties of the cathode rays studied by Sir J.J. Thomson and others
are given below:
Shadow
Properties of Cathode rays
Object
(1) These rays travels in straight lines away from cathode
with very high velocity ranging from 107 to 109 m/sec. – +

(2) A shadow of metallic object placed in the path is cast

on the wall opposite to the cathode.
Light mica wheel ZnS Screen
Mounted on axle

(3) These rays produce a green glow when strike the

glass wall matter. Light is emitted when they strike the zinc-sulphide screen.

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 CHAPTER 2 STRUCTURE OF ATOM (JEE-NEET)
(4) When a small paddle wheel is placed in their path, the blades of the wheel are set in motion. Thus,
we can say that the cathode rays consist of material particles, which have mass and velocity.

(5) These rays are deflected by the electric and magnetic

fields. When the rays are passed between two electrically – +
charged plates, these are deflected towards the positively
charged plate. It shows that cathode rays carry -ve charge.
These particles carrying negative charge. The name Light mica wheel
Mounted on axle
Railing

'electron' was given by Stoney.

(6) These rays produce heat energy when they collide with the matter. It shows that cathode rays
possess Kinetic energy, which is converted into heat energy when stopped by matter.
(7) These rays affect the photographic plate. Wall Coated
With ZnS
(8) Cathode rays can penetrate the thin foil of solid
+
materials. +
–
(9) Cathode rays can ionize the gases through which
they pass.
–
(10) They produce Xray when they strike a metal like
+

tungsten and molybdenum. High

Voltage Anode with
10,000 Volits A Hole Electri Field

(11) No cathode ray was produced when the tube was completely evacuated. The nature of cathode rays
is independent of (a) The nature of cathode and (b) The gas in discharge tube. Different gases produce
same cathode rays as they have the same e/m (charge/mass) ratio. This indicates that the particles
present in cathode rays are fundamental constituent of all matter.
(12) The mass of a particle present in cathode rays is found to be 1/1837 of Hatom. This shows that the
particle is of subatomic nature.

Sir J.J. Thomson named these negatively charged subatomic particles as electron.
“A subatomic particle which is a fundamental constituent of all matter having a mass 1/1837 th of a
Hatom and which carries the smallest unit of negative charge is called an electron”.

Charge to Mass Ratio of Electron

In 1897, British physicist J.J. Thomson measured the ratio of electrical charge (e) to the mass of electron
(me ) by using cathode ray tube and applying electrical and magnetic field perpendicular to each other as
well as to the path of electrons (Fig. 2.2 in tbk).

Thomson argued that the amount of deviation of the particles from their path in the presence of
electrical or magnetic field depends upon:
(i) The magnitude of the negative charge on the particle, greater the magnitude of the charge on the
particle, greater is the interaction with the electric or magnetic field and thus greater is the deflection.
(ii) The mass of the particle — lighter the particle, greater the deflection.
(iii) The strength of the electrical or magnetic field — the deflection of electrons from its original path
increases with the increase in the voltage across the electrodes, or the strength of the magnetic field.
When only electric field is applied, the electrons deviate from their path and hit the cathode ray tube at
point A. Similarly, when only magnetic field is applied, electron strikes the cathode ray tube at point C.
By carefully balancing the electrical and magnetic field strength, it is possible to bring back the electron
to the path followed as in the absence of electric or magnetic field and they hit the screen at point B. By
carrying out accurate measurements on the amount of deflections observed by the electrons on the
electric field strength or magnetic field strength, Thomson was able to determine the value of e/me as:

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 CHAPTER 2 STRUCTURE OF ATOM (JEE-NEET)
Where me is the mass of the electron in kg and e is the magnitude of the charge on the electron in
coulomb (C). Since electrons are negatively charged, the charge on electron is –e.

Determination of Velocity and Charge/mass (e/m) ratio of Electrons:

Sir J.J. Thomson (1897) extended the cathode ray experiment for the determination of velocity of
electrons and their charge/mass ratio, The value of e/m for an electron = 1.76  108 C/g.
For the H+ ion (proton), e/m = 96500/1.008 C/g.

Millikan’s Oil Drop Method: Determination of Charge on an Electron:

In 1909, Millikan measured the charge on an electron by his oil drop method. In this method an
atomizer, some of which pass through an opening into a viewing chamber, where we can observe them
with a microscope, produces a spray of oil droplets. Often these droplets have an electric charge, which
is picked up from the friction forming the oil droplets. A droplet may have one or more additional
electrons in it, giving it a negative charge.
As the droplet falls to the bottom of the chamber, it passes between two electrically charged plates. The
droplet can be suspended between them; we adjust the voltage in the plates so that the electrical
attraction upward just balances the force of gravity downward. We then use the voltage needed to
establish this balance to calculate the mass - to charge ratio for the droplet. Because we already know
the mass of the droplet, we can find the charge on it.
Millikan's found that the charge on all droplets could be expressed as whole number multiples of e,
where the value of e is 1.60210-19 C. By combining e/m. ratio and 'e' we calculate mass of the electron
e 1.6022  1019
Me   = 9.10410-31 kg
e/m 1.76  108
This very small value shows that the electron is a subatomic particle. Thus charge on an electron =
1.602  10–19C.
This mass is termed as the rest mass of electron. It has been found that the mass of an electron is
approximately1/1837 th, the mass of hydrogen atom. The mass of electron in relative units is
0.0005486 amu.
𝑟𝑒𝑠𝑡 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑒𝑙𝑒𝑐𝑡𝑟𝑜𝑛
The mass of moving electron = 2
√1−(𝑣)
𝑐

Here ‘v’ is the velocity of electron and ‘c’ is the velocity of light. When ‘v’ becomes equal to ‘c’, mass of
the moving electron becomes infinity.

Positive rays - (Discovery of Proton)

The first experiment that lead to the discovery of the +ve particle was conducted by 'Goldstein'.
He used a perforated cathode in the modified cathode ZnS
Oasting
ray tube.
It was observed that when a high potential difference was
applied between the electrodes, not only cathode rays
+
were produced but also a new type of rays were produced
simultaneously moving from anode to cathode. In actual
it does not produce from anode but it looks like to be –
Perforated
produced from anode and passed through the holes or Cathode H2 gas inside
At low Pressure
canals of the cathode. These rays were termed canal rays
since these rays passed through the canals of the cathode. These were also named anode rays as these
moves from anode to cathode.
When the properties of these rays were studied by Thomson, he observed that these rays consists of
positively charged particles and named them as positive rays.
The following characteristics of the positive rays are as follows.
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 CHAPTER 2 STRUCTURE OF ATOM (JEE-NEET)
(i) These rays travel in straight lines and cast a shadow of the object placed in their path.
(ii) Like cathode rays, these rays also rotate the wheel placed in their path and also have heating effect.
Thus, the rays possess K.E. i.e. mass particles are present.
(iii) These rays are deflected by electric and magnetic fields towards the negatively charged plate
showing thereby that these rays carry +ve charge.
(iv) These rays produce flashes of light on ZnS screen
(v) These rays can pass through thin metal foil.
(vi) Positive particles in these rays have e/m value much smaller than that of e-. For a small value of
e/m, it is definite that positive particles possess high mass.
(vii) e/m value is dependent on the nature of the gas taken in the discharge tube, i.e. the mass of the
positive rays depends on the atomic weights or molecular weights of the gases in the discharge tube.
The charge/mass ratio also varies because the change in positive charge on the rays. It may be either
equal to or integral multiple of the charge on an electron +ve particles are different in different gases.
(viii) The lightest of all particles identified in positive rays from different elements was one with a mass
very slightly less than that of hydrogen atom (or nearly equal to Hatom). The lightest positively charged
particle is called a proton (P or P+). Positive rays are atomic or molecular resides from which some
electrons have been removed. The removed electrons constitute the cathode rays and the positive
residues form the positive or canal rays.

J.J. Thomson made accurate measurements of the charge and the mass of the particles in the discharge
tube containing hydrogen, the lightest of all gases, in 1906. These particles were found to have the e/m
value as +9.579 ×104 coulomb/g. This was the maximum value of e/m observed for any +ve particle.
It was assumed that the positive particle given by the hydrogen represents a fundamental particle of +ve
charge. This particle was named proton. Its charge was found to be equal in magnitude but opposite in
sign to that of electron.
Thus Charge on proton = + 1.602 ×10-19 coulomb i.e. One unit +ve charge
The mass of the proton thus can be calculated.
e 1.602 1019
Mass of the proton =  = 1.672 × 10-24 g = 1.672 × 10-27 kg
e / m 9.579 10 4

1.672  1024
Mass of proton in amu = = 1.0072 amu. (atomic mass unit)
1.66  1024
DISCOVERY OF NEUTRON
After the discovery of electrons and protons. Rutherford (1920) had predicted the existence of a neutral
fundamental particle. In 1932, Chadwick bombarded the element Beryllium with particles and noticed
the emission of a radiation having the following characteristics.
 The radiation was highly penetrating.
 The radiation was unaffected by magnetic and electric fields which show that it is electrically neutral.
 It was found to have approximately the same mass as the protons.
 The name ‘neutron’ was given to this subatomic particle. It is denoted by n or 1o n .
 Bombardment of beryllium by particles results in the formation of carbon and neutrons are
emitted. 9
4𝐵𝑒 + 42𝐻𝑒 → 12
6𝐶 + 10𝑛
 At present there are a number of evidences which confirm that like electron, proton and neutron is
also a fundamental constituent of atoms (a single exception is 11 H atom which does not contain any
neutron)
 Mass of a neutron is 1.008930 amu (1.6753  10–24g or 1.6753  10–27 kg)
 Neutron “A subatomic particle, which is a fundamental constituent of matter having mass
approximately equal to the hydrogen atom and which is electrically neutral, is called a neutron”.

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 CHAPTER 2 STRUCTURE OF ATOM (JEE-NEET)
Thomson's model of atom [1904]
 Thomson was the first to propose a detailed model of the atom.
 Thomson proposed that an atom consists of a uniform sphere of
positive charge in which the electrons are distributed more or
less uniformly.
 Thomson assumed that an atom is a sphere of positive electricity
in which the electrons are embedded like seeds in water melon.
The seeds represent the electrons and fibrous material, the
massive positive charge. Thomson’s model was called water melon model (or) Plum pudding, or
Raisin pudding model.
Drawbacks:
 An important drawback of this model is that the mass of the atoms is considered to be evenly spread
over that atom.
 It is a static model. It does not reflect the movement of electron.
 It could not explain the stability of an atom.

Rutherford’s Atomic Model:

Rutherford's scattering experiment -scattering experiment
thin gold foil (.00004 cm)

most of 
particles
strike here

(Ray)

Zns Screen
source (Ra) of slit system
rays (lead plate)
=[He] circular
4+2
2

[doubly ionised He particle] fluorescent screen

Rutherford, performed 𝛼 −ray scattering experiments in which he bombarded thin foils of metals like
gold, silver, platinum or copper with a beam of fast moving 𝛼 particles. The source of 𝛼 particles was a
radioactive substance, placed in a block of lead. The presence of 𝛼 particles at any point around the thin
foil of gold after striking it was detected with the help of a circular zinc sulphide screen. The point at
which a𝛼 particle strikes this screen, a flash of light produced.
Observations: In Rutherford’s alpha ray scattering Nucleus
experiment, it was observed that:
i. Most of the -particles (more than 99%) passed
particles
through the gold foil without any deflection from their Un deflected
-particles
original path.
ii. A few of the alpha particles (approximately 0.005%)
are deflected fairly at large angles (more than 90°) or even largely deflected Slightly deflected
particles particles
come back in more or less the direction from which they
have come. While some are deflected through small angles.
iii. A very few -particles ‘1 in 20000’ are deflected back along their path.

Conclusions: Following conclusion were drawn from the above observations.

 Since most of the -particles went straight through the metal foil without deflection, it means that
there must be very large empty space with in the atom.
 A few of the -particles were deflected from their original paths through moderate angles; it was
conclude that whole of the positive charge is concentrated and the space occupied by this positive
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 CHAPTER 2 STRUCTURE OF ATOM (JEE-NEET)
charge is very small in the atom. When -particles come closer to this point, they suffer a force of
repulsion and deviate from their paths.
 The positively charged heavy mass that occupies only a small volume in an atom is called nucleus. It
is supposed to be present at the centre of the atom.
 A very few of the -particles suffered strong deflections or even returned on their path indicating
that the nucleus is rigid and -particles recoil due to direct collision with the heavy positively
charged mass.
 Rutherford concluded that the number of particles N scattered at an angle  is such that
1
N

sin 4  
2
 Later Rutherford concluded that mass number is twice the nuclear charge this forced him to modify
his own model as ‘Atomic nucleus consists of protons and enough electrons to reduce the positive
charge to about half the mass number and the remaining positive charge on the nucleus was
balanced by the planetary electrons’.
According to Rutherford,
1. An atom is spherical and mostly hollow with a lot of empty space in it.
2. It has a small positively charged part at its centre known as nucleus. The entire mass of the atom is
concentrated in its nucleus.
3. The nucleus is surrounded by electrons. The electrons revolve round the nucleus with very high
speeds in circular paths called orbits.
4. The number of extra nuclear electrons is equal to the number of units of positive charge in the
nucleus. Therefore, the atom is electrically neutral. Electrons and the nucleus are held together due
to electrostatic forces of attraction.
5. Rutherford’s model has resemblances with solar system. Just as planets revolve round the Sun, the
electrons revolve round the nucleus. This model of the atom is also known as planetary model of the
atom.
6. X-ray investigations have revealed that the nucleus has a diameter of the order of 10 –13 to 10–12 cm
and the atom has a diameter of the order of 10–8 cm. The size of the atom is 105 times the size of
the nucleus. Nucleus has a diameter of the order of 10-12 to 10-13 cm and the atom has a diameter of
the order of 10-8 cm.
DA Diameter of the atom 108
  = 105, DA = 105 DN
DN Diameter of the nucleus 1013
Thus, diameter (size) of the atom is 105 times the diameter of the nucleus.
The radius of a nucleus is proportional to the cube root of the no. of nucleons within it.
R  A1/3  R = R0A1/3 cm
Where R0 = 1.33 ×10 (a constant) an, A = mass number (p + n)
-13

R = radius of the nucleus.

R = 1.33 × 10–13 A1/3 cm
7. There is an empty space around the nucleus called extra nuclear part. In this part, electrons are
present. As the nucleus of the atom is responsible for the mass of the atom, the extra nuclear part
is responsible for its volume.
The volume of the atom is about 1015 times the volume of the nucleus.

108 
3
vol. of the atom
  1015
vol. of the nucleus 10 
13 3

Drawbacks:
1. It could not explain how the electrons and protons could be close-packed to give a stable nucleus.
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 CHAPTER 2 STRUCTURE OF ATOM (JEE-NEET)
2. According to the electromagnetic theory of Maxwell (law of electro–dynamics),
when a charged particle moves under the influence of attractive force it loses energy
continuously in the form of electromagnetic radiation. Therefore, an electron in an
orbit will emit radiation. +
As a result of this, the electron should lose energy at every turn and move closer and
closer to the nucleus following a spiral path.
The ultimate result is that it will fall into the nucleus thereby making the atom unstable. Thus the
Rutherford’s model cannot explain the stability of the atom.
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 outside 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. If the electrons lose energy continuously, the spectrum is expected to be continuous but the actual
observed spectrum consists of well-defined lines of definite frequencies. Here the loss of energy by the
electrons is not continuous in an atom. Thus, Rutherford’s model could not explain the origin of spectral
line.
4. Electron is too large to be in the small space of the nucleus. How were the objections remedied?
The drawbacks of Rutherford’s model could be overcome in the following way
(a) The first and fourth objections found their answer in the discovery of neutron and Moseley’s work on
atomic number.
(b) The second and third objections were solved by Niel Bohr who developed his own theory on the basis
of the quantum theory.

