ATOMIC STRUCTURE

A tomic S tructure
1. ATOM & MOLECULES

(a) The smallest particle of a matter that takes part in a chemical reaction is called an atom. The atom of all gases
except those of noble gases, cannot exist in free state. These exist in molecular form. The molecules of
hydrogen, nitrogen, oxygen and halogens are diatomic (H2, N2). Phosphorus molecule is tetratomic and that of
sulphur is octa atomic.

(b) The smallest particle of a matter that can exist in free state in nature, is known as a molecule.

(c) Some molecules are composed of homoatomic atom, e.g., H2, O2, N2, Cl2, O3 etc., while the molecules of
compounds are made up of two or more heteroatomic atoms e.g., HCl, NaOH, HNO3, CaCO3, etc.

2. DALTON’S ATOMIC THEORY

The concepts put forward by John Dalton regarding the composition of matter are known as Dalton’s atomic
theory. Its important points are as follows.
(a) Every matter is composed of very minute particles, called atoms that take part in chemical reactions.
(b) Atoms cannot be further subdivided.
(c) The atoms of different elements differ from each other in their properties and masses, while the atoms of the
same element are identical in all respects.
(d) The atoms of different elements can combine in simple ratio to form compounds. The masses of combining
elements represent the masses of combining atoms.
(e) Atom can neither be created nor destroyed.
2.1 Modern Concept :
Many of the concepts of Dalton’s atomic theory cannot be explained. Therefore, foundation of modern atomic
theory was laid down by the end of nineteenth century. The modern theory is substantiated by the existence of
isotopes, radioactive disintegration, etc. The important points of the modern atomic theory are as follows.
(a) Prof. Henri Bacquerel discovered the phenomenon of radioactivity and found that an atom is divisible.
(b) An atom is mainly composed of three fundamental particles, viz. electron, proton and neutron.
(c) Apart from the aforesaid three fundamental particles, many others have also been identified, viz. positron,
meson, neutrino, antiproton, etc.
(d) Soddy discovered the existence of isotopes, which were atom of the same element having different masses.
For example, protium, deuterium and tritium are atoms of hydrogen having atomic masses 1, 2 and 3 a.m.u.
respectively.
(e) Atoms having same mass may have different atomic numbers. These are known as isobars. For example,
40 40
18 Ar and 20 Ca .

(f) Atoms of elements combines to form molecules.

(g) It is not necessary that the atoms should combine in simple ratio for the formation of compounds. The atoms in
non-stoichiometric compounds are not present in simple ratio. For example, in ferrous sulphide crystals, iron
and sulphur atoms are present in the ratio of 0.86 : 1.00.
(h) Atoms participate in chemical reactions.
 ATOMIC STRUCTURE

3. CATHODE RAYS (DISCOVERY OF ELECTRON)

Dry gases are normally bad conductors of electricity. But under low pressure, i.e., 0.1 mm of mercury or lower,
electric current can pass through the gases. Julius Plucker in 1859 found that a type of rays, called cathode
rays, emit from the cathode when electricity is passed through a discharge tube. William Crookes (1879),
J.J.Thomson and many other scientists studied the properties of cathode rays and came to the conclusion that
the cathode rays of same properties are obtained using any gas or any cathode material.

To vacuum pump
Cathode rays
Fluorescence

Cathode
Anode +
High voltage

Production of cathode rays

The salient features of cathode ray are as follows.

(a) Cathode rays travel in a straight line. This indicates that the formation of a shadow when an opaque object is
placed in its path.

Cross

Shadow –
Cathode

Anode
+
Cathode rays travel in a straight line

(b) If a light metal pinwheel is placed in the path of cathode rays, the wheel starts revolving. This proves that is
cathode rays consist of tiny particles having momentum.