Mass Number : It is represented by capital A The sum of number of Neutrons and protons is called the
mass Number. of the element.
A = number of protons + number of Neutrons
Atomic Number :
It is represented by Z. The number of protons present in the Nucleus is called atomic number.of an
element. It is also known as nuclear charge.
For neutral atom: Number of proton = Number of electron
For charged atom: Number of e– = Z – (charge on atom)
Z= number of protons only

Example : 17Cl
35

n = 18, p = 17, e = 17
Two different elements cannot have the same Atomic Number
Number of Neutrons = Mass number – Atomic number
= A–Z
= (p + n) – p
= n
Isotopes : Given by Soddy
They are the atoms of a given element which have the same atomic number but different mass number
i.e. They have same Nuclear charge but different number of Neutrons.
Example : 17Cl35 17Cl
37

n = 18 n = 20
e = 17 e = 17
p = 17 p = 17
Isotopes have same chemical property but different physical property.

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 CHAPTER 2 STRUCTURE OF ATOM (JEE-NEET)
Isotopes do not have the same value of
Example : (Proteium Dueterium Tritium)
1H 1H 1H
1 2 3

e=1 e=1 e=1

p=1 p=1 p=1
n=0 n=1 n=2
1H is the only normal hydrogen which have n = 0 i.e. no nuetrons
1

Duetrium is also called as heavy hydrogen. It represent by D

Example : 6C
12
6C
13
6C
14

e=6 e=6 e=6

p=6 p=6 p=6
n=6 n=7 n=8
Isobars : Given by Aston
They are the atoms of different element which have the same mass number but different Atomic number
i.e They have different number of Electron, Protons & Neutrons But sum of number of neutrons & Protons
remains same.
Example : 1H3 2He
3

p=1 p=2
e = 1 1+2 =3 e=2 2+1=3
n=2 n=1
p+n=3 p+n=3
Isobars do not have the same chemical & physical property
They do not have the same value of e/m
Example : 19 K40 20 Ca
40

p = 19 p = 20
n = 21 40 n = 20 40 = n + p
e = 19 e = 20
Number of Nucleons same
Isodiaphers :
They are the atoms of different element which have the same difference of the number of Neutrons &
protons.
Example : 5B
11
6C
13

p=5 p=6
n = 6] n – p =1 n = 7] n – p =1
e=5 e=6
9F
19
Example : 7N
15

p=7 p=9
n = 8] n – p =1 n = 10] n – p =1
e=7 e=9
Isotones/ Isonuetronic species / Isotonic :
They are the atoms of different element which have the same number of neutrons.
Example : 1H
3
2He
4

p=1 p=2
n=2 n=2
e=1 e=2
Example : 19 K
39
20 Ca
40

e = 19 e = 20
p = 19 p = 20
n = 20 n = 20

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 CHAPTER 2 STRUCTURE OF ATOM (JEE-NEET)
Isosters : They are the molecules which have the same number of atoms & electrons.
Example : CO2 N2O
Atoms =1+2 Atoms =2+1
=3 =3
Electrons =6+8× 2 Electrons =7× 2+8
= 22 e– = 22e–
Example : CaO KF
Atoms 2 2
Electrons 20 + 8 19 + 9
28 e– 28 e–

Example : OF2 HClO

Atoms =3 3
Electrons = 8 + 18 1 + 17 + 8
= 26 e– 17 + 9
26 e–
Isoelectronic Species :
They are the atoms, molecules or ions which have the same number of electrons.
Example : Cl– Ar
Electron 18 e – 18 e–
Example : H2O NH3
e=2+8 e=7+3
10 e– 10 e–
Example : BF3 SO2
e = 5 +9 × 3 16 + 8 × 2
5 + 27 16 + 16
32 e– 32 e–
Question : If the mass of neutrons is doubled & mass of electron is halved then find out the atomic
mass of 6C12 and the percent by which it is increased.
Ans. Step-1 6C12
e=6
p = 6 = 6 amu
n = 6 = 6 amu] =12 amu
If the mass of neutrons is doubled and mass of e– is halved then. Co, 27



n = 12 amu Fe, 26
p = 6 amu ] =18 amu 
Mn, 25
Note : mass of e– is negligible, so it is not considered in atomic mass.
Atomic Numbers

Final mass  Initial mass Cr, 24 

Step-2 % increment = × 100
Initial mass V, 23 

18  12 
= × 100  50% Ti, 22
12
Sc, 21 
Mosley Experiment (for understanding only)
Moseley (a brilliant student of Rutherford) in 1913 made the first detailed Ca, 20 
0 10 11 12 13 14
study of the characteristic x-ray spectrum emitted by different elements
Frequency  108

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 CHAPTER 2 STRUCTURE OF ATOM (JEE-NEET)
and showed that the square root of the frequency ( v ) of a spectral line is directly related with the
nuclear charge (Z), if the excitation potential is fixed.
When a graph was plotted between v × 10–8 and the atomic number (Z), a straight line was obtained.
The results obtained led to the suggestion that ( v ) must be directly proportional to the atomic number
of an element. v Z
To give accurate results, Mosley modified this equation as v (Z – b)
Where b is a constant and is known as screening constant.
For K and K lines, b = 1.
Hence, v = a(Z – 1) .....(1) where a is proportionality constant.
This equation is very useful for the calculation of Z, if the frequency of K  or K lines are known.

Electromagnetic waves (EM waves) or Radiant Energy

It is the energy transmitted from one body to another in the form of waves and these waves travel in
the space with the same speed as light ( 3 × 108 m/s) and these waves are known as Electromagnetic
waves or radiant energy.
The radiant Energy do not need any medium for propagation.
Example: Radio waves, micro waves, Infra red rays, visible rays, ultraviolet rays, x–rays, gama rays
and cosmic rays.
The radiant Energy have electric and magnetic fields and travel at right angle to these fields.
low  RW MW IR Visible U.V Xray  Cosmic high 
low E Rays high E
longer  Shorter 
10
3×10 Å 7600Å 150Å 0.01Å
14 6 6 –4
3×10 Å 6×10Å 3800Å 0.1Å 10 Å

R O Y G B I V
7600Å 3800Å

A wave is characterized by following six characterstics

= Wave length, a = amplitude
Nature of Electromagnetic Radiation
THEORY
According to Newton, light is propagated in the form of corpuscles i.e minute particles, which are
invisible. Corpuscular theory of light could explain some properties like reflection and refraction but failed
to explain interference and diffraction. To explain these properties Huygens proposed wave theory of
light by stating that an illuminated body sent out a disturbance in the form of waves and these waves
propagate through a medium.

Maxwell modified Huygens wave theory and he proposed that radiant energy is transmitted continuously
in the form of electromagnetic waves requiring no medium.
An Electromagnetic radiation is generated by oscillation of a charged body in a magnetic field or a
magnet in an electric field.
The frequency of the wave is the frequency of oscillation of the oscillating charged particle.
These radiations have electric and magnetic fields that oscillate in directions perpendicular to each other
and perpendicular to the direction in which the wave is travelling.

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 CHAPTER 2 STRUCTURE OF ATOM (JEE-NEET)

Electic Field

Magnetic
Field
l = Wavelength Direction

 
E = ELECTRIC FIELD, B = MAGNETIC FIELD DIRECTION OF WAVE PROPOGATION.
The vertical component of the wave indicates the change in the strength of the electric field. The
Horizontal component of the wave indicates the change in the strength of the magnetic field.

Electromagnetic radiation is characterized by the following characteristics:

The upper most point of the wave is called crest and the lower most portion is called trough. Some of the
terms employed in dealing with the waves are described below.
1. Wavelength  (Lambda) :
It is defined as the distance between two nearest crest or trough. It
is measured in terms of a Å (Angstrom), pm (Picometre), nm
(nanometer), cm(centimetre), m (metre) 1Å = 10–10 m, 1 pm = 10–
12
m, 1nm = 10–9 m, 1cm = 10–2m
2. Frequency () (nu) :
Frequency of a wave is defined as the number of waves which pass
through a point in 1 second. It is measured in terms of Hertz (Hz ),
second–1 , or cycle per second (cps) 1 Hertz = 1 second–1
1
3. Time period (T) : Time taken by a wave to pass through one point. T  second

4. Velocity (c) :Velocity of a wave is defined as distance covered by a wave in 1 second.
c =  /T =  or n = c/ or c = n (s–1) ×  (m) or c = (m s–1)
Since c is constants, i.e. frequency is inversely proportional to 
5. Wave number (  ) ( nu bar) : It is the reciprocal of the wave length that is number of waves
1
present in 1cm   It is measured in terms of cm–1, m–1 etc,

6. Amplitude (a) : The amplitude of a wave is defined as the height of crust or depth of trough.
c  1
Imp. note.    c   
  
Solved questioins
Question : The vividh Bharti station of All India Radio broadcast on a frequency of 1368 Kilo Hertz
Calculate the wave length of the Electromagnetic waves emited by the transmitter.
Ans. As we know velocity of light (c) c = 3 × 108 m/s.
Given  (frequency) = 1368 kHz = 1368 × 103 Hz = 1368 × 103 s–1
c 3 108 m s 1
     = 219.3 m
 1368 103 s 1
Question: Calculate  in cm–1 and  of yellow radiations have wavelength of 5800 Å.
Ans. As we known c = 3 × 108 m/s.
1 1
 
 5800 Å

11
 CHAPTER 2 STRUCTURE OF ATOM (JEE-NEET)
1 108
   { 1Å = 10–8 cm} = cm–1 = 17241.44 cm–1
5800  108 cm 5800
v c
= 3 × 1010 cm s–1× 1.7 × 104 cm–1 = 3 × 1.7 × 1014 = 5.1 × 1014 s–1

Question: How long would it take a radio wave of frequency 6 × 103 sec–1 to travel from mass to the
earth, a distance of 8 × 107 km?
Ans. Distance to be travelled from mass to earth = 8 × 107 km = 8 × 1010 m
 Velocity of EM waves = 3 × 108 m/s
Dis tan ce 8 1010 m
 Time = = = 2.66 × 102 s = 4 min 26 s
Velocity 3 108 m / s
Electromagnetic spectrum:
The arrangement of different types of electromagnetic radiations in the order of increasing wavelengths
or decreasing frequencies is known as electromagnetic spectrum.
Electromagnetic radiations Wave length (Å)
Radio waves 31014 to 3 107
Micro waves 3109 to 3 106
Infrared (IR) 6106 to 7600
Visible 7600 to 3800
Ultra violet (UV) 3800 to 150
X–rays 150 to 0.1
Gamma rays 0.1 to 0.01
Cosmic rays 0.01 to zero
Visible radiation: Visible light is produced from stars, arc lamps and glass enclosed tungsten filament. It
lies in a narrow range of wave lengths between 3800 Ao to 7600 Ao.
A white light is composed of seven different colours. Violet colour corresponds to a radiation of maximum
frequency and minimum wavelength. The red colour corresponds to the radiation of minimum frequency
and maximum wavelength.
Ultraviolet radiation: The radiation with frequencies greater than those of violet light is called ultraviolet
radiation. It is a component of sun’s radiation. Wavelength range of u.v. radiation is 1850A 0 to 3750 A0.
A high-pressure hydrogen or deuterium discharge lamp is the source for u.v. radiation.
Infrared radiation: The radiation with the frequencies lower than those of red light is known as infrared
radiation.
Black body is the best source for infrared radiation. Nernst glower or Globar source is the source for far
infrared radiation. A mixture of zirconium and yttrium oxides shaped in small hollow rod about 2mm in
diameter and 20 mm in length is Nernst glower. The glower is heated to a surface temperature between
15000 C and 20000C. The Globar source of light is a rod of sintered silicon carbide, which is heated to
13000 - 17000C.
Limitations of Electromagnetic Wave Theory :
Electromagnetic wave theory was successful in explaining the properties of light such as interference,
diffraction etc. but it could not explain the following:
(i) The phenomenon of black body radiation.
(ii) The photoelectric effect.
(iii) The variation of heat capacity of solids as a function of temperature.
(iv) The line spectra of atoms with special reference to hydrogen.
These phenomena could be explained only if electromagnetic waves are supposed to have particle
nature.
Black body radiation:
12
 CHAPTER 2 STRUCTURE OF ATOM (JEE-NEET)
When a radiant energy falls on the surface of a body, a part of it is absorbed, a part of it is reflected and
the remaining energy is transmitted.
The body does not absorb all the incident radiant energy completely because ordinary bodies are not
perfect absorbers of radiant energy. The ideal body, which emits and absorbs all frequencies, is called a
black body and the radiation emitted by such a body is called black body radiation. Thus an ideal black
body is perfect absorber and emitter of all kind of electromagnetic radiation.
When solids are heated, they emit radiation over a wide range of wavelengths. For example, when an
iron rod is heated in a furnace, it first turns to dull red and then progressively becomes more and more
intense red as the temperature increases. As this is heated further, the radiation emitted becomes white
and then becomes blue as the temperature becomes very high.
In terms of frequency, it means that the radiation emitted goes from a lower frequency to a higher
frequency as the temperature increases. The red colour lies in the lower frequency region while blue
colour belongs to the higher frequency region of the electromagnetic spectrum.
The exact frequency distribution of the emitted radiation (i.e., intensity versus frequency curve of the
radiation) from a black body depends only on its temperature. At a given temperature, intensity of
radiation emitted increases with decrease of wavelength, reaches a maximum value at a given
wavelength and then starts decreasing with further decrease of wavelength, as shown in Fig.
The above experimental results cannot be explained satisfactorily on the basis of the wave theory of
light.
A graph is obtained by plotting the intensity of radiation against wave length gives the following details
1. The nature of radiation depends upon the temperature of the black body.
2. If the energy emitted is continuous the curve should be as shown by the dotted lines.
3. At a given temperature the intensity of radiation increases with the wavelength, reaches maximum
and then decreases.
4. The intensity of radiation is greatest at the medium wave lengths and least at highest and lowest
wavelengths.
5. As the temperature increases the peak of maximum intensity shifts towards the shorter wavelengths.
10 ultraviolet visible infrared

8
Internsity / (arb, units)

6
T=
max 6000 K

4
5000 K
max
2 4000 K

3000 K
0
0 10 20 30
Wavelength  (m)

Planck’s quantum theory:

In order to explain black body radiation, Max Planck proposed quantum theory of radiation.
Postulates
1. The emission of radiation from a body is due to the vibrations of the charged particles in the body.
2. The radiant energy is emitted or absorbed by a body not continuously but takes place discontinuously
in the form of small packets of energy called quanta.
3. The energy of each quantum of light is directly proportional to the frequency of the radiation.
E ∞ 𝜈 or E = h 𝜈, Where ‘h’ is known as Planck’s constant. The value of ‘h’ is 6.6256 × 10–34 J-sec or
6.6256 × 10–27ergs-sec
4. In case of light, the quantum of energy is called a photon. The total amount of energy emitted or
absorbed by a body will be some whole number multiple of quantum, E = h, where n is an integer

13
 CHAPTER 2 STRUCTURE OF ATOM (JEE-NEET)
such as 1,2,3 . . . . . This means that a body can emit or absorb energy equal to hv, 2hv, 3hv . . . .
Or any other integral multiple of h. This is called quantization of energy.
5. The emitted radiant energy is propagated in the form of waves.
Question: Calculate the energy of a photon of sodium light of wavelength 5.862 × 10 –16 m in Jules.
Ans.  = 5.886 × 10–16 m c = 3 × 108 m s–1
nhc
E = nh or  { n=1}

hc 1 6.6 1034 J  3 10 m s 1 6.6  3
E= or E= 16
=  10 10 J = 3.38 × 10–10 J
 5.862 10 m 5.862
Question : Calculate the frequency & energy of a photon of wave length 4000 Å
Ans.
(a) Calculation of frequency :
 = 4000 Å  = 4000 × 10–10 m
c 3 108 m / s
  = 0.75 × 1015 s–1 = 7.5 × 1014 s–1
 4 107 m
(b) Calculaion of energy :
E = h = 6.626 × 10–34 J × 7.5 × 1014 s–1 = 4.96 × 10–19 J
Question : Calculate the l and frequency of a photon having an energy of 2 electron volt
Ans.  1eV = 1.602 × 10–19 J  2eV = 3.204 × 10–19 J = E
hc hc
(a) Calculation of wavelength () : E or 
 E
6.626 1034 Js  3 108 m s1
 = = 6.204 × 10–7 m
3.204 1019 J
c 3 108 m s 1
(b) Calculation of frequency () :   = = 0.48 × 1015 s–1 = 4.8 × 1014 s–1
 6.204 107 m
Question : Which has a higher energy ?
(a) A photon of violet light with wave length 4000 Å
(b) A photon of red light with wave length 7000 Å
Ans.
hc 6.626 1034 J s 3 108 m s1
(a) Violet light : Eviolet = Eviolet = = 4.97 × 10–19 J
 4000 1010 m
hc 6.626 1034 J s 3 108 m s1
(b) Red light : Ered = Ered = = 2.8 × 10–19 J
 7000 1010 m
So, Eviolet > Ered

Question.How many photons of lights having a wave length of 5000 Å are necessary to provide 1 Joule
of energy.
nhc E 1J  5000  10 10 m
Ans.  E =  n n= = 2.5 × 1018 photons
 hc 6.626  10 34 J s  3  108 m s 1
Photoelectric Effect:
In 1887, H. Hertz performed a very interesting experiment in which electrons (or electric current) were
ejected when certain metals (for example potassium, rubidium, caesium etc.) were exposed to a beam
of light as shown in Fig.2.9. The phenomenon is called Photoelectric effect. The electrons emitted are
called photoelectron.The results observed in this experiment were:

(i) The electrons are ejected from the metal surface as soon as the beam of light strikes the surface, i.e.,
there is no time lag between the striking of light beam and the ejection of electrons from the metal
surface.