– +

Anode
Cathode
Cathode rays Pin wheel

Cathode rays consist of tiny particles

 ATOMIC STRUCTURE

(c) Cathode rays get deviated in electrical and magnetic fields. This proves that they are composed of charged
particles. Their derivation towards anode indicates their negatively charged nature. The direction of their
deviation in magnetic field depends on pole of the magnet which has been placed near the cathode ray tube.
S
Electric field
–
– + – +
Cathode Anode Cathode Anode
+

To vacuum pump N To vacuum pump

(a) Electric Field (b) Magnetic Field

(d) Cathode rays produce green fluorescence on the walls of the glass tube.

(e) Cathode rays produce incandescence in at thin metal foil.

(f) Cathode rays effect the photographic plate.

(g) Cathode rays ionize gases proving that they are charged.

(h) Cathode rays penetrates across a thin metal foil.

(i) Cathode rays produce X-rays when they hit a piece of tungsten or any other metal having high melting point.

3.1 Nature of Cathode Rays :

J.J. Thomson (1897) proved through experiments that.

(a) Cathode rays are composed of extremely tiny negatively charged particles (electrons).

(b) The ratio of negative charge (e) and mass (m) for cathode ray particle (electrons) is a constat. This ratio is
independent of the material used in the preparation of the electrodes of the discharge tube or the gas filled in it.
Thus, e/m of an electron is a universal constant.

ch arg e on electron e 8
mass of electron = = 1.76 × 10 Coulomb/gm
m

In addition to the above proofs, photoelectric effect, thermionic effect and emission of beta particles from
radioactive elements also confirm that electron is an essential constituent of matter. These negatively charged
– 0
tiny particles discovered by Thomson. It is denoted by e or –1e .

Electrostatic Fluorescence
field plate screen

Electron ray

–
Cathode X

Slitted anode Slit Y

Empty glass tube

Electromagnet

e
Determination of of an electron
m
 ATOMIC STRUCTURE

4. POSITIVE RAYS OR CANAL RAYS : DISCOVERY OF PROTON

Eugene Goldstein in 1886 found that a dim glow is visible behind the cathode when an electric discharge is
passed through a perforated cathode in a discharge tube filled with a gas at low pressure. These new type of
rays travel from anode to that cathode. Goldstein gave the name canal rays to these rays because these rays
cross the canals of the cathode and reach the other side. W.Wein in 1897 proved through experiments that the
canal rays consist of positively charged particles. J.J. Thomson gave the name positive rays to them be-
cause they are composed of positively charged particles.
4.1 Properties of Positive Rays :
(a) Positive rays travel in the direction opposite to that of cathode rays.
(b) Positive rays travel in straight line.
(c) Positive rays affect photographic plate.
(d) Positive rays are deviated in the electric and magnetic fields. The direction of their deviation proves the presence
of positive charge on their particles.
(e) Positive rays pass across a very thin sheet of metal. But their penetrating power is less than that of cathode
rays.
(f) Positive rays produce fluorescence and phosphorescence.
4.2 Nature of Positive Rays :
Thomson and Wein studied the nature of positive rays and proved with the help of experiments that.
(a) Positive rays are composed of positively charged particles.
(b) The ratio (e/m), of positive charge (e) and mass (m) for the particles of positive rays depends on the nature of the
gas filled in the discharge tube. The value of e/m for the particles of positive rays obtained from different gases
is different. The e/m value for positive rays is not a universal constant. Thomson and Wein found out through
experiments that the maximum value of e/m is for particles of positive rays of hydrogen gas.
+
(c) Experiments proved that for a positively charged particle (H ) of the positive rays of hydrogen gas

e 4 –19
= 9.578 × 10 coulomb per gram. If we suppose that the charge (e) of this particle is 1.602 × 10 coulomb
m
–24 +
unit positive charge, the mass (m) of the particle will be 1.6725 × 10 gram. The particle (H ) of the positive
–19 –24
rays of hydrogen gas having 1.602 × 10 coulomb positive charge and 1.6725 × 10 gram mass is called a
proton.