14
 CHAPTER 2 STRUCTURE OF ATOM (JEE-NEET)
(ii) The number of electrons ejected is proportional to the intensity or brightness of light.
(iii) For each metal, there is a characteristic minimum frequency,0 (also known as threshold frequency)
below which photoelectric effect is not observed. At a frequency  >0, the ejected electrons come out
with certain kinetic energy. The kinetic energies of these electrons increase with the increase of
frequency of the light used.
All the above results could not be explained on the basis of laws of classical physics. According to latter,
the energy content of the beam of light depends upon the brightness of the light. In other words,
number of electrons ejected and kinetic energy associated with them should depend on the brightness
of light. It has been observed that though the number of electrons ejected does depend upon the
brightness of light, the kinetic energy of the ejected electrons does not.
On increasing the intensity of light of a given frequency, the number of photons striking the surface is
increased but kinetic energy remains unchanged. Consequently greater the intensity of light, higher is
the number of electrons ejected.
E = hv0 E > hv0

Incident Photoelectron
beam

K. Emax = 0
K. E = 0

Metal
Metal
e
Photoelectrons

E = hv
Photoelectrons

K.E of
K.E of

V0 Slope = h
ETh = hv0

V0  V  Intensity (If ETh > ETh)

For example, red light [ = (4.3 to 4.6) × 1014 Hz] of any brightness (intensity) may shine on a piece of
Potassium metal for hours but no photoelectrons are ejected. But, as soon as even a very weak yellow
light ( = 5.1–5.2 × 1014 Hz) shines on the potassium metal, the photoelectric effect is observed. The
threshold frequency (0) for potassium metal is 5.0× 1014 Hz.
Einstein (1905) was able to explain the photoelectric effect using Planck’s quantum theory of
electromagnetic radiation as a starting point, shining a beam of light on to a metal surface can,
therefore, be viewed as shooting a beam of particles, the photons. When a photon of sufficient energy
strikes an electron in the atom of the metal, it transfers its energy instantaneously to the electron
during the collision and the electron is ejected without any time lag or delay. Greater the energy
possessed by the photon, greater will be transfer of energy to the electron and greater the kinetic
energy of the ejected electron. In other words, kinetic energy of the ejected electron is proportional to
the frequency of the electromagnetic radiation. Since the striking photon has energy equal to hand
the minimum energy required to eject the electron is h0 (also called work function, W0; Table 2.2),
then the difference in energy (h – h0) is transferred as the kinetic energy of the photoelectron.
Following the conservation of energy principle, the kinetic energy of the ejected electron is given by the
equation 2.7.

hv = h𝜈0 + KE

Where me is the mass of the electron and v is the velocity associated with the ejected electron. Lastly,
a more intense beam of light consists of larger number of photons, consequently the number of
electrons ejected is also larger as compared to that in an experiment in which a beam of weaker
intensity of light is employed.

Electromagnetic spectrum or EM spectrum :

15
 CHAPTER 2 STRUCTURE OF ATOM (JEE-NEET)
The arrangement obtained by arranging various types of EM waves in orders of their increasing
frequency or decreasing wavelength is called as EM SPECTRUM
Spectrum :
When a radiation is passed through a spectroscope for the dispersion of the radiation, the pattern
(photograph) obtained on the screen (photographic plate) is called as spectrum of the given radiation
Classification of Sepctrum

(1) Emission (2) Absroption

(a) Continuous (b) line (c) band (a) line (b) band

(1) Emissions spectrum :

When the radiation emitted from Incandescence source (eg. from the candle, sun, tubelight, burner,
bulb, or by passing electric discharge through a gas at low pressure, by heating some substance at
(high temp) is passed directly through the prism and the pattern obtained on the screen is known as
emission spectrum
(a) Emission continuous spectrum or continuous spectrum :
When a narrow beam of white light is passed through a prism, it is dispersed into 7 colours from violet
to Red.
Screen U V Region
Narrow beam
of white light V
I
B
G Visible
region
y

O
R
Infra red region
(b) Emission line spectrum :
When an atomic gas is raised to incandescence source or subjected to electrical excitation, it first
absorbs energy & then gives it out as radiation. On examining these radiation through a spectro scope
a spectrum is obtained which have well defined lines, each corresponding to a definite wave length &
these lines are separated from each other by dark space.
This type of Emission spectrum is called as Emission line spectrum.
Screen
Line Spectrum

Incandescence
source
Atomic Gas

Stoped after
a short Slit system
period
Special Note :
1. No two Elements will have identical line spectrum since no two elements have identical energy level
therefore the line spectrum of the elements are described as finger prints differing from each other like
the finger prints of the human beings.
2. Since line spectrum is obtained by the emission of energy through the atoms of the element
therefore line spectrum is also called as atomic spectrum.
(c) Emission band spectrum:

16
 CHAPTER 2 STRUCTURE OF ATOM (JEE-NEET)
If molecular form of the gas is used, it first absorbs energy for not only electron transition but for
rotational vibrational and electron translation then emits radiations.
On examining these radiations through a spectroscope a spectrum is obtained on the screen, which
consists group of closely packed lines called Bands, therefore this type of Emission spectrum is called
as emission band spectrum. Bands are separated from each other by dark space.
Screen

Band Spectrum
Coloured

Moleculus
Coloured

Gas
Incandescence
source Coloured

Stoped after Coloured

a short
period
Note : Since band spectrum are caused by molecules therefore band spectrum are also called as
molecular spectrum.

Line spectrum Band spectrum

The line spectrum has sharp, distinct well The band spectrum has many closed lines.
defined lines.
The line spectrum is the characteristic of The band spectrum is characteristic of
atoms and is also called atomic spectrum. molecules and is also called molecular
spectrum.
The line spectrum is due to transition of The band spectrum is due to vibrations and
electrons in an atom. rotations of atoms in a molecule
The line spectrum is given by inert gases, The band spectrum is given by hot metals
metal vapours and atomised nonmetals. and molecular nonmetals.

(2) Absorption spectrum :

When white light is first passed through a solution or vapours of a chemical substance or gas and then
analyzed by spectroscope, it is observed that some dark lines are obtained in otherwise continuous
spectrum.
This type of spectrum is called as Absorption spectrum.
Screen
Coloured
Coloured
Incandescence
source
Gas
Coloured
Coloured

If white light is passed through atomic gas then the obtained spectrum is called as Absorption line
spectrum.
If white light is passed through molecular gas then the obtained spectrum is called as Absorption band
spectrum.
EMISSION SPECTRA ABSORPTION SPECTRA
Emission spectrum is obtained when the radiation Absorption spectrum is obtained when the
from the source are directly analyses in the white light is first passed through the substance
spectroscope. and the transmitted light is analyzed in the
spectroscope.
It consists of bright coloured lines separated by It consists of dark lines in the otherwise
dark spaces. continuous spectrum.

17
 CHAPTER 2 STRUCTURE OF ATOM (JEE-NEET)
Emission spectrum can be continuous spectrum Absorption spectrum is always discontinuous
(if source emits white light) or discontinuous, spectrum of dark lines.
i.e., line spectrum if source emits some coloured
radiation.
Hydrogen line spectrum or Hydrogen spectrum :
When an electric excitation is applied on hydrogen atomic gas at Low pressure, a bluish light is
emitted. when a ray of this light is passed through a prism, a spectrum of several isolated sharp line is
obtained. The wavelength of various lines show that spectrum lines lie in visible, Ultraviolet and Infra-
red region. These lines are grouped into different series.
7 Q
6
Far I.R. region P
Humphery series
5 O
I.R. region
P fund series
4 N
I.R. region
Bracket series
3 M
Infra Red region
or
Paschen series
2 L
Visible region
or
Balmer series
1 K
Ultra violet region
or
Lyman series

Series Discovered by regions n2- n1 Trick of

no. of lines
lyman lyman U.V. region n2 =2, 3, 4 / n1=1 (n2 – 1)
Balmer Balmer Visible region n2 = 3,4,5 / n1 =2 (n2 – 2)
Paschen Paschen Infra red (I. R.) n2=4, 5, 6 / n1 =3 (n2 – 3)
Bracket Bracket I. R. region n2 =5, 6, 7 / n1 =4 (n2 – 4)
Pfund Pfund I.R. region n2 =6, 7 / n1 = 5 (n2 – 5)
Humphery Humphery far I.R. region n2 = 7 / n 1 = 6 (n2 – 6)

Question : In a hydrogen spectrum if electron moves from 7 to 1 orbit by transition in multi steps then
find out the total number of lines in the spectrum.
Ans.
Lyman = (n1 – 1) = 7 – 1 = 6
Balmer = (n2 – 2) = 7 – 2 = 5
Paschen = (n2 – 3) = 7 – 3 = 4
Bracket = (n2 – 4) = 7 – 4 = 3
Pfund = (n2 – 5) = 7 – 5 = 2
Humphrey = (n2 – 6) = 7 – 6 = 1
Total = 21
Total number of lines can be calculated as follows :
 n2  n1   n2  n1   1  7  1 6  1
42
Total number of lines =    21
2 2 2
Question: In a hydrogen spectrum if electron moves from6Th to 2nd by transition in multi steps then
find out the number of lines in spectrum
Ans. Total number of line = 4 + 3 + 2 + 1 + 0 = 10
or

18
 CHAPTER 2 STRUCTURE OF ATOM (JEE-NEET)
 n2  n1   n2  n1   1  6  2  4  1 45
Total number of lines = = =  10
2 2 2
Question : In a hydrogen spectrum if electron moves from 6th to 3rd orbit by transition in multi steps
then find out the following steps :
(a) Total number of lines in spectrum (b) Total number of lines in U.V. region
(c) Total number of lines in visible region (d) Total number of lines in IR region
Ans. (a) Calculation of total number of lines :
 n2  n1   n2  n1   1  6  3  6  3  1
3 4
= = = =6
2 2 2
(b) Calculation of number of lines present in U.V. region.
e– moves from 6th to 3rd orbit in multisteps.
For U.V. region, e– should be comes into 1st shell. So there is number of lines in U.V. region is zero.
(c) Calculation of total number of lines in visible region.
For visible region, e– should be comes into 2nd shell, so there is number lines in visible region zero.
(d) Calculation of total number of lines in I.R. region.
In I.R. region, Paschen, Bracket and Pfund sereis are present.
Number of lines in Paschen series = n2 – 3 = 6 – 3 = 3
Number of lines in Bracket series = n2 – 4 = 6 – 4 = 2
Number of lines in Pfund series = n2 – 5 = 6 – 5 = 1
So total number of lines =3+2+1=6
Question : In Balmer series of H atom/spectrum which electronic transitions represents 3 rd line ?
Ans. In Balmer series
3rd to 2nd  1 line
4 Th
to 2 nd
 2 line
5Th to 2nd  3 line
Infinite to 2 nd
 Last line or limiting line
So, answer is 5nd to 2nd line  3rd line

Question : In H atom if e– moves, from nth orbit to 1st orbit by transition in multi steps, if there are
total number of lines in spectrum are 10 then find out the value of n
 n2  n1   n2  n1   1
Ans. Total number of lines =
2
 n2  1 n2 
So, 10 =
2
i.e. n22
– n2 – 20 = 0
n22 – 5n2 + 4n2 – 20 = 0
n2 (n2 –5) + 4 (n2 – 5) = 0
(n2 + 4) (n2 –5) = 0
n2 = 5
Rydberg formula :
In 1890, Rydberg gave a very simplest theoretical Equation for the calculation of the wavelength of
various lines of hydrogen like spectrum and the equation is
1 1 1
  = RZ 2  2  2 
  n1 n2 
R = Rydberg constant = 109678 cm –1 ~ 109700 cm–1
= 9.12 × 10–6 cm
n1 and n2 are orbits and for a particular series n 1 is constant and n2 varies.
For Lyman n1 = 1, n2 = 2, 3, 4,.....
19
 CHAPTER 2 STRUCTURE OF ATOM (JEE-NEET)
For Balmer n1 = 2, n2 = 3, 4, 5,....
For Paschen n1 = 3, n2 = 4, 5, 6,....
For Bracket n1 = 4, n2 = 5, 6, 7,...
For Pfund n1 = 5, n2 = 6, 7, 8,...
For Humphery n1 = 6, n2 = 7, 8, 9,...
Derivations of Rydberg formula:
E = En2  En1

2 2 mK 2 Z 2 e4  2 2 mK 2 e4 Z 2  2 2 mK 2 Z 2 e 4 2 2 mK 2 e 4 Z 2
E =    = 
n22 h 2  n12 h 2  n12 h 2 n22 h 2
hc
E = h 


hc 2 2 mK 2 Z 2 e4 1 1 1 2 2 mK 2 e4 Z 2 1 1
=  2  2  =  2  2
 h2  n1 n2   ch3  n1 n2 
2 2 mK 2 e4
Where is a constant which is equal to rydberg constant (R).
ch3
1 1 1
= RZ  2  2 
2

  n1 n2 

Question : Calculate the wavelength of 1st line of Balmer series in Hydrogen spectrum.
Ans. For first line of Balmer series
n1 = 2, n2 = 3
1 1 1 1 9  4  1 5
 R(1)2      R    R 
 4 9   36    36 
36 36 1
    
5R 5 R
36
=  9.12 106 cm
5
= 65.66 × 10–6 cm { 1 Å = 10–8cm,  1Cm = 108 Å }
= 65.66 × 10– 6 × 108 Å
= 65.66 × 102 Å = 6566 Å
Question: Calculate the frequency of the last line of the lyman series in hydrogen spectrum. For last
line of Lyman series n1= 1, n2 = 
1  1 1  1 1  1
= Rz2  2  2  = R   0  =R
  n1 n2   1  
1
 = 109678 cm–1

C 1
 = =C× =C × R
 
= 3 × 108 m s–1 × 1096700 cm—1
= 3 × 1010 cm s–1 × 1096700 cm–1
= 3.29 × 1015 sec–1
Question : Calculate Wavelength of 3rd line of Bracket series in hydrogen spectrum.
Ans. For 3rd line of Bracket series n1 = 4, n2 = 7
1  1 1  1 1 1 1  49  16 
= RZ2  2  2   = R    = R 
  (4) (7)   16 49    16  49 

20
 CHAPTER 2 STRUCTURE OF ATOM (JEE-NEET)
1 33 1 33 R 784
 =R  = Therefore,  =
 784  784 33R

Question : The wave number of 1St line of Balmer series of hydrogen spectrum is 15200 cm–1 The
wave number of 1St line of Balmer series of Li+2 spectrum will be ?
Sol. Wave number of Ist line of Balmer series of hydrogen spectrum.
1  1 1   1 1   1 1 
   RZ 2  2  2  or   Z2  R  2  for H, Z = 1   R  2  2  = 15200 cm–1
  n1 n2 
2
 n1 n2   n1 n2 
Wave number of Ist line of Balmer series of Li+2 ion is.
 1 1 
  Z2  R 2
 2 { Z = 3 for Li+2 }
 n1 n2 
  = 32 × 15200 = 9 × 15200 = 136800 cm–1

Question : Calculate the ratio of maximum of Lyman & Balmer series ?