5. PROTON
(a) Proton is a fundamental particle of an atom. It is an essential constituent of every matter.
(b) The credit for the discovery of proton goes to Goldstein.
(c) Proton bears one unit positive charge.
4
(d) Thomson and Wein estimated the value of e/m as 9.578 × 10 coulomb per gram for the positively charged
particle proton.
–19 –10
(e) The amount of positive charge (e) on proton is 1.602 ×10 coulomb or 4.8 × 10 e.s.u.
–24 –17
(f) Mass of proton (m) = 1.6725 × 10 gram ; = 1.6775 × 10 kilogram
–29
= 1.6725 × 10 quintal ; = 1837 times that of electron
= 1.00757 a.m.u. ; = Mass of hydrogen atom

1.6725 × 10−24
Mass of proton (m) in a.m.u = = 1.00757 a.m.u.
1.66 × 10−24
 ATOMIC STRUCTURE

23
(g) Mass of proton (m) multiplied by Avogadro number (6.023 × 10 ) gives molar mass of proton. Thus
–24 23
Gram molecular mass of proton = 1.6725 × 10 × 6.023 × 10 = 1.008 (Approx)
(h) Proton is present in the nucleus of an atom.
(i) The number of electrons is equal to the number of protons in a neutral atom.
(j) The atomic number of an atom is equal to the number of protons present in the nucleus of that atom.
(k) Proton is the nucleus of protium i.e. the common hydrogen atom.
+
(l) Proton is ionized hydrogen atom, i.e. (H )
(m) Proton is obtained when the only one electron present in hydrogen atom is removed. Hydrogen atom consists of
only one electron and one proton.

– 0
6. ELECTRON (e or –1e )

(a) Electron is a fundamental particle of an atom, which is an essential constituent of every matter.
(b) The credit for discovery of cathode rays goes to Sir William Crookes while the credit for discovery of negatively
charged electron goes to J.J. Thomson. The name ‘electron’ was first given by Stony.
(c) A unit negative charge is present on electron.

e 8
(d) The value of was found to be 1.76 × 10 coulomb/gram by Thomson.
m

(e) R.A. Mulliken calculated the charge on an electron by his famous Oil Drop Experiment. The value came out
–19 –10
to be 1.6012 × 10 coulomb or 4.803 × 10 e.s.u.
(f) The value of e/m of an electron is known as its specific charge. With the help of this specific charge and the
charge on the electron (determined by Mulliken), the mass of the electron could be calculated as follows.

e 1.6012 × 10 −19 coulomb –28

= = 9.1091 × 10 gram
e/m 1.76 × 10 8 coulomb / gram

= 0.0005486 a.m.u.
th
= 1/1837 of H atom
23
(g) Molar mass of electron is obtained on multiplying mass of electron by Avogadro number (6.023 × 10 ).
Therefore gram molecular mass of electron is as follows.
–28 23
= 9.1091 × 10 × 6.023 × 10
–4
= 5.483 × 10
(h) Electron is very much lighter than an atom of the lightest element hydrogen. The gram molecular mass of
hydrogen is 1.008. Therefore the ratio of gram molecular mass of hydrogen and that of electron is

1.008
= 1837. In other words, an atom of hydrogen (or a proton) is 1837 times heavier than electron.
5.483 × 10 − 4

Mass of H atom 1.67 × 10 −24

= = 1837
Mass of electron 5.483 × 10 − 28
27
(i) The mass of 1.1 × 10 electrons is one gram.
(j) The mass of one mole of electrons is 0.5583 mg.
 ATOMIC STRUCTURE

(k) The amount of charge on one mole of electrons is one faraday or 96500 coulomb.
–28
(l) The mass of an electron at rest is called static electron mass and its value is 9.1091 × 10 gram.
(m) The mass of an electron in motion is calculated with the help of the following expression.

Re st mass of electron
Mass of electron in motion (m) =
  v 2 
1 –   
  c  

where v is velocity of electron and c is velocity of light.