1
Ans. E 

Maximum  of Lyman series 1st line of Lyman series

Maximum  of Balmer series 1st line of Balmer series
1 1 1  1 1  3
R 2  2  R   R 
Lyman  L 1 2  = 1 4  =  4  = 27
 =
Balmer 1 1 1 1 1 5 5
R 2  2  R   R 
B  2 3   4 9   
36
L 5
  
B 27
Question : A certain electronic transition from an excited state to Ground state of the Hydrogen atom
in one or more steps gives rise of 5 lines in the ultra violet region of the spectrum.How many lines does
this transition produce in the Infra red region of the spectrum?
Ans. (Lyman Series) ultra violet region : 5 Lines i.e. e– is coming from 6th to 1st Orbit
n2 –1 = 5  n2 = 6
Infrared region line
(i) Paschen series = (6–3) = 3
(ii) Bracket = (6–4) = 2
(iii) Pfund = (6–5) = 1
Total Number of lines are = 6

Bohr's Atomic Model

Some Important formulae :
kq1q2 mv 2
Coulombic force = , Centrifugal force =
r2 r
Angular momentum = mvr
It is a quantum mechanical model. This model was based on quantum theory of radiation and Classical
law of physics.
The important postulates on which Bohr's Model is based are the following :
1st Postulate :
Atoms has a nucleus where all protons and neutrons are present.
The size of nucleus is very small and it is present at the centre of the atom.
2nd Postulate :

21
 CHAPTER 2 STRUCTURE OF ATOM (JEE-NEET)
Negatively charged electron are revolving around the nucleus in the same way as the planets are
revolving around the sun.
The path of electron is circular.
The attraction force (Coloumbic or electrostatic force) between nucleus and electron is equal to the
centrifugal force on electron. i.e. Attraction force towards nucleus = centrifugal force.
3rd Postulate :
h
Electrons can revolve only on those orbits whose angular momentum (mvr) is integral multiple of
2
Where h = Plank's constant,  = Constant
nh
i.e. = mvr = n = Whole number
2
h h h h
Angular momentum can have values such as ,2 ,3 ,4 , ........but cannot have fractional
2 2 2 2
h h
values such as 1.5 , 1.2 , .......
2 2
The orbits in which electron can revolve are known as stationary Orbits.
4th Postulate:
By the expiry of time, if electons remains in the stationary state then it does not lose energy. Such a
state is called as "GROUND STATE".
5th Postulate:
Each stationary orbit is associated with definite amount of energy therefore these orbits are also called
as energy levels and are numbered as 1, 2, 3, 4, 5, .... or K, L, M, N, O, ..... from the nucleus
outwards.
E1 < E2 < E3 < E4 < E5............ and
(E2 – E1) > (E3 – E2) > (E4 – E3] > (E5 – E4) >..........
6th Postulate: Shell 5
The emission or absorption of energy in the form of radiation can only occur Shell 4
Shell 3
when electron jumps from one stationary state to another.
Shell 2
Energy is absorbed when electron Jumps from inner to outer orbit and is Shell 1
emitted when electron moves from outer to inner orbit.
Nucleus +
When electron moves from inner to outer orbit by absorbing definite amount
of energy the new state of the e– is said to be excited state of the electron. Shell K
If electrons is in 1st excited state it means now electron is exist in 2nd orbits. Shell L
Similarly if electrons is in 2nd excited state it means now electron is exist in Shell M
3 orbit and so on .........
rd Shell N
Shell O
Ionization energy :
The required energy to liberate an electron from the ground state of an isolated atom is called the
ionization energy.
Separation energy :
v(Tangential velocity)
Required energy to escape out an electron from its excited state
is called as separation energy.
Application of Bohr's Model :
e¯
1. Radius of various orbits (shell)
n2 h2
Derivation r 
42 mKZe2 Coulambic or Electrostatic
Kqq
kq1q2 force
1 2

Columbic force = +Ze Nucles r

2

r2
K .Ze.e
=
r2
22
 CHAPTER 2 STRUCTURE OF ATOM (JEE-NEET)
KZe 2
= (Where K is Constant)
r2
K = 9 × 109 Nm2 /coulumb2
As we know that Coulombic force = Centripetal force
KZe 2 mv 2 2 KZe2
 v  ......(1)
r2 r mr
nh nh
As we know that mvr =  v= ......(2)
2 2mr
Now putting the value of v from eq.(2) to eq.(1)
2
 nh  KZe2
  
 2mr  mr
n2 h2 KZe2

4 2 m 2 r 2 mr
n2 h2
r ......(3)
42 m  KZe2
Putting the value of  h, m, K, & e (Constants) in the above eq (3)
n2
r = 0.529 × 10–8 × cm { 1Å = 10–10m = 10–8 cm}
Z
n2 0
rn  0.529 A
Z
This formula is only applicable for hydrogen and hydrogen like species i.e. species contains single
electron.
Question :Calculate the radius of 1st,2nd,3rd,4th Bohr's Orbit of hydrogen.
n2
Ans. Radius of Bohr's orbit r = 0.529 ×
Z
12
(a) Radius of Ist orbit : r = 0.529 × = 0.529A0
1
22
(b) Radius of IInd orbit : r = 0.529 × = 0.529 × 4 = 2.116A0
1
32
(c) Radius of IIIrd orbit : r = 0.529 × = 0.529 × 9 = 4.761A0
1
42
(d) Radius of 4th orbit : r = 0.529 × = 0.529 × 16 = 8.464A0
1
n2 0
Question : Calculate the radius ratio of 3rd & 5th orbit of He+ r = 0.529 × A
Z
Atomic Number of He = 2
 3
2
9 (5) 2 25
Ans.  r3 = 0.529 × = 0.529 × r5 = 0.529 × = 0.529 ×
2 2 2 2
 3
2

r3 0.529 
r3
2 9
    r3 : r5 = 9 : 25
 5
2
r5 r5 25
0.529 
2
Question: Calculate the radius ratio of 2nd orbit of hydrogen and 3rd orbit Li+2
Ans. Atomic number of H = 1 Atomic number of Li = 3
22
2nd orbit radius of Hydrogen (r2)H = 0.529 ×
1

23
 CHAPTER 2 STRUCTURE OF ATOM (JEE-NEET)
32
3rd orbit radius of Li+2 = 0.529 ×
3
22
 r2 H 0.529 
  1 =4   r2 H :  r3 Li2 = 4 : 3
 r3 Li2 0.529  32 3
3
Question: The ratio of the radius of two Bohr's orbit of Li +2 is 1:9 What Would be there nomenclature
(1) K & L (2) L & M (3) K & M (4) K & N
2
n
0.529 
rx 1 3
Ans.  
ry 9 n2
0.529 
3
x2 1 x 1
=  x=1 y=3
y2 9 y 3
Question : Calculate the radius of 2nd excited state of Li +2
Ans. 2nd excited state, means e– is present in 3rd shell so,
3 3
r3 = 0.529 × = 0.529 × 3 A° = 1.587A0
3
Question : Calculate the radius ratio of 2nd excited state of H & 1st excited state of Li+2
Ans. 2nd excited state, means e– is present in 3rd shell of hydrogen

 3
2

r3 = 0.529 × = 0.529 × 9
1
1st excited state, means e– exist in 2nd shell of Li+2

 2
2
4
r2 = 0.529 × = 0.529 ×
3 3
nd
radius of 2 excited state of hydrogen  r3  H 27
= = 
radius of 1st excited state of Li +2  r2  Li
2 4
2. Energy of an electron :
Let the total energy of an electron be E. It is the sum of kinetic and potential Energy.
i.e. E = K.E.+ P.E.
 1 2   Kq1q2 
mv     Kze 2 
E =  2   r 

 P. E .   
 r 
( K .E.) ( P.E.)
1 2  K .Ze.e  1 2 KZe 2
E= mv     = mv 
2  r  2 r
Now putting the value of mv2 from eq. (1)
KZe 2 KZe 2 KZe 2
E=  E = –
2r r 2r
Now putting the value of r from eq. (3)
KZe2  42 mKZe2 22 m  K 2 Z 2 e4
En =  E n = 
2n2 h2 n2 h2
Now putting the value of p, K, e, m, h, we get :
21.69 1019  Z 2
E=  J / atom
n2

24
 CHAPTER 2 STRUCTURE OF ATOM (JEE-NEET)
Z2
E = – 13.6 × 2 e V / atom
n
This formula is applicable for hydrogen atom & hydrogen like species i.e. single electron species.
Since n can have only integral values, it follows that total energy of the e– is quantised.
The –ve sign indicates that the e– is under attraction towards nucleus.

Some extra points :

KZe 2 1
(i) K.E = i.e. K.E.  On increasing radius, K.E. decreases.
2r r
KZe 2 1
(ii) P. E. = – i.e. P.E.  – On increasing radius, P.E. increases.
r r
KZe 2 1
(iii) E = – i.e. E. –
2r r
Results : On in incresing radius, total energry increases.
P.E = –2KE
KE = –E
P.E = 2E
Energy diff. between two energy levels :
1 1
En2  En1 = – 13.6 × Z2  2  2 
 2
n n1 

For example For H :

E2 – E1 = –3.4 + 13.6 = 10.2 eV
E3 – E2 = –1.51 + 3.4 = 1.89 eV
E4 – E3 = – 0.85 + 1.51 = 0.66 eV
E5 – E4 = – 0.54 + 0.85 = 0.16 eV
i.e. (E2 – E1) > (E3 – E2) > (E4 – E3) > (E5 – E4).....
Energy level for H atom can be represented as follows :
n = 6 or P E6 = – 0.38eV
n = 5 or O E5 = –0.54 eV
n = 4 or N E4 = – 0.85 eV E5 – E4 = 0.16 eV
n = 3 or M E3 = – 1.51 eV E4 – E3 = 0.66 eV
n = 2 or L E2 = – 3.4 eV E3 – E2 = 1.89 eV
n = 1 or K E1 = – 13.6 eV E2 – E1 = 10.2 eV
SOLVED QUESTION
Question : Calculate the energy of Li+2 atom for 2nd excited state
Z2
Ans. E = –13.6 ×
n2
 Z = 3 and e– exist in 2nd excited state, means e– present in 3rd shell i.e. n = 3
 3
2

 E = –13.6 × = – 13.6 eV/atom

 3
2

Qusstion :Calculate the ratio of energies of He+ for 1St & 2nd excited state .
Ans.(He+) 1st Excited state : (He+)2nd Excited state
i.e. (He+)2nd shell : (He+)3rd shell
 2  2
2 2
4 4 1 1
–13.6 × : – 13.6 ×  :  :  9:4
 2  3
2 2
4 9 4 9
Question : If the P.E. of an electron is –6.8 eV in hydrogen atom then find out K.E., total energy & the
orbit where electron exist & radius of orbit
25
 CHAPTER 2 STRUCTURE OF ATOM (JEE-NEET)
Ans. 1. P.E. = –2K.E.
–6.8 = –2K.E.
6.8
= K.E.
2
K.E. = 3.4 eV
2. T.E. = – K.E.
= – 3.4 eV
3. Orbit = 2nd
Z2
 E = – 13.6 ×
n2
12
 3.4 = – 13.6 ×
n2
13.6
 n2 = =4 i.e. n = 2
3.4
n2
4. r = 0.529 × Å
z
 2
2

r = 0.529 × Å = 0.529 × 4Å = 2.116 Å

1
Question :The ionization energy for the hydrogen atom is 13.6 eV then the required energy in ev to
excite it from the ground state to 1st excited state
Ans. Ionization energy = 13.6 eV
i.e. energy is ground state = – 13.6 eV
Energy of Ist excited state
i.e. 2nd orbit = = –3.4 eV
so, E2 – E1 = – 3.4 + 13.6 = 10.2 eV
3. Velocity of an electron :
Since Coulombic force = Centrifugal force
KZe 2 mv 2 KZe 2
=  = mv2
r2 r r
KZe2 = mv2r
KZe 2
= (mvr)(v)
nh
Now putting the value of Angular momentum m.v.r. =
2
nh 2KZe2
KZe2 = (v ) V 
2 nh
Now putting the value of , k, e & h
Z
V = 2.188 × 108 × cm/s
n
Question : If the total energy of an electron is –1.51 eV in hydrogen atom then find out K.E, P.E, orbit,
radius and Velocity of the electron in that orbit.
Ans. Given E = –1.5 eV
(i) E = – KE
K.E = – E { Z = 1} = 1.51 ev
(ii) PE = – 2 × 1.51 = – 2.02 ev
(iii) Orbit = 3rd
Z2 12
E = – 13.6 × ev – 1.51 = – 13.6 ×  n=3
n2 n2

26
 CHAPTER 2 STRUCTURE OF ATOM (JEE-NEET)
3 3
(iv) r = 0.529 × = 0.529 × 9 = 4.761Å
1
1
v = 2.188 × 108 × cm/s = = 0.729 × 108 cm/ s
3
Explanation of Hydrogen Spectrum by Bohr’s Theory:
Bohr’s theory successfully explains the origin of lines in hydrogen emission spectrum. Hydrogen atom
has only one electron. It is present in K shell of the atom (n = 1). When hydrogen gas is subjected to
electric discharge, energy is supplied. The molecules absorb energy and split into atoms. The electrons
in different atoms absorb different amounts of energies. By the absorption of energy, the electrons are
excited to different higher energy levels.
Atoms in the excited state are unstable. Therefore, the electrons jump back into different lower energy
states in one or several steps. In each step, the energy is emitted in the form of radiation and is
indicated by a line.

Each line has a definite frequency and thus the emission spectrum of hydrogen has many spectral lines.
The spectral lines in Lyman series are obtained in UV region, when electron returns to the ground state
from higher energy levels 2, 3, 4, 5 ......... and so on.
The lines in Balmer series are obtained in visible region when electron returns to second energy level
from higher energy levels 3, 4, 5, 6 and so on.
The lines in Paschen series are obtained in near infrared region, when electron returns to third energy
level from higher energy levels 4, 5, 6.... And so on.
The lines in Brackett series are obtained in mid infrared region when electron returns to fourth energy
level from higher energy levels 5, 6, 7 . . . and so on.
The lines in Pfund series are obtained in far infrared region when electron returns to the fifth energy
level from higher energy levels 6, 7. . . . And so on.
The maximum number of lines produced when electrons jumps from nth level to ground level is equal to,
n(n−1)
Or ∑(n2 − n1 )
2
Where, n2 = higher energy level, n1 = lower energy level.
n = difference in the two energy levels.
Merits and demerits of Bohr’s Atomic model:
1. Bohr’s model explains the stability of the atom. The electron revolving in a stationary orbit does not
lose energy and hence it remains in the orbit forever.
2. Bohr’s theory successfully explains the atomic spectrum of hydrogen.
3. This theory not only explains hydrogen spectrum but also explains the spectra of one electron species
such as He+, Li2+ and Be3+ etc.
4. The experimentally determined frequencies of spectral lines are in close agreement with those
calculated by Bohr’s theory.
5. The value of Rydberg constant for hydrogen calculated from Bohr’s equation tallies with the value
determined experimentally.
Limitations of Bohr’s model:
1. Bohr’s theory fails to explain the spectra of multi-electron atoms.
2. It could not explain the fine structure of atomic spectrum.
3. It does not explain the splitting of spectral lines into a group of finer lines under the influence of
magnetic field (Zeeman Effect) and electric field (Stark effect).
4. Bohr’s theory predicts definite orbits for revolving electron. It is against the wave nature of electron.
5. Bohr’s theory is not in agreement with Heisenberg’s uncertainty principle.