When v = c, the mass of the electron in motion becomes infinity.
Therefore the mass of an electron increases with increase in its velocity due to which specific charge e/m on it
decreases.
(n) Electron, being the fundamental particle of an atom, takes part in chemical combination.
(o) The physical and chemical properties of an element depend on the distribution of electrons in its outermost
energy level.

7. DISCOVERY OF NEUTRON
Penetrating rays are emitted on bombarding α-particles on the elements like beryllium, boron and aluminium.
James Chadwick in 1932 studied the nature of these radiation and came to the conclusion that these rays are
composed of very tiny electro neutral particles. The mass of these particles is almost equal to that of the
1
hydrogen atom. This particle is called neutron and is denoted by the symbol, 0n .
1
7.1 Neutron (0n )
(a) It is a fundamental particle of atom that is present in the nuclei of all atoms except hydrogen or protium.
(b) It was discovered by James Chadwick in 1932.
(c) It is an electro neutral particle, i.e. it does not have any positive or negative charge on it.
(d) The mass of a neutron is almost equal to that of a proton. Actually it is a little bit heavier than proton. Its mass
(m) is as fallows :
–24
Mass (m) of a neutron = 1.6748 × 10 gram = Approximately mass of a proton
(e) Neutron is relatively heavier out of the three fundamental particles of an atom.
(f) Molar mass of a neutron is obtained by multiplying the mass (m) of a neutron with Avogadro number
23 –24 23
(6.023 × 10 ). Therefore the gram molecular mass of a neutron is 1.6748 × 10 × 6.23 × 10 = 1.00893.
(g) The atomic mass is equal to the total mass of all the protons and neutrons present in the atom.
(h) Isotopes are formed as a result of difference in the number of only neutrons in the nuclei of atoms.
(i) It is assumed that a neutron is a result to joining together of an electron and a proton. A neutron, being unstable,
decays as fallows :
1 1– 0 0
0n +1P + –1e + 0q (antineutrino)
Its half-life is 20 minutes.
12
(j) The density of neutrons is of the order of 1 × 10 Kg/c.c.
 ATOMIC STRUCTURE

8. OTHER PARTICLES OF ATOM

(a) Positron : It was discovered by C.D. Anderson in 1932. It beards a unit positive charge and its mass is equal
to that of an electron. Thus its mass regarded as negligible. It merges with an electron and emit electromagnetic
+
radiations. It is denoted by e .
(b) Meson : Yukawa in 1935 discovered this particle. Different types of meson particles are possible in the atom.
These are called meson family.
(c) Neutrino : Pauling discovered these particles in 1927. They do not bear any charge, i.e. they are electro
neutral particle.
(d) Antiproton : Segre discovered this particle in 1956. It bears a unit negative charge and its mass is equal to that
of a proton.

9. CLASSIFICATION OF ATOMIC PARTICLES

9.1 Stable Particles
Properties of Stable Fundamental Particles
Particle Symbol Charge Mass* Mass** Spin***
1
1. Proton p + 1.00758 1, 836
2
1
2. Electron e–, β– – 0.0005486 1
2
1
3. Positron e+, β+ + 0.0005486 1
2
1
4. Neutrino v 0 0.000022 0.04
2
1
5. Antiproton p– – 1.00758 1, 836
2
6. Graviton G 0 0 0 2

7. Photon γ 0 0 0 1

16
*Physical atomic weight unit 8O = 16,00,000
–28
**Mass with respect to e, where e = 9.11 × 10 gram
h
*** unit
2π
9.2 Unstable Particles
Properties of Some Unstable Fundamental Particles
Particle Symbol Charge Mass* Mass** Spin***
1
1. Neutron n 0 1.00893 1, 836
2
1
2. Negative µ meson µ– – 0.1152 210
2
1
3. Positive µ meson µ+ + 0.1152 210
2
4. Neutral π meson π0 0 0.1454 265 0