27
 CHAPTER 2 STRUCTURE OF ATOM (JEE-NEET)
Sommerfeld’s Atomic Model: (additional)
It is an extension of Bohr’s model. In this model, the electrons in an atom revolve around the nuclei in
elliptical orbit. The circular path is a special case of ellipse. Association of elliptical orbits with circular
orbits explains the fine line spectrum of atoms.
The main postulates are:
(i) The motion of electron in closed circular orbits is influenced by its n=3, K = 3
n=3, K = 2
own nucleus and is set up into closed elliptical paths of definite n=3, K = 1
energy levels.
(ii) The nucleus is one of the foci for all these orbits.
(iii) The angular momentum of electron in closed elliptical paths is also Nucleus

quantized i.e. k (h/2), where k is another integer except zero.

n length of major axis
(iv)The ratio  suggests for the possible number somerfield’s orbit in H atom
k length of min or axis
of subshells in a shell.
(v) Possible values of k for n = 4 are 1, 2, 3, 4 respectively. For any given value of n, k cannot be zero as
in that case, the ellipse would degenerate into a straight line passing through the nucleus. When n =
k, path becomes circular.
DUAL NATURE OF MATTER (DE BROGLIE’S WAVE THEORY)
Light exhibits different properties such as diffraction, interference, photoelectric effect, Compton Effect,
reflection and refraction. The phenomenon of diffraction and interference can be explained by the wave
nature of the light. However, the phenomenon of photoelectric effect and Compton Effect can be
explained by the particle nature of the light. Thus, light has dual nature. De-Broglie proposed that matter
like radiation, should also exhibit dual behaviour.

Any material particle in motion is a wave. All micro particles like electrons, protons, atoms and
molecules moving with high velocities are associated with wave nature.
hc
Einstein’s generalization of Planck’s theory is given as, E = hν =
λ
Einstein’s mass energy relationship is E = mc2
hc h h
Equating above two equations, we get = mc 2 or = mc or λ =
λ λ mc
h
Where ‘c’ is the velocity of light. If the velocity of micro particle is ‘v’ then, λ=
mV
This is de Broglie’s equation, Where ‘λ’ is the de Broglie’s wave length or material wave length or particle
wavelength, ‘m’ is the mass of the moving particle and ‘h’ is Planck’s constant.
Thus a moving electron is associated with a definite wave length.
Momentum (P) is given as product of mass and velocity.
h
P = mv or λ = Here λ signifies wave nature and P signifies particle nature.
P
This is applicable to micro particles like electron, proton, etc., and not applicable for macro bodies like
cricket ball, bullet etc.
The electron moving with high speed possesses both the particle nature and the wave nature. The waves
associated with material particles are known as matter waves or particle waves.
Let the Kinetic Energy of the particle of mass ‘m’ be K.E.
1
K. E = mv 2
2
2K. E. = mv 2
2K. E. m = m2 v 2
⇒ √2K. E m = mV = P
h h
λ= =
P √2 K. Em

28
 CHAPTER 2 STRUCTURE OF ATOM (JEE-NEET)
Modifications made by Davisson and Germer:
Davisson and Germer demonstrated the physical reality of the wave nature of electrons by showing that
a beam of electrons could also diffracted by crystals just like light of X-rays. Let a charged particle, say
an electron, be accelerated with a potential of V, then kinetic energy 1/2mv2 acquired by this electron
due to the electric field shall be equal to the electrical force.
1 1
mv2 = eV  m2v2 = meV; m2v2 = 2meV
2 2
 mv = √2meV  mv = λ (According to de Broglie)
h

 mv = hλ = √2meV  λ = √2meV
h

De-Broglie’s Concept and Bohr’s theory: Two types of waves are possible for an electron moving
around the nucleus in the circular path
a) A standing or stationary, or non-energy radiating wave
b) A non-stationary or energy radiating wave

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. It means there is constructive interference of electron waves.
The necessary condition to get an electron wave in phase is that the circumference of the Bohr’s orbit is
equal to the integral (whole number) multiple of the wavelength of the electron wave.
i.e.,2 πr = nλ
2πr
λ= (∴ n =Integer or whole number)
n
h
We know that, λ =
mv
2πr h nh
⇒= ⇒ mvr =
n mv 2π
Hence de-Broglie’s theory and Bohr’s theory are in agreement with each other. i.e., de-Broglie’s concept
supports the postulate of Bohr that the angular momentum of an electron in an orbit is quantized.
In case if the circumference of the electron orbit (2πr) is bigger or smaller than nλ, the
electron wave is said to be out of phase. Then there occurs destructive interference of electron waves
causing radiation of energy, such an orbit cannot exist.

a b

Question : The mass of a particle is 1 mg and its velocity is 4.5 × 105 cm per second. What should be
the wavelength of this particle if h = 6.652 × 10 –27 erg second.
(1) 1.4722 × 10–24 cm (2) 1.4722 × 10–29 cm (3) 1.4722 × 10–32 cm (4) 1.4722 × 10–34 cm
Ans. b Given that
1
m = 1 mg = 1 × 10–3 g c=
10
c = 4.5 × 105 cm/s
h = 6.652 × 10–27 erg s
h 6.652 1027 6.652 1029
  =  = cm = 1.4722 × 10–29 cm
mc 1 103  4.5 105 4.5
Question : Which of the following should be the wavelength of an electron it its mass is 9.1× 10 –31 Kg
and its velocity is 1/10 of that of light and the value of h is 6.6252× 10 –24 joule second?
(1) 2.446 × 10–7 metre (2) 2.246 × 10–9 metre
(3) 2.246 × 10 –11
metre (4) 2.246 × 10–13 metre
29
 CHAPTER 2 STRUCTURE OF ATOM (JEE-NEET)
Ans. Given that m = 9.1 × 10–31 kg
1 1
c= of velocity of light or c = × 3 × 108 metre/second i.e. 3 × 107 metre/second
10 10
h = 6.6252 × 10–34 joule second
h 6.6252 1034 6.6252 1034
 = =
mc 9.11031  3 107 27.3 1024
or 2.2426 × 10–10 metre
or 2.426 × 10–11 metre
Question : What should be the momentum (in gram cm per second) of a particle it its De Broglie
wavelength is 1Å and the value of h is 6.6252 × 10–27 erg second ?
(1) 6.6252 × 10–19 (2) 6.6252 × 10–21
(3) 6.6252 × 10 –24
(4) 6.6252 × 10–27
Ans. Given that
= 1Å = 1 × 10–8 cm h = 6.6252 × 10–27 erg second
6.6252 1027
Or p  = 6.6252 × 10–19 gram cm/sec.
1108
Question. What should be the mass of the photon of sodium if its wavelength is 5894Å, the velocity of
light is 3 × 108 metre/second and the value of h is 6.6252 × 10–34 Kg m2/sec.?
(1) 3.746 × 10–26 (2) 3.746 × 10–30
(3) 3.746 × 10 –34
(4) 3.746 × 10–36
h h
Ans.   or (  = 5894Å or 5894 × 10–10 m)
mc c
6.652 1034 6.652
m or  1032
3 108  5894 1010 17682
= 0.0003746 × 10–32 or 3.746 × 10–36 Kg

The Heisenberg’s uncertainty principle:

The uncertainty principle is one of the basic principles of wave mechanics. It is the consequence of dual
behaviour of matter and radiation. Heisenberg formulated the uncertainty principle.
To view any object, a light of shorter wavelength than its dimensions is to be focused on it and the
reflected beam of light should be observed. As electron is an extremely smaller particle, a light of
extremely shorter wavelength (higher energy) is required. By absorbing this higher energy, the velocity
or momentum of electron increases further which automatically changes its position due to this
simultaneous determination of position and momentum or velocity of an electron cannot be done
accurately. Based on this Heisenberg stated uncertainty principle as follows:

“It is impossible to determine simultaneously and accurately the exact position and
momentum or velocity of a sub-atomic particle like electron in an atom”.
One can determine the position of a particle very accurately, and then the determination of its velocity
becomes less accurate. Similarly, one can determine the velocity of a particle very accurately, and then
the determination of its position becomes less accurate. The certainty in one factor introduces the
uncertainty in another factor.
If the uncertainty in the determination of the position of a small particle is given by Δx and uncertainty in
its momentum is Δp, then
h
(Δx) (Δp) ≥ Where n = 1,2,3,4.........
nπ
For an electron, revolving around the nucleus in an atom the value of n is nearly 4.
Thus, Heisenberg’s principle can also be stated as the product of uncertainty in position and momentum
of an electron like micro particle moving with high speed cannot be less than h/4.
h
Heisenberg’s equation can also be written as, (Δx) (Δv) ≥
4πm
Where m is the mass of the particle and Δv is uncertainty in velocity.
If the position of the particle is known exactly (Δx = 0), Δv becomes infinity (∞) and vice versa.
Heisenberg's uncertainty principle is not applicable to those objects, which cannot change their position
by themselves when a light falls on them i.e. to macro particles. It is applicable for micro particles like
electrons.
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 CHAPTER 2 STRUCTURE OF ATOM (JEE-NEET)
On the basis of this principle, therefore, Bohr's picture of an electron in an atom, which gives a fixed
position in a fixed orbit best we can think of in terms of probability of locating an electron with a
probable velocity in a given region of space at a given time. The space or a three-dimensional region
round the nucleus where there is maximum probability of finding an electron of a specific energy is called
an atomic orbital.

Significance of Heisenberg’s uncertainty principle:

Like de Broglie equation, although Heisenberg’s uncertainty principle holds good for all objects but it is
significance only for microscopic particles. The reason for this is quite obvious. The energy of the photon
is insufficient to change the position and velocity of bigger bodies when it collides with them. For
example, the light from a torch falling on a running rat in a dark room, neither change the speed of the
rat nor its direction, i.e., position.
This may be further illustrated with the following examples:
h 6.625×10−34 kgm2 s−1
For a particle of mass 1 mg, we have Δx. Δυ = = = 10−28 m2 s −1
4πm 4×3.1416×(10−6 kg)
Thus, the product of Δx and Δυ is extremely small. For particles of mass greater than 1 mg, the product
will still smaller. Hence, these values are negligible.
For a microscopic particle like an electron, we have
h 6.625 × 10−34 kgm2 s −1
Δx. Δυ = = ≈ 10−4 m2 s −1
4πm 4 × 3.1416 × (9 × 10−31 kg)
Thus, if uncertainty in position is 10−4 m, uncertainty in velocity will be = 1.0ms −1 which is quite
significant. It is for this reason that Bohr’s concept of fixed circular path with definite position and
momentum of the electron have been replaced by stating that the electron or wave mechanical model of
atom.
Since in everyday life, we come across big objects only, the position and velocity of which can be
measured accurately, Heisenberg’s uncertainty principle has no significance in everyday life.

Question : It the uncertainity in position of a moving particle is 0 then find out p

Ans. (1) 0 (2) 1 (3)  (4) Can not predict
h h h
x p > p > p > p > 
4 4x 4o
Question : A ball weight 25 gm moves with a velocity of 6.6 × 104 cm/sec then find out the de
Broglie associated with it.
1038
Ans. = 1
25
6.6 1034 107 1038
= erg sec = 1 
25  6.6 104 cm / sec 25
= 0.04 × 10–38 × 107 =0 .04 × 10–31 cm = 0.4 × 10–33 cm

Question : Which of the following has least de Broglie l

(1) e– (2) p (3) CO2 (4) SO2
38
10
Ans.  = 1  mass of SO2 is greater than the mass of e– , p, CO2
25
= h constant
= V Same  least  will be SO2
1

m
Qustion : If uncertainty in position of an e– is same as the x of He atom. If p of e– is 32 × 105
then find p in He atom.
hc
Ans. x × p =
4
Since x is same for p ot
therefore p will be same by

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 CHAPTER 2 STRUCTURE OF ATOM (JEE-NEET)
xe  pe  4h Pe
= = 1
h PHe
x( He )  PHe 
4
 Pe  PHe
 32 × 105 = 32 × 105  PHe = 32 × 105

Question : Calculate the uncertainity in the position of a particle when the uncertainity in momentum
is (a) 1 × 10–3 g cm sec–1 (b) zero.
Ans. (a) Given p = 1 × 10g cm sec–1
h = 6.62 × 10erg sec.
p = 3.142
According to uncertainity principle
h
x.p 
4
h 1 6.62 1027 1
So, x  .   3 = 0.527 × 10cm
4 p 4  3.142 10
(b) When the value of p = 0, the value of x will be infinity.

Question : The uncertainty in position and velocity of a particle are 10–10 m and 5.27 × 10–24 ms–1
respectively. Calculate the mass of the particle (h = 6.625 × 10 –34 Joule Sec.)
Ans. According to Heisenberg's uncertainty principle,
h h 6.625 1034
x.m v  or m = = 0.099 Kg
4 4x.v 4  3.143 1010  5.27 1024
Question : Calculate the uncertainty in velocity of a cricket ball of mass 150 g if the (uncertainity in its
position is of the order of 1Å (h= 6.6 × 10–34 Kg m2 s–1).
h h 6.6 1034
Ans. x . m v =  v = = = 3.499 × 10–24 ms–1
4 4x.m 4  3.143 1010  0.150
Wave mechanical model of atom
Classical mechanics, based on Newton’s laws of motion, was successful in explaining the motion of
macroscopic bodies like falling stones or motion of planets around the sun etc. But it failed when applied
to microscopic particles like electrons, atoms, molecules etc. This was mainly because it did not take into
account the concept of dual nature of matter and Heisenberg’s uncertainty principle. Hence, a new
branch of science, which takes dual nature of matter into consideration, has been put forward. This is
known as ‘Quantum mechanics’.

Schrodinger Wave Equation:

Quantum mechanics, as developed by Erwin Schrodinger is based on the wave motion associated with
the particles. For the wave motion of the electron in the three-dimensional space around the nucleus, he
put forward an equation, known as Schrodinger wave equation. The wave equation describes the
electron in motion as a three dimensional wave travelling in the electric field of positive nucleus. The
Schrodinger differential wave equation is given by
∂2 ψ ∂2 ψ ∂2 ψ 8π2 m
+ + + 2 (E − V)ψ = 0
∂x 2 ∂z 2 ∂y 2 h
Here x, y, z are Cartesian coordinates of the electron
m = mass of electron, h = Planck’s constant
E = total energy of the electron (KE + PE), V = potential energy of the electron (PE)
 = wave function of the electron.
82 m
2  (E  V)  0
h2
 2 is Laplacian Operator
h2  h2 
   E  V   0 
2
V   2    E. Ĥ   E
8 m
2
 8 m 
2

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 CHAPTER 2 STRUCTURE OF ATOM (JEE-NEET)
Ĥ is Hamiltonian Operator. It means whenever Hamiltonian operator is applied on the wave function ,
we get total energy associated with the wave function, 

Significance of :
is the wave function. It gives the amplitude of the electron wave. is expressed in terms of
coordinates x,y and z. The wave function may have positive or negative value depending upon the
values of coordinates.

Wavelength

Vibration
Direction of Propagation

The main aim of Schrodinger equation is to give a solution for the probability approach. When the
equation is solved, it is observed that for some regions of space, the value of  is positive and for other
regions, the value of ψ is negative. However, the probability must always be positive and it cannot be
negative. It is thus proper to use  instead of .

The acceptable solutions of the wave equation are called Eigen wave functions denoted by . The
probability of finding an electron at a point in space is given by (x, y, z), where x, y and z are
Cartesian coordinates. Acceptable solutions to the wave equation, which are physically possible, must
have certain properties.
1) must be continuous,
2) must be finite,
3) must be single valued,
4) The probability of finding the electron over all the space from plus infinity to minus infinity must be
equal to one.

The intensity of light is proportional to the square of amplitude (). Just as  indicates the density of
photons in space,  in case of electron wave denotes the probability of finding an electron in the space
around the nucleus or electron density around the nucleus. is directly proportional to electron
density. is a probability function. It indicates the probability of finding the electron at a given point or
in an infinitesimal volume of space around the nucleus. If  is maximum, the probability of finding the
electron is also maximum (95%).

Atomic Orbital:
The three dimensional space around the nucleus where the probability of finding the electron
is maximum is called an atomic orbital.

Differences between orbit and orbital:

Orbit Orbital
1. An orbit is a well-defined circular path 1. An orbital is the region of space around the around
around the nucleus in which the electron the nucleus where the probability of finding the
revolves. electron is maximum (95%)
2. An orbit represents the movement of 2. An orbital represents the movement of electron in
electron in one plane. three dimensional spaces.

3. An orbit means the position as well as 3. In an orbital it is not possible to find the position as
the velocity of the electron can be known well as velocity of the electron can be known with
with Certainty. certainty.