5. Negative π meson π– – 0.1514 276 0

6. Positive π meson π+ + 0.1514 276 0

 ATOMIC STRUCTURE

9.3 Distinction of α, β and γ Rays

Property α Ray β Ray γ Ray

1. Velocity 2 × 109 cm/sec 2.8 × 1010 cm/sec Equal to velocity of light.

3 × 1010 cm/sec
2. Penetration power Very low About 10 times to About 1000 times to that
that of α rays that of α rays
3. Charge and mass 2 unit positive charge 1 unit negative charge Magnetic radiations of
and 4 unit mass and zero mass very high frequency
4. Effect of ZnS plate Produce fluoresence No effect No effect
+2
5. Nature He or helium nuclei, Denoted by the symbol denoted by the symbol
denoted by the symbol 1e0 or electron 0
γ0
4
2
He .
6. Megnetic field Deviation towards Deviation towards No effect
cathode anode
α β γ
A9 →
–
A9 →
–
A9 →
–
7. Nature of the product 4 2
A5 4 5
A9 4 4
A9

10. NUCLEUS
(i) Rutherford discovered the nucleus in an atom by α-particle scattering experiment. He showered α-par-
4
ticles, 2He (obtained from radium) on a 0.01 mm thin gold film and allowed them to collide with a screen coated
with zinc sulphide and placed behind the gold film. He observed fluorescence on the screen.
(a) Most of the α-particle passed through the gold film without deviating from their path.
(b) Some particles got deviated from their path on colliding with the gold film.
(c) A very small number of particles rebounded after colliding with the gold film.

α-Particles deviated from

their path
Uneviated α-particles

α-Particles Nucleus

α-Particle rebounded by the nucleus

Deviated α -particles

(ii) The following are the inferences derived from the above experiment.
(a) Most of the α-particles pass through the gold foil without deviation in their path, showing that most of the part
if an atom is vacant.
(b) Whole of the mass of an atom is confined to its nucleus, which consists of positively charged protons and
neutral neutrons. These together are termed as nucleons.
–13 –12
(c) It has been found on the basis of calculation that the radius of the atomic nucleus is 1 × 10 to 1 × 10 cm
–15 –14 –8
or 1 × 10 to 1 × 10 meter, while radius of an atom is 1 × 10 cm.
 ATOMIC STRUCTURE

Radius of atom
(d) Magnitude of atomic nucleus = Radius of atomic nucleus

Mass(M)
(e) Nuclear density Density (D) = Volume (V)

Since, the shape of atom is regarded as spherical, therefore, if radius of the nucleus is r, then

4 3
Volume of nucleus = πr
3

Ex.1 Calculate the density of fluorine nucleus supposing that the shape of the nucleus is spherical and its radius is
–13
5 × 10 . (Mass of F = 19 amu)
–24
Sol. ∴ Mass of the nucleus of F atom = 19 × 1.66 × 10 gm
–24
(1 amu = 1.660 × 10 gm)

4 3
Volume of the nucleus of F atom = πr
3

4 –13 3
= × 3.14 (5 × 10 )
3
–39 3
= 525 × 10 cm

Mass
Density of the nucleus of F atom =
Volume

19 × 1.66 × 10−24 gm
=
525 × 10–39 cm3
13 –3
= 6.0 × 10 gm cm

11. NUCLEAR CHARGE AND ATOMIC NUMBER

Positive charge on the nucleus of an atom is equal to the atomic number of that atom. A scientist named
Mosley studied the frequency of X-rays emitted by showering high velocity electrons on a metal and established
the following relationship.

ν = a (z – b)
where ν = frequency of X-rays
z = atomic number or nuclear charge
a and b are constants.
Thus nuclear charge of an atom is equal to the atomic number of that atom. Since an atom is electro neutral,
the number of positively charged protons in its nucleus is equal to the negatively charged electrons moving
around the nucleus in the atom. Thus
Atomic number = number of protons in the atom or
number of electrons in the atom
 ATOMIC STRUCTURE

12. ATOMIC WEIGHT OR MASS NUMBER

The value of mass number of an atom (in amu) is always a whole number.
Mass number of an atom is the sum of number of protons and number of neutrons present in that atom.
Mass number = Number of protons (Z) + Number of neutrons (n)
= Atomic number + Number of neutrons
16 14 23
For example 8O 7N 11Na