4. Orbits are circular or elliptical shaped. 4. Orbitals have different shapes. s-orbital is
spherical and p orbital is dumb bell shaped.
5. Orbits do not have directional 5. Except ‘s’ orbitals, all other orbitals have
characteristics. directional characteristics

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 CHAPTER 2 STRUCTURE OF ATOM (JEE-NEET)
6. An orbit can have maximum number 6. An orbital can accommodate a maximum of only
of2n2 electrons. two electrons.

Wave function and quantum numbers:

The amplitude function  in the Schrodinger wave equation is called wave function as it describe the wave
motion of the electrons in an atom and its value at any point depends on the co-ordinate x,y and z i.e. it is
a function of the co-ordinates x,y and z. That is why it is represented in a more exact way as  (x,y,z).
To solve schrodinger wave equation it is found convenient to express it in spherical polar co-ordinates (r,
θ,Φ) instead of Cartesian co-ordinates (x,y,z). For example for the hydrogen atom the co-ordinates of
electron with respect to the nucleous are shown in fig 1.10. the cartesian co-ordinates are related to polar
2
co-ordinates as follows: x  r sin  cos  , y  r sin  sin  and z  r cos  ( x  y2  z2  r 2 )
Thus Schrodinger wave equation has three variables r, θ and Φ so it can be express in the form
 (r) = R(r)  () ()
Where R(r) is a function of the radial distance r only and is independent of  and it is called Radial
wave function. Similarly  () is a function of  only and () is a function of only. These are called
Angular wave functions. Thus complete wave function is made up of two parts as follow:
 (r) = R(r) () ()
Radial part angular part
By suitable mathematical treatment, now three separate equations can be obtained involving r, θ and Φ
respectively. While solving these equations, certain quantum restrictions are introduced. These
restrictions are appear in the form of quantum numbers. For example,
(i) The function of R depends only on r. it therefore, describes the radial distribution of the electron.
It depends on two quantum numbers n and l. The values allowed for these numbers are as
follows. For different values of n and l the functions R are different.
n= 1,2,3,4,……..
l= 1,2,3……..(n-1)
(ii) The function depends on angle It therefore describes distribution as a function of angle It
depends on two quantum numbers l and m. the values permitted for ’m’ are –l to +l integer
values including zero. m is called magnetic quantum number.
(iii) The function  depends on angle therefore it describes distribution as a function of angle It
is found to depend only on the value of m.

From the above discussion, it is clear that the three quantum numbers viz. n, l and m can be
obtained from the solution of the Schrodinger wave equation. The fourth quantum number,
which is known as spin quantum number, was introduced to explain the spin motion of electron.

Quantum numbers:
The behavior of an electron in an atom is described mathematically by a wave function or orbital.
Quantum mechanics tells us that three quantum numbers are required to distinguish atomic orbitals
precisely. They are principal quantum number, azimuthal quantum number and magnetic quantum
number. These quantum numbers describe the energy level of an orbital and define the shape and
orientation of the region in space where the electron will be found. A fourth quantum number known as
spin quantum number is needed to specify the direction of the spin of the electron in an atomic orbital.
The first three quantum numbers - principal, azimuthal and magnetic quantum numbers can be deduced
as solutions of Schrodinger wave equation but not the spin quantum number.

Principal quantum number:

 Niels Bohr introduced the principal quantum number. It is denoted by ‘n’.
 For single electron system n indicates total energy of electron but for multielectron system it indicates
distance of electron from the nucleous.
 ‘n’ can be any whole number value such as 1,2,3,4, etc. The energy shells corresponding to these
numbers are K, L, M, N, etc.
 Principal Quantum no. indicates the main energy level to which the electron belongs. It also indicates
the average distance of an electron from nucleus and also the speed of the atomic electron.
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 CHAPTER 2 STRUCTURE OF ATOM (JEE-NEET)
 As the ‘n’ value increases the distance of electron from the nucleus increases and its energy also
increases.
 The maximum no. of electrons that can be present in an orbit is given by 2n2 . The maximum no. of
electron in K, L, M, and N shells are 2,8,18 and 32 respectively.
0.529×n2
 The radius of the orbit is given by the expression: rn = Ao. r1 < r2 < r3 < r4 < r5 – – – –
Z
−13.6×Z2
 The energy of the electron/orbit is given by the expression.En = cm/sec E1 < E2 < E3 < E4 – –
n
2.18×108 ×Z
 The velocity of the electron is given by the expression. Vn = cm /sec.
n

Azimuthal Quantum Number:

 Azimuthal Quantum number was introduced by Somerfield to explain the fine lines in the spectrum
along with main lines.
 To explain the presence of fine lines it was suggested that the electrons present in main shell of a
multi-electron atom do not have the same energy. This because they move along different paths and
hence have different angular momentum. Thus within same principal shell there are number of sub-
shell or sub energy levels. As a result number of electronic jump increases and so is the number of
lines.
 It is also called as secondary quantum no. or orbital angular momentum quantum number or subsidiary
quantum number.
 It is denoted by .
 ‘’ can have the values from 0 to (n-1), a total of ‘n’ values. ‘’ values 0,1,2,3 indicates s,p,d,f. s,p,d
and f are spectroscope terms which indicates sharp. Principle, diffuse and fundamental respectively.
 Azimuthal Quantum number indicates the sub-shell to which the electron belongs. It also determines
the shapes of the orbital in which the electron is present.
 Each main energy shell can have ‘n’ number of sub-shells.
n 
1 0 (1s)
2 0 (2s), 1 (2p)
3 0 (3s), 1 (3p), 2(3d)
4 0 (4s), 1(4p), 2(4d), 3(4f)
h
 The orbital angular momentum (L) of an electron is given by the expression: L = √𝑙(𝑙 + 1)
2π
Example:
If n = 1 then l = 0  1s i.e. in n =1 shell, only one subshell 's' is present.
If n = 2 then l = 0,1 2s,2p i.e. in n =2 shell, two subshell 's' & 'p' are present.
If n = 3 then l = 0,1,2 3s, 3p, 3d i.e. in n =3 shell, three subshell 's' , 'p' & 'd' are present.
If n = 4 then l = 0,1,2,3  4s,4p, 4d, 4f i.e. in n =2 shell, four subshell 's' , 'p' , 'd' & 'f' are present.
If the value of n is same then the order of energy of the various subshell will be s < p < d < f
Example: 4s < 4p < 4d < 4 f
3s < 3p< 3d
2s < 2p
If Value of  is same but value of n is different then the order of energy will be.
Example: 1s < 2s < 3s < 4s < 5s < 6s
3d < 4d < 5d < 6d
4P < 5P <6p
h  h 
The orbital angular momentum is equal to = (  1) =   1    or { is called
2  2 
as 'hash' }
Orbital angular momentum
For s subshell =0
h
For p Subshell 2 = or 2 h
2
The number of electron in a particular subshell is equal to 2(2 l +1)
for s Subshell = 2 e—
35
 CHAPTER 2 STRUCTURE OF ATOM (JEE-NEET)
for p subshell = 6 e—
for d subshell = 10 e—
for f subshell = 14 e—
Shape of the subshell :
s  spherical
p  dumb bell shape
d  double dumb bell shape
f  complex shape
Magnetic Quantum number:
 Magnetic quantum number explain the splitting of spectral line in external magnetic field. It was
introduced by Lande to explain Zeeman Effect.
 It is denoted by m or ml.
 This quantum number refers to different orientations of electron could in a particular subshell. These
orientations are called the orbitals.
 An electron due to its orbital motion around the nucleus generates an electric field.This electric field in
turn produces a magnetic field, which can interact with the external magnetic field. Thus, under the
influence of the external magnetic field, the electrons of a subshell can orient themselves in certain
preferred regions of space around the nucleus called orbitals. The magnetic quantum number
determines the number of preferred orientations of the electron present in a subshell.
 Since each orientation corresponds to an orbital, therefore, the magnetic quantum number determines
the number of orbitals present in any subshell.
 ‘m’ can have values from – 𝑙 to +𝑙 including zero, a total (2 𝑙+1) values.
Subshell 𝒍 m values No. of orientations
(Orbitals)
s 0 0 1
p 1 -1, 0, +1 3
d 2 -2, -1, 0, +1, +2 5
F 3 -3, -2, -1, 0, +1, +2, +3 7
 When  = 0, m has only one value, m = 0. The sub-level‘s’ has one orbital called s orbital.
 When =1, m can have 3 values m = –1, 0, +1. The sub-level ‘p’ has three space orientations or three
orbitals. The three orbitals are designated as p x, py and pz.
 When  = 2, m can have 5 values m = –2,–1, 0, +1, +2. The sub-level ‘d’ has five space orientations
or five orbitals. The five orbitals are designated as dxy, dyz, dzx, dx2 −y2 anddz2 .
 When  = 3, m can have 7 values m = –3,–2,–1,0,+1,+2,+3. The sub-level ‘f’ has seven space
orientations or seven orbitals.
 The magnetic quantum number gives orientation of orbitals in space. All the orbitals present in a
sublevel have same energy and shape. They are called ‘degenerate orbitals’, which differ in their spatial
orientation.
 Each value of ‘m’ constitutes an orbital in the sublevel.
 The maximum no. of electrons in a subshell is given by: 2(2𝑙+1) or (4 𝑙+2).

Spin Quantum Number:

 Spin Quantum number was proposed by Uhlenbeck and Goudsmith.
 It is denoted by ‘s’ or ‘ms’.
 It indicates the direction of spinning of electron present in any orbital.
 Since the electron in an orbital can spin either in the clockwise direction or in anti-clockwise direction,
hence for a given value of m, s can have only two values, i.e., +1/2 and -1/2 or these are very often
represented by two arrows pointing in the opposite direction, i.e.,↑and ↓.
 This quantum number helps to explain the magnetic properties of the substances. A spinning electron
behaves like a micro magnet with a definite magnetic moment. If an orbital contains two electrons, the
two magnetic moments oppose and cancel each other.
 Thus, in an atom, if all the orbitals are fully filled, net magnetic moment is zero and the substance is
diamagnetic (i.e., repelled by the external magnetic field). However, if some half-filled orbitals are

36
 CHAPTER 2 STRUCTURE OF ATOM (JEE-NEET)
present, the substance has a net magnetic moment and it is paramagnetic (i.e., attracted by the
external magnetic field).
h
 The spin angular momentum (μs) of an electron is given by μs = √s(s + 1)
2π

Orbitals:
The wave equation shows that the orbitals fall into different groups.
1. In the 1st group, the value of Ψ & hence ψ2 depends only on the distance ‘r’ from the nucleus. This
is same in all directions in space. This leads to spherical orbitals(s).

ψ = f(r)
2. In the 2 group of solutions, Ψ & Ψ2 depends both on the distance from the nucleus (r) & the
nd

direction in space (x y z)

ψ𝑥 = 𝑓(𝑟)𝑓(𝑥) ψ𝑦 = 𝑓(𝑟)𝑓(𝑦) ψ𝑧 = 𝑓(𝑟)𝑓(𝑧)

Ex:- ψ3,1,0 = 3pz , ψ3,2,0 = 3dz2

3. The 3rdgroup of solutions depends on the distance from the nucleus (r) & also in two directions in
space. ψ = f(r). f(x). f(y)
All these different groups of orbitals differ in their  values
Shapes of orbital
As already defined an orbital is the region of space around the nucleus within which the probability of
finding an electron of given energy is maximum. The shape of this region gives the shape of the orbital.
The probability at any point around the nucleus is calculated using Schrodinger wave equation and is
represented by the density of the electron cloud i.e. by the density of the points.
However as already explained for the coordinates (r) of the electron with respect to the
nucleus, Schrodinger wave equation can be solved to get the value of the orbital wave function but
has no physical meaning. On the other hand value of ||2 has the significance as it gives electron
probability density of the electron at that point. It has also been discussed that is a function of three co-
ordinates of the electron (r). it can be separated into three parts each being a function of one co-
ordinate i.e.  (r) = R(r)  () ()
The part of R(r) is called radial part where as the product  () () is called angular part. To
study the variation of and hence ||2 at different distances and different directions from the nucleus, we
simplify our study by first studying separately the variation of radial function and the angular function and
then we combine them to study the variation of complete wave function.

Probability distribution curve

An atomic orbital is a one electron wave function r obtained from the solution of Schrodinger
wave equation this can be represented by
 (r) = R(r)  ()  ()
Where R = Radial function, which gives the dependence of orbital upon distance r.
() &  () Angular function giving the angular dependence of orbital on  and  respectively.
The orbital wave function  does not have any physical significance but the square of () provides the
information regarding the probability of electron at a point in an atom.
To draw the representation of variation of 2 in space we required following functions:
(a) Radial wave function (b) Radial probability density (R2) (c) Radial probability function (4r2R2)

(a) Radial wave functions (R) :

By drawing these, we can get the information that how the radial wave function changes with distance
r.
In each case as r approaches infinity, R approaches zero.
For 1s orbital, the wave function continuously decreases with increases in r & approaches zero as ‘r’
approaches infinity.
By drawing this curve, we can find the node in 2s, radial function. At node as figure indicates the value
of radial function changes from positive to negative. At this value of r,R is zero.
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 CHAPTER 2 STRUCTURE OF ATOM (JEE-NEET)
The wave function for 1s orbital is positive for all values of r while for 2s orbital it is positive as well as
negative depending on the value of r.
It is found that ns orbital have (n-1) radial node and np orbitals have (n-2) radial node.
These plots give the information how radial wave function changes with distance ‘r’ and also give the
information of number of node and their distance.

2s 2p 
1s 3p
2 3s
R R
R

+ +
Node –
x –
r r r

(b) Radial probability density (R2):

The Square of radial wave function R2 for an orbital give the radial density & this radial density give the
probability density of finding the electron at a point along a particular radius line.
By drawing the curve, we can obtain the useful information about probability density or relative
electron density at a point as a function of radius.
Graphs plotted ψ2 versus r represents the variation of ψ2 with distance from nucleus & are known as
probability distribution curves. The distance where value of ψ2 is high shows the area of high probability
of finding electron. The distance at which Ψ 2 is zero shows node.
For s-orbitals, the electron density is maximum at the nucleus while for other orbitals it is zero at the
nucleus.
The plot for 1s orbital indicates that probability is maximum near the nucleus & decreases with
increases of r but it never becomes zero even at a large distance.
The plot for 2s-orbital indicates that probability decreases & becomes zero at a particular distance. This
is point is called nodal point or node. After the nodal point, the probability again increases & follows the
trend as shown in figure below
Nodes

1s 2s 2p


2
2 2
R
2
R R 3s

Node

r r r r
(c) Radial probability function (4 r2R2):
As discussed earlier that 2 gives the probability distribution for electron with respect to the nucleus. In
order to understand the concept of radial probability let us assume that the space around the nucleus is
divided into large number of concentric shells of thickness dr.
So, volume of the radial shell
 Volme of the sphere   Volme of sphere 
=   –  
 with radius (r  dr )   with radius r  r
4 4
=  (r + dr)3 – r3 r + dr
3 3

=
4
3

 r  3r dr  3r (dr )  ( dr )
3 2 2 3
  43 r 3

4
=  × 3r2dr = 4r2dr [Since (dr)2 and (dr)3 are very small and can be
3
neglected]
Now, radial probability = probability density × volume of the radial shell
= 2 × 4r2dr.