Protons 8 7 11
Neutrons 8 7 12

Atomic weight 16 14 23

(a) The protons and neutrons present in the nucleus are known as nucleons.
(b) The weight of electrons is neglected during calculation of the atomic weight, because the mass of an electron is
negligible in comparison to that of a proton or a neutron.
(c) In the nucleus of an electro neutral atom, the number of positively charged protons is equal to that of negatively
charged electrons.
16 14 23 12 17
Particle 8O 7N 11Na 6C 9F

Protons 8 7 11 6 9

Neutrons 8 7 12 6 8

Atomic 16 14 23 12 17
weight

Electrons 8 7 11 6 9

(d) The number of protons present in an atom is called atomic number of that atom.
For example O F Ne
Protons 8 9 10
Atomic number 8 9 10
(e) Kernel : The group of all the electrons except those of the outermost energy level, is called that kernel of that
atom and the electrons present in the kernel are known as electron of the kernel.
For example, if the electronic configuration of an atom is 2, 6, then the number of kernel electrons is 2.
If the electronic configuration of an atom is 2, 8, 8, then the number of kernel electrons is 10.
If the electronic configuration of an atom is 2, 8, 8, 8, then the number of kernel electrons is 18.

13. IONS
When an atom loses electron, it is converted into a cation, while it is converted into an anion on gaining electron.
(a) Number of electrons in a cation = Number of protons - charge present on the cation
(b) Number of electrons in a anion = Number of protons + Charge present on the anion
 ATOMIC STRUCTURE

+ +2 +3
For example Na Mg Al
Protons 11 12 13
Electrons 10 10 10
– –2 –
Cl O F
Protons 17 8 9
Electrons 18 10 10
Ex.2 What difference will appear in the mass number if the number of neutrons is halved number of electrons is
16
doubled in 8O .
[1] 25% decrease [2] 50% increase [3] 150% increase [4] No difference Ans.[1]
16
Sol. 8O Initial weight – final weight
Protons 8p → 8p
Neutrons 8n → 4n
Weight 16 → 12
Thus decrease in mass number = 25%
+2
Ex.3 If the atomic weight of Zn is 70 and its atomic number is 30, then what will be the atomic weight of Zn ?
[1] 70 [2] 68 [3] 72 [4] 74 Ans. [1]
+2
Sol. Two electrons are removed in the formation of Zn from Zn. The numbers of protons and neutrons remain
unchanged.
Ex.4 The mass of one mole electrons should be -
[1] 0.55 mg [2] 1.0008 gm [3] 1.000 gm [4] 0.184 gm Ans. [1]
23
Sol. The number of electrons in one mole = Avogadro number = 6.023 × 10
–28
Mass of one electron = 9.1 × 10 gm
23
Therefore Mass of 6.023 × 10 electrons
–28 23
= 9.1 × 10 × 6.023 × 10 = 0.55 mg
Ex.5 The number of atoms present in 20 grams of calcium will be equal to the number of atoms present in

1
(20 gm Ca = mole Ca)
2

6.023 × 10 23 23
Ca = = 3.012 × 10
2

[1] 12 gm C [2] 12.15 gm Mg [3] 24.0 gm C [4] 24.3 gm Mg Ans. [2]

1
Sol. 24.3 gm Mg = 1 mole, therefore 12.15 gm = mole
2

14. ISOTOPES
(a) The atoms of the same element having same atomic number but different atomic weights, are called isotopes.
(b) Isotopes of an element have same number of protons but different number of neutrons in their atoms. Hence
their atomic weight are different. For example, oxygen has the following three isotopes.
 ATOMIC STRUCTURE

16 17 18
8O 8O 8O

Protons 8 8 8

Neutrons 8 9 10

Atomic weights 16 17 18

(c) Hydrogen has the following three isotopes.