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 CHAPTER 2 STRUCTURE OF ATOM (JEE-NEET)
The shape of an atom is assumed spherical so it better to discuss the probability of finding the electron
in a spherical shell between the radius (r + dr) and r. This probability which is independent of direction
is called radial probability & equal to (4r2 dr R2) By the drawing the curve we can obtain the
information regarding the variation of radial probability function (4 r2, R2) with distance r.
An important feature of the radial probability function is that it gives the probability of finding the
electron at a distance r from the nucleus irrespective of the direction.
1s 2s 2p

4r2R2

2
4 r2R2

4r R
2
r r r

Ex: For 1s orbital:

in case of 1s orbital, the radial probability (R2) of finding electron is maximum near the nucleus. However
the volume element 4r2dr is very small because r is very small near the nucleus. Hence their product is
quite small. As the distance r from the nucleus increases value of R 2 also increases but the volume of
4r2dr increases. their product goes on increasing till it reaches maximum value at distance of 52.9 pm
(0.53A0) and then begin to decrease abruptly and becomes negligible at large distances. This distance of
maximum probability is called radius of maximum probability and in case of H-atom it is equal to 52.9
pm (0.53A0) i.e. is equal to Bohr’s radius for the first orbit. [For Bohr model the electron revolves at a
constant distance of 52.9 pm (0.53A0) from the nucleus. While in case of wave mechanical model
electron is most likely to be found at this distance but there is a probability of finding the electron at
distances shorter as well as larger than 52.9 pm.
For 2s and 2p orbitals:
The radial probability distribution curve for 2s orbital shows two maxima, a smaller one near the
nucleus and bigger one at a larger distance.
In-between two maxima, there is a distance r from the nucleus at which the radial probability function
become zero. This shows that the probability of finding the electron at this distance is zero. This point is
called the nodal point.
The radius of maximum probability of 2s orbital is (at 2.7A0) greater distance than 2p (at 2.1A0) orbital.
However, in the case of 2s orbital, one additional maxima appears at small distance, this confirms that the
2s electrons spends more time near the nucleus than 2p electrons. Hence, 2s orbital is more penetrating
than 2p orbital. In other words 2s electron is more stable and has lower energy than 2p-electron.
The distance of maximum probability for 2p and 2s orbitals are same and this distance is greater than
that of 1s orbital. Hence 1s orbital is nearer to the nucleus in comparison to 2s and 2p orbitals.
 radial wave function, 2  radial probability density, 4r2dr. 2 radial probability function

Plots based on angular wave function ()[additional]

As already explain, the angular wave function depends only on the quantum number l and m and is
independent of principal quantum number n. This implies that orbitals of a particular type will have the
same angular wave function  irrespective of the value of n. the plots of angular wave function and the
angular probability density ||2 for s and pz orbitals are shownin the figure. (it is important to remember
that in these plots, it is the numerical value of that is plotted in that direction not the distance from
the nucleus).
Each of these are briefly described below.

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 CHAPTER 2 STRUCTURE OF ATOM (JEE-NEET)





(a) (b) (c)

Plots of angular wave function,:

for s-orbitals it is found that for any ns orbital,    (1 / 4 )1/2 i.e. it is independent of angle and
thus is constant and therefore the plot will be circular in two dimensions or more correctly, spherical in
three dimensions as shown in the figure above. In other words, all s-orbitals have spherical symmetry.
The expression for  of pz orbital involves angle while those px and py orbitals involves both and
. Plotting the values of for pz orbital, two tangent spheres are obtained as shown in the figure (b).
The plots of px and py orbitals are identical to that of pz orbital in shape but they are oriented along X-
axis and Y-axis respectively.
The plots of the angular wave function for d-orbitals have four lobes while those for f-orbitals have six
lobes.
Plots of angular probability density ||2
For s orbital as || independent of angle and the plots of squared value do not undergo any change
in shape i.e. they remain spherical. In case of p and d orbitals the plots of squared value becomes
elongated as shown for pz orbital in figure (c)

 radial wave function, 2  radial probability density, 4r2dr. 2 radial probability function

Types of Nodes:
Nodes are of two types: a) Radial Node b) Angular Node
A radial node is the spherical region around then nucleus, where the probability if finding the electron is
zero (Ψ 2 = 0). Similarly, nodal plane (angular plane) have zero probability of finding electron.

Calculation of no. of nodes:

No. of Radial nodes = n− −1 Ex: In a3p-orbital
No. of Radial nodes = 3-1-1 = 1
No. of angular nodes = 
No. of angular nodes = 1
Total no. of nodes = n-1 Total no. of nodes = 2.

Boundary surface diagrams

Boundary surface diagrams of constant probability density for different orbitals give a fairly good
representation of the shapes of the orbitals. In this representation, a boundary surface or contour
surface is drawn in space for an orbital on which the value of probability density ||2 is constant. In
principle many such boundary surfaces may be possible.
However, for a given orbital, only that boundary surface diagram of constant probability density* is
taken to be good representation of the shape of the orbital which encloses a region or volume in
which the probability of finding the electron is very high, say, 90%. The boundary surface diagram
for 1s and 2s and 3s orbitals are given in Fig.

2S 3S
1S Node Node

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 CHAPTER 2 STRUCTURE OF ATOM (JEE-NEET)
One may ask a question: Why do we not draw a boundary surface diagram, which bounds a region in
which the probability of finding the electron is, 100 %? The answer to this question is that the
probability density ||2 has always some value, howsoever small it may be, at any finite distance
from the nucleus. It is therefore, not possible to draw a boundary surface diagram of a rigid size in
which the probability of finding the electron is 100%. Boundary surface diagram for a‘s’ orbital is
actually a sphere centered on the nucleus. In two dimensions, this sphere looks like a circle. It
encloses a region in which probability of finding the electron is about 90%.
Thus, we see that 1s and 2s orbitals are spherical in shape. In reality all the s-orbitals are spherically
symmetric, that is, the probability of finding the electron at a given distance is equal in all the
directions. It is also observe that the size of the s orbital increases with increase in n, that is, 4s > 3s
> 2s > 1s and the electron is located further away from the nucleus as the principal quantum
number increases.

Boundary surface diagrams for three 2p orbitals ( = 1) are shown in Fig. below. In these diagrams,
the nucleus is at the origin. Here, unlike s-orbitals, the boundary surface diagrams are not spherical.
Instead, each p orbital consists of two sections called lobes that are on either side of the plane that
passes through the nucleus. The probability density function is zero on the plane where the two lobes
touch each other. The size, shape and energy of the three orbitals are identical. They differ however,
in the way the lobes are oriented. Since the lobes may be considered to lie along the x, y or z axis,
they are given the designations 2px, 2py, and 2pz. It should be understood, however, that there is no
simple relation between the values of ml (–1, 0 and +1) and the x, y and z directions. For our
purpose, it is sufficient to remember that, as there are three possible values of ml. Therefore, three p
orbitals whose axes are mutually perpendicular. Like s orbitals, p orbitals increase in size and energy
with increase in the principal quantum number and hence the order of the energy and size of various
p orbitals is 4p > 3p > 2p. Further, like s orbitals, the probability density functions for p-orbital also
pass through value zero, besides at zero and infinite distance, as the distance from the nucleus
increases. The number of nodes are given by the n –2(n− −1), that is number of radial node is 1 for
3p orbital, two for 4p orbital and so on.

(Nodal plane)
y

xy plane
y yz plane y
(Nodal plane)
xz plane
(Nodal plane)
x x x
z Px z z
Pxy Pxz

For  = 2, the orbital is known as d-orbital and the minimum value of principal quantum number (n)
has to be 3. As the value of cannot be greater than n–1. There are five ml values (– 2, –1, 0, +1
and +2) for  = 2 and thus there are five d orbitals. The boundary surface diagram of d orbitals are
shown in Fig.
y
z z
z
z z
y y
y
x
x x
x y x
dxy dyz dxz dx2-y2

The five d-orbitals are designated as dxy, dyz, dxz, dx2 –y2 and dz2 . The shapes of the first four d-
orbitals are similar to each other, where as that of the fifth one, dz2, is different from others, but all

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 CHAPTER 2 STRUCTURE OF ATOM (JEE-NEET)
five 3d orbitals are equivalent in energy. The d orbitals for which n is greater than 3 (4d,5d...) also
have shapes similar to 3d orbital, but differ in energy and size.
Besides the radial nodes (i.e., probability density function is zero), the probability density functions
for the np and nd orbitals are zero at the plane (s), passing through the nucleus (origin). For
example, in case of pz orbital, xy-plane is a nodal plane, in case of dxy orbital, there are two nodal
planes passing through the origin and bisecting the xy plane containing z-axis. These are called
angular nodes and number of angular nodes are given by ‘’, i.e., one angular node for p orbitals, two
angular nodes for ‘d’ orbitals and so on. The total number of nodes are given by (n–1),
i.e., sum of  angular nodes and (n –  – 1) radial nodes.
Case-I
If  = 0 then m = 0 it implies that s subshell 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 s electron is
same in all directions from the nucleus. The size of the orbital depends on the value of principal quantum
number, there is one spherically symmetrical orbital. The 1s orbital is smaller than 2s-orbital and 2s-
orbital is smaller than 3s, but all are spherical in shape as shown in fig.
y
Nodal
suface

1s
z 2s
2S 3S
1S Node Node 3s
Although the s-orbitals belonging to different shells are spherically symmetrical, yet they differ in
certain respects as explained below:
(i) The probability of 1s electron is found to be maximum near the nucleus and decreases as the
distance from the nucleus increases. In case of 2s electrons, the probability is again maximum near the
nucleus and then decreases to zero and increases again and then decreases as the distance from the
nucleus from the nucleus increases. The intermediate region (a spherical shell) where the probability is
zero is called a nodal surface or simply node. Thus, 2s-orbital differs from 1s-orbital in having one node
within it. Similarly, 3s has two nodes.
In general, any ns orbital has (n -1) nodes.
(ii) The size and energy of the s-orbital increases as the principal quantum number increases, i.e., the
size and energy of s-orbital increases in the order 1s < 2s < 3s ....
The s orbital of higher energy levels are also symmetrically spherical and can be represented as above.
Case-II
 1 0 1
If l = 1 ( p - subshell) then m=
px pz p y
It implies that, p subshell have three orbitals called as px, py and pz.

Shape of p-orbitals :
There are three p-orbitals, commonly referred to as px, py and pz. These 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 another and
are directed along x, y and z axes (fig.)

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 CHAPTER 2 STRUCTURE OF ATOM (JEE-NEET)

(Nodal plane)
y

xy plane
y yz plane y
Nodal y
surface (Nodal plane)
xz plane
(Nodal plane)
x
2Px x x x
z 3Px Px z z
4Px z
Pxy Pxz
Nodal point

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).
The two lobes of each orbital are separated by a plane of zero electron density called nodal plane.
Each p orbital of higher energy level are also dumb bell shape but they have nodal surface.
Nodal surface
Nodal surface : Orbital Nodal surface
2 px 0
3 px 1
4 px 2
npx (n – 2)
Nodal Plane : Orbital Nodal plane
px yz plane
py xz plane
pz xy plane
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-y2contain four lobes while fifth orbital consists of only two lobes. The lobes of dxy orbital lie
between x and y axes at 450 angle. Similar is the case for dyz and dxz. In dx2-y2 four lobes of orbital
are lying along x and y axes while in dz2 the two lobes of orbital are lying along z axes and contain a
ring of negative charge surrounding the nucleus in xy plane.
2 1 0 1 2
2 2 2
m = dxy dyz dz dzx dx -y

z axis
The value can be interchange

Geometry of these d xy , d yz , d zx , d x2  y2  orbitals  Double Dumb bell or like cloverleaf
Shape of d z 2 orbital is like donought shape.
Nodal plane :
dxy  xz & yz nodal plane :
dxz  xy & zy nodal plane :
dzy  dzx & yx nodal plane :
d x2  y 2  0, nodal plane :

d z2  0, nodal plane :
Note: Orbitals of d subshell are Equivalent in energy.

(iii)
f subshell :
When  = 3 (f subshell)
Then
m=–3 –2 –1 0 +1 +2 +3
fx3
fy3
fxzy fz 3
fx(y – z) fy(z – x) fz(x2 – y)2
22 2 2

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 CHAPTER 2 STRUCTURE OF ATOM (JEE-NEET)
The structure of f-orbital is very complex
The number of values of f-orbitals in f subshell show that f subshell has 7 orbitals which are equivalent
in Energy.
Representation of the orbitals :
s
s
s subshell 
p
px p y pz
p subshell 
d
d xy dyz d z2 d xz d x2  y2
d subshell 
f
fx3 fy3 fz3 fxyz fx (y2  z2 ) fy (z2  x2 ) fz(x2  y2 )
f subshell 

ENERGY OF ORBITALS
The energy of an electron in a hydrogen atom is determined only by the principal quantum number.
Within a shell, all hydrogen orbitals havethe same energy, independent of the other quantum numbers.
1s < 2s = 2p < 3s = 3p = 3d < 4s = 4p = 4d = 4f
Although the shapes of 2s and 2p orbitals are different, an electron has the same energy when it is in 2s
orbital or 2p orbital. The energy of an electron in a multi electron atom depends, not only on its principal
quantum number, but also on its azimuthal quantum number. The s, p, d and f orbitals within a given
shell have slightly different energies in a multi electron atom.
Electronic configuration of multi electron atoms:
The distribution and arrangement of electrons in the main shells, subshells and orbitals of an atom is
called electronic configuration of the element.
The electronic configuration of different atoms can be best represented in two ways.
a) nlxmethod
b) Orbital diagram method
nlxmethod is a way of representing the electronic arrangements in an atom. Here n is principal quantum
number which represents the main energy level.  is azimuthal quantum number expressed in terms of s,
p, d or f and x is the number of electrons in the given value of .
Ex: 1s 2
The filling of electrons into the orbitals of atoms takes place according to the Aufbau principle, the Pauli’s
exclusion principle and Hund’s rule of maximum multiplicity.

Aufbau Principle:
Aufbau is a German word which means building up or construction. The building up of orbitals means
the filling up of orbitals with electrons.
“In the ground state of the atoms, the orbitals are filled in order of their increasing energies”.
In other words electrons first occupy the lowest energy orbital available to them and enter into higher
energy orbitals only after the lower energy orbitals are filled.
The relative energy of an orbital is given by (n + ) value. As (n + ) value increases, the energy of
orbital increases. The orbital with the lowest (n + ) value is filled first. When two or more orbitals have
the same (n +) value, the one with the lowest ‘n’ value (or) highest ‘’ value is preferred in filling.
Consider two orbitals 3d and 4s. The n +  value of 3d = 3 + 2 = 5 and of 4s = 4 + 0 = 4. Since 4s has
lowest (n +) value, it is filled first before filling taking place in 3d.
Consider the orbitals 3d, 4p and 5s
The (n + ) value of 3d = 3 + 2 = 5
The (n +) value of 4p = 4 + 1 = 5

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 CHAPTER 2 STRUCTURE OF ATOM (JEE-NEET)
The (n +) value of 5s = 5 + 0 = 5
These three values are same. Since the ‘n’ value is lower to 3d orbitals, the electrons prefer to enter in
3d, then 4p and 5s.
The order of increasing energy of atomic orbitals is: 1s < 2s < 2p < 3s < 3p < 4s < 3d < 4p < 5s
< 4d < 5p < 6s < 4f < 5d < 6p < 7s and so on.
The sequence in which the electrons occupy various orbitals can be easily remembered with the help of
Moeller’s diagram as shown in Fig
1s 2s 3s 4s 5s 6s 7s
Starting
point 2p 3p 4p 5p 6p 7p

3d 4d 5d 6d

4f 5f

Pauli’s Exclusion principle:

Electrons, which have the same spin strongly, repel each other and tend to occupy different regions of
space. This is a result of a fundamental law of nature known as the Pauli’s exclusion principle.
Pauli’s principle may be stated as “No two electrons in an atom can have the same set of
values for all the four quantum numbers”.
This means that two electrons in an orbital may have the same n, same l and same m but differ in spin
quantum number. In an orbital if one electron has clockwise spin, the other has anticlockwise spin. It
follows that an orbital can hold a maximum of two electrons with opposite spins.
For example helium atom has two electrons in its 1s orbital. Quantum numbers for first electron are n
=1,  = 0, m = 0 and s = +1/2.
Quantum numbers for second electron are: n =1,  = 0, m =0, s = –1/2.
The two electrons have the same value for n, same value for l and same value for m but differ in s. The
maximum capacity of a main energy shell is equal to 2n2 electrons and that of a sub-shell is equal to (4 
+ 2).Pauli’s principle is useful in the determination of the maximum number of electrons that can be
accommodated in an orbital, a sub-shell and a main shell.
Example: 6C12  1s2 2s2 2p2
  
px pz py
n 1 2 2
 0 0 1
m 0 0 + 1, –1, 0
1 1 1 1 1 1
s + ,– + ,– + ,+
2 2 2 2 2 2
Example:
8O  1s2 2s2 2p4
16

    

n = 1 2 px pz py
 = 0 0 1
m = 0 0 +1 0 –1
1 1 1 1 1 1 1 1
s = + ,– + ,– + ,– + +
2 2 2 2 2 2 2 2
Hund’s rule of maximum multiplicity:
According to this rule, when electrons are filled in degenerate orbitals of a subshell, pairing of an electron
takes place only when each orbital of the subshell is filled with one electron each.It can be also stated
that, in ground state of an atom, the configuration which has more number
45
 CHAPTER 2 STRUCTURE OF ATOM (JEE-NEET)
of unpaired electrons is most stable.
Thus in s, p, d and f subshells, pairing starts from 2nd, 4th, 6th and 8th electrons respectively.
Ex: Electronic configuration of N (7) is 1s 2 2s2 2p3.

The electrons in 2p subshell are occupied singally. i.e., 1s2 2s2 2p1x 2p1y 2p1z
Example : 26Fe  1s2 2s2 2p6 3s2 3p6 4s2 3d6
      
7N  1s2 2s2 2p3
  
17Cl  1s2, 2s2, 2p6, 3s2, 3p5
    
8O  1s2, 2s2, 2p4
  
19K  1s2, 2s2, 2p6 , 3s2 3p6, 4s1
    
27Co 1s2, 2s2, 2p6 , 3s2 3p6, 4s2 3d7
      
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 region behind this is that half filled & full filled subshell have got
extra stability.
Example :
24Cr  1s2 2s2 2p6 3s2 3p6 4s2 3d4 (wrong configuration)
 
24Cr  1s2 2s2 2p6 3s2 3p6 4s1 3d5 (right configuration)

29Cu  1s2 2s2 2p6 3s2 3p6 4s2 3d9 (wrong configuration)
 
29Cu  1s2 2s2 2p6 3s2 3p6 4s1 3d10 (right configuration)
 
( n+) rule :
According to it the sequence in which various subshell are filled up can also be determined with the
help of (n +) value for a given subshell.
Principle of ( n+) rule :
The subshell with lowest( n+) value is filled up first, When two or more subshell have same (n+)
value then the subshell with lowest value of n is filled up first.
Sub Shell n l n+
1s 1 0 1
2s 2 0 2
2p 2 1 3 (1)
3s 3 0 3] (2)

3p 3 1 4 (1)
4s 4 0 4] (2)

3d 3 2 5 (1)
4p 4 1 5 (2)
5s 5 0 5] (3)

4d 4 2 6 (1)
5p 5 1 6 (2)
6s 6 0 6] (3)
Rules for finding the Group No
(i) If the last shell contains 1 or 2 electrons then the group number is 1 and 2 respectively'

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 CHAPTER 2 STRUCTURE OF ATOM (JEE-NEET)
(ii) If the last shell contains more than 2 electrons then the group number is the total number of
electrons in the last shell plus 10'
(iii) If electrons are present in (n - 1) d orbital in addition to those in the ns orbital then the group
number is equal to the total number of electrons present in the (n -1) d orbital and ns orbital'

Electronic configuration of elements from 1 to 30

1 H 1s1 1s1
2 He 1s2 1s2
3 Li 1s2 2s1 [He] 2s1
4 Be 1s2 2s2 [He] 2s2
5 B 1s2 2s2 2p1 [He] 2s2 2p1
6 C 1s2 2s2 2p2 [He] 2s2 2p2
7 N 1s2 2s2 2p3 [He] 2s2 2p3
8 O 1s2 2s2 2p4 [He] 2s2 2p4
9 F 1s2 2s2 2p5 [He] 2s2 2p5
10 Ne 1s2 2s2 2p6 [He] 2s2 2p6
11 Na 1s2 2s2 2p6 3s1 [Ne] 3s1
12 Mg 1s2 2s2 2p6 3s2 [Ne] 3s2
13 Al 1s2 2s2 2p6 3s2 3p1 [Ne] 3s2 3p1
14 Si 1s2 2s2 2p6 3s2 3p2 [Ne] 3s2 3p2
15 P 1s2 2s2 2p6 3s2 3p3 [Ne] 3s2 3p3
16 S 1s2 2s2 2p6 3s2 3p4 [Ne]3s2 3p4
17 Cl 1s2 2s2 2p6 3s2 3p5 [Ne] 3s2 3p5
18 Ar 1s2 2s2 2p6 3s2 3p6 [Ne] 3s2 3p6
19 K 1s2 2s2 2p6 3s2 3p6 4s1 [Ar] 4s1
20 Ca 1s2 2s2 2p6 3s2 3p6 4s2 [Ar] 4s2
21 Sc 1s2 2s2 2p6 3s2 3p6 3d1 4s2 [Ar] 3d1 4s2
22 Ti 1s2 2s2 2p6 3s2 3p6 3d2 4s2 [Ar] 3d2 4s2
23 V 1s2 2s2 2p6 3s2 3p6 3d3 4s2 [Ar] 3d3 4s2
24 Cr 1s2 2s2 2p6 3s2 3p6 3d5 4s1 [Ar] 3d5 4s1
25 Mn 1s2 2s2 2p6 3s2 3p6 3d5 4s2 [Ar] 3d5 4s2
26 Fe 1s2 2s2 2p6 3s2 3p6 3d6 4s2 [Ar] 3d6 4s2
27 Co 1s2 2s2 2p6 3s2 3p6 3d7 4s2 [Ar] 3d7 4s2
28 Ni 1s2 2s2 2p6 3s2 3p6 3d8 4s2 [Ar] 3d8 4s2
29 Cu 1s2 2s2 2p6 3s2 3p6 3d10 4s1 [Ar] 3d10 4s1
30 Zn 1s2 2s2 2p6 3s2 3p6 3d10 4s2 [Ar] 3d10 4s2

Stability of atoms
Extra stability is associated with atoms in which degenerate orbitals are either half-filled or completely
filled due to (1) symmetrical distribution of electrons and (2) exchange energy. The amount of energy
released when two electrons with similar energy and same spin exchanges their position without the
change in electronic configuration is called exchange energy. Greater the exchange energy greater is the
stability. The number of exchange pairs is maximum when the given subshell is either half-filled or
completely filled.

The presence of half-filled and completely filled degenerate orbitals gives greater stability to atoms. It is
for this reason the electronic configurations of Cr and Cu are represented as [Ar] 4s 1 3d5 and [Ar] 4s1
3d10 respectively.
This can be explained on the basis of lowering of energy for a set of two electrons with parallel spins.
Two electrons with parallel spin remain farther apart than with two electrons with opposite spin.
Consequently, the coulombic repulsion energy is lowered between the electrons when their spins are
parallel. The extra stability of a parallel spin configuration is given by exchange energy
(Eex)
N(N−1)k
Eex=
2

47
 CHAPTER 2 STRUCTURE OF ATOM (JEE-NEET)
Here N is the number of electrons having parallel spins. As the number of parallel spins increases, the
exchange energy also increases. The exchange means the shifting of electrons from one orbital to
another in the same sub-shell. This can be easily illustrated by considering chromium as example.

 Cause of Stabilisty of Completely Filled and Half Filled Sub-Shells

The completely filled and completely half-filled sub-shells are stable due to the following
reasons.
1. Symmetrical distribution of electrons
It is well known that symmetry leads to stability. The completely field or half-filled subshells have
symmetrical distribution of electros in them and are therefore more stable. Electrons in the same subshell
(here 3d) have equal energy but different spatial distribution. Consequently, their shielding of one-another
is relatively small and the electrons are more strongly attracted by the nucleus

2. Exchange Energy
The 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 relesed
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. As a result the exchange energy is maximum
and so is the stability.
You may not that the exchange energy is at the basis of Hund’s rule that electrons which enter orbitals of
equal energy have parallel spins as far as possible.In other words, the extra stability of half-filled and
completely filled subshell is due to: (i) relatively small shielding, (ii) smaller coulombic repulsion energy,
and (iii) larger exchange energy. Detals about the exchange energy will be dealt with in higher classes.

1 2 3 4

4exchange by electron 1 3 exchange by electron 2 2 exchange by electron 3 1 exchange by electron 4

Question : The number of unpaired e– in Cr
Ans. 24Cr  1s2 2s2 2p6 3s2 3p6 4s1 3d5
 
(unpaired e–) in 24Cr, 6e– s are unpaired.
Question : The number of unpaired e– in Cr+3
Ans. Cr+3  1s2 2s2 2p6 3s2 3p6 4s0 3d3
in Cr+3, 3e– s are unpaired.
Question : The number of unpaired e– in 3d subshell of Cr+3
Ans. 3
Question : The number of unpaired e– in 3d subshell of Zn+2
30Zn  1s2, 2s2 , 2p6 , 3s2, 3p6, 4s2 ,3d10
Ans. Zero
paired e–  10, so there will be not any unpaired electron
Question : The number of unpaired e– in Co+2
1s2, 2s2 , 2p6 , 3s2, 3p6, 4s2 , 3d7
Ans. 3
Question : The number of unpaired e– in Fe+2 & Fe+3
Ans. Fe+2  1s2 2s2 2p6 3s2 3p6 4s0 3d6 = 4 unpaired e–
Fe +3
 1s2 2s2 2p6 3s2 3p6 4s0 3d5 = 5 unpaired e–

MISCELLANEOUS SOLVED QUESTIONS

Question : A Particular radiostation broadcast at a frequency of 1120 Kilo Hertz. Another radio station
broadcast at a frequency of 98.7 mega Hertz. What are the wave length of radiations from each station.
Ans. Station Ist

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 CHAPTER 2 STRUCTURE OF ATOM (JEE-NEET)
1
C 3 10 m sec
8
  = 267.86 m
 1120 103 sec 1
Station IInd
C 3 108 m sec1
  = 3.0395 m
 98.7 106 sec 1
Question : K.E. in a hydrogen atom of a particular e– is 13.6 eV, then find out P.E. of the electron,
total energy of e– & the orbit where the e– exist ?
Ans. 1. P.E. = – 2K.E.
= – 2 × 13.6
= – 27.2 ev
2. E. = – K.E.
= – 13.6 ev
3.  It will lie in 1st Orbit
Z2
 E = – 13.6 ×
n2
12
– 13.6 = – 13.6 ×
n2
n2 = 1
n=1
Question : A ball weight 25 gm moves with a velocity of 6.6 × 104 cm/sec. then find out the De
Broglie  associated with it.
h
Ans. =
mv
6.6 1034 107
= erg sec
25  6.6 104 cm / sec
1038
= 1 × 107
25
= 0.04 × 10–38
= 0.04 × 10–31 cm
= 4.0 × 10–33 cm

Question : Calculate the energy of one mole photons of radiations whose frequency is 5 × 10 10 s–1.
Ans. Energy of one photon [E] = h = (6.62 × 10–34 Js) × (5 × 1010 s–1)
= 33.1 × 10–24 J
Energy of one mole photons = Energy of one photon × Avagadro' number.
= (33.1 × 10–24 J) × (6.022 × 1023)
= 19.93 J

Question : Answer the following :

(a) How many electrons can be filled in all the orbitals with n + l = 5
(b) Which of two is paramagnetic, V(iv) or V(v)
(c) How many unpaired electrons are present in Pd (Z = 46)?
(d) The ion of an element has configuration [Ar] 3d4 in +3 oxidation state. What will be the
electronic configuration of its atom.
Ans.
(a) (n + ) = 5 has 5s, 4p and 3d orbitals with two, six and ten electrons respectively. Therefore, the
total number of electrons is 18.
(b) The configuration are : V(iv), [Ar]18 3d1 and V(v) : [Ar]18. Therefore V(iv) is paramagnetic in
nature.
(c) The electronic configuration of the element palladium (Z = 46) is [Kr]36 4d 10 5s0. Therefore, it has
no unpaired electron.
(d) The configuration of ion is [Ar] 3d4. Therefore, the configuration of the atom is [Ar]3d5 4s2.

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 CHAPTER 2 STRUCTURE OF ATOM (JEE-NEET)
Question : A bulb emits light of  = 4500Å, The bulbs is rated as 150 watt and 8% of this energy is
emitted as light. How many photons are emitted by the bulb per second?
nhc
Ans. According to Planck's theory E  , (n = number of photons)

Energy of bulb (E) = = 12w = 12 Js–1 (  1w = 1 Js–1)
 = 4500 Å = 4500 × 10–10 m
C = 3 × 108 ms–1, h = 6.62 × 10–34 Js
n   6.62 1034 J    3 108 ms 1 
12 Js–1 =
 4500 1010 m 
n=
12 Js    45 10 m 
1 8

= 2.72 × 1019 s–1

 6.62 10 Js   3 10 ms 
34 8 1

Question : Consider the following two electronic transition possibilities in a hydrogen atom as below :

n=3
n=2
n=1

(a) The electron drops from third Bohr's orbit to second Bohr's orbit followed with the next transition
from second to first Bohr's orbit.
(b) The electron drops from third Bohr's orbit to first Bohr's orbit directly. Show that the sum of
energies for the transitions n = 3 to n = 2 and n = 2 to n = 1 is equal to the energy of transition for n
= 3 to n = 1.
n=3
n=2
 1 1 
Ans. Applying  E = RH  2  2  n=1
 n1 n2 
For n = 3 to n = 2
 1 1 5
 E3 2 = RH  2  2  = RH × ......(1)
2 3  36
for n = 2 to n = 1
3
 E2  1 = RH × ................(2)
4
n = 3 to n = 1
8
 E3  1 = RH ×
9
5 3 8
adding (1) & (2) RH  RH  RH
36 4 9

so  E31 =  E3 2 +  E2 1

Question : An electron moves in an electric field with a kinetic energy of 2.5 eV. What is the associated
de Broglie wavelength?
1 p2
Ans. K.E. = mV 2 =
2 2m
so p  2mE
h h
 = =
p 2mE
6.626 1027
 =
2  9.11028  2.5 1.6 1012
 = 7.7 × 10–8 cm
50
 CHAPTER 2 STRUCTURE OF ATOM (JEE-NEET)
Question : Which hydrogen-like ion has the wavelength difference between the first lines of Balmer and
Lyman
series equal to 59.3 nm[RH = 109678 cm–1]
Ans. for 1st line of Balmer series
1  1 1 36
 Z 2 RH  2  2   B 
B 2 3  5RH Z 2
wavelength of 1st line of Lyman series
1 1 1  4
 Z 2 RH  2  2    L 
L  1 2  3 RHZ
2

Difference B –L = 59.3 × 10–7

36 4
= 2

5RH Z 3RH Z 2
on solving Z = 3
so Li2+
Question : What should be the ratio of velocities of CH4 and O2 molecules so that they are associated
with de Brogile waves of equal wave lengths ?
h
Ans. According to de Broglie equation =  
m
h
For methane (CH4)  CH 4 
mCH 4  CH 4
h
For oxygen (O2)  O2 
mO2  O2
Since the wavelength of CH4 and O2 are to be equal
CH4 =  O2
h h
or 
mCH 4  CH 4 mO2  O2
mCH4  CH4 = mO2  O2
CH 4 mO2 32
or   2
O2 mCH 4 16
Question : A dust particle has mass equal to 10–11 g, diameter 10–4 cm and velocity 10–4 cm sec–1. The
error in measurement of velocity is 0.1%. Calculate uncertainty in its position. Comment on the result.
Ans.  = 10–4 cm sec–1
0.1104
  =  1107 cm sec–1
100
h
Now, x =
4m
6.625 1027
 x = = 5.27 × 10-10 cm
4  3.14 1011 107
The uncertainty in position as compared to uncertainty in velocity is very low.

Question : An atom has 2K, 8L, 5M, electrons. Write down its electronic configuration and indicate in it
(i) number of subshells (ii) number of orbitals
(iii) number of unpaired electrons (iv) number of electrons having  = 1.
Ans. In the given atom there are ( 2 + 8 + 5) = 15 electrons. The electronic configuration of the atom
is 1s2, 2s2, 2p6, 3s2, 3px1, 3py1, 3pz1
(i) number of subshells is 5 (ii) number of orbitals is 9
(ii) number of unpaired electrons is 3 (iv) number of electrons having = 1 is 9.

51