1 2 3
1H (Protium) 1D (Deuterium) 1T (Tritium)

Protons 1 1 1

Neutrons 0 1 2

Atomic weights 1 2 3

(d) Chlorine has the following two isotopes.

35 37
17C and 17Cl

Ex.6 What should be the percentage of deuterium in heavy water ?

[1] 20% [2] 80% [3] 60% [4] 40% Ans. [1]

Sol. Deuterium in 20 parts of D2O = 4 parts

4
Deuterium in 100 parts of D2O = × 100 = 20%
20

Ex.7 Which of the following pairs consists of molecules having same mass number ?

[1] H2O and D2O [2] H2O and HTO [3] D2O and HTO [4] D2O and HCl Ans. [3]

Sol. Mass number of H2O = 18

Mass number of D2O = 20

Mass number of HTO = 20

Mass number of HCl = 36.5

Ex.8 The mass number of three isotopes of an element are 11, 12 and 13 units. Their percentage abundance is 80,
15 and 5 respectively. What should be the atomic weight of the element ?

[1] 11.25 [2] 20 [3] 16 [4] 10 Ans. [1]

Sol. 80 : 15 : 5

Thus the ratio is 16 : 3 : 1

Total = 16 + 3 + 1 = 20

11× 16 + 12 × 3 + 13 × 1
Average weight = = 11.25
20

Ex.9 If two neutrons are added to an element X, then it will get converted to its

[1] isotope [2] isotone [3] isobar [4] None of the above Ans. [1]

Sol. The number of neutrons are different in the isotopes of the same element.
 ATOMIC STRUCTURE

15. ISOBARS
(a) Isobars are the atoms of different elements having same atomic weight.
(b) Isobars have different numbers of protons as well as neutrons.
(c) The sum of number of protons and neutrons in isobars is same. For example
40 40 40
Atomic weight of three elements 18Ar , 19K and 20Ca is 40.
40 40 40
(i) Ar K Ca
Protons 18 19 20
Neutrons 22 21 20
76 76
(ii) 32Ge 34Se

Protons 32 34
Neutrons 44 42

16. ISOTONES
The atoms having same number of neutrons are called isoneutronic or isotones. For example
30 31 32
14Si 15P 14S

Protons 14 15 16
Neutrons 16 16 16
Atomic weight 30 31 32

Ex.10 In two elements Z1 A M1 and Z2 BM2 , M1 ≠ M2 and Z1 ≠ Z2 but M1 – Z1 = M2 – Z2. These elements are

[1] isotonic [2] isotopic [3] isobaric [4] isoprotonic Ans [1]
Sol. M1 = Atomic weight Z1 = Atomic number
In isobars M1 = M2 and in isotopes Z1 = Z2
In isotones (isoneutronic elements) M1 – Z1 = M2 – Z2
Ex.11 Two nuclides A and B are isoneutronic. Their mass numbers are 76 and 77 respectively. If atomic number of A
is 32, then the atomic number of B will be
[1] 33 [2] 34 [3] 32 [4] 30 Ans. [1]
76 77
Sol. 32A PB

Protons = 32 Protons + Neutrons = 77

Protons + Neutrons = 76 Neutrons = 44
Neutrons = 44 Protons = 33

17. ISOELECTRONIC
The chemical species in which number of electrons is same are called isoelectronic. For example
+ +2 +3
(a) Li Be B
Electrons 2 2 2
+ +2 +3 – –2
(b) Na Mg Al F O
Electrons 10 10 10 10 10
+ +2
(c) K Ca Ar
Electrons 18 18 18
 ATOMIC STRUCTURE

Ex.12 The isoelectronic pair of 32 electron is

–3 –2 –3 –2
[1] BO3 and CO3 [2] PO4 and CO3 [3] N2 and CO [4] All of the above Ans. [1]
–3 –2
Sol. BO3 CO3
5 + 24 + 3 = 32 6 + 24 + 2 = 32
Ex.13 The pair NH3 + BH3 is isoelectronic with
[1] B2H6 [2] C2H6 [3] C2H4 [4] CO2 Ans. [2]
Sol. NH3 + BH3 C2H6
7 + 3 + 5 + 3 = 18 6 × 2 + 6 = 18
Ex.14 Which of the following is a one-electron species ?
[1] He [2] N [3] H2 [4] N2 Ans. [4]
+
Sol. There is only one electron in H2
Ex.15 The molecular weight of an oxide of nitrogen is 30. What should be the number of electrons in it ?
[1] 15 [2] 30 [3] 45 [4] 20 Ans. [1]
Sol. The molecular weight of NO is 30. It will have 15 electrons.
Ex.16 A diapositive ion has 16 protons. What should be the number of electrons in its tetrapositive ion.
[1]16 [2] 14 [3] 12 [4] 10 Ans. [3]
+2
Sol. X has 16 protons, then In X – 16 protons and 16 electrons
In X+2 – 16 protons and 14 electrons In X+4 – 16 protons and 12 electrons
Ex.17 If atomic weights of C and Si are 12 and 28 respectively, then what is the ratio of numbers of neutrons in them
[1] 1 : 2 [2] 2 : 3 [3] 3 : 4 [4] 3 : 7 Ans. [4]
12 28
Sol. Number of neutrons in 6C = 12 – 6 = 6 ; Number of neutrons in 14Si = 28 – 14 = 14
The ratio of number of neutrons in C and Si is 6 : 14 or 3 : 7.

18. ATOMIC MODEL

18.1 Thomson’s Model of an Atom
(i) Atom is a very minute, spherical, electro neutral particle that consists of positively and negatively charged
matter.
(ii) The positively charged matter is uniformly distributed in the atom and the negatively charged electrons are
embedded in it just as the seeds in water melon. Therefore, Thomson model of an atom is also called “water
melon model”.
(iii) Thomson’s model of an atom failed to explain the production of the atomic spectrum. It cannot explain Rutherford’s
α particle scattering experiment also.
18.2 Rutherford’s Model of an Atom
Ernest Rutherford in 1911put forward the “nuclear model” of atom on the basis of α particle scattering
+2
experiment. In this experiment, Rutherford showered α−particles (Helium nuclei, He ) on a thin gold foil and
observed that most of the α-particles travelled straight without deviation in the direction of their path, some of
them deviate from their path by different angles, while very few get rebounded after colliding with the foil.
Rutherford gave the following nuclear model on the basis of the experiment.
 ATOMIC STRUCTURE

Fluorescence of
light

Gold foil

ZnS screen

Slit

Source of α particles

Rutherford's α particle scattering experiment

(i) Atom is a very minute, spherical, electro neutral particle composed of the following two parts :
(a) Positively charged nucleus and (b) a vast extranuclear space in which electrons are present.
(ii) whole of the positive charge and almost all the mass of atom is confined to a very minute part at the centre of the
–13 –12 –15 –14
atom, called the nucleus of the atom. The radius of nucleus is about 10 to 10 cm (or 10 to 10 meter),
–8
while the radius of atom is in the order of 10 cm.
(iii) The number of electrons in an atom is equal to the number of protons present in the nucleus. That is why an
atom is electroneutral.
(iv) This model of an atom is also called “solar model” of “planetary model”. This is because, the movement of
electrons around the nucleus in this model has been compared to that of planets moving around the sun in the
solar system.
18.2.1 Demerits of Rutherford’s Model of an Atom
(i) According to Clark Maxwell’s theory of electrodynamics, an electrically charged particle in motion continuously
emits energy. This results in regular decrease in the energy of that particle. On the basis of this principle, it can
be concluded that an electron moving around the nucleus will continuously emit the energy. This will result in
decrease in the radius of the electron orbit, due to which the electron would ultimately plunge into the nucleus.

e–
An electron emitting energy and pluging into nucleus

(ii) Plunging of an electron into the nucleus would definitely mean destruction of the atom or end of the existence of
the atom. But we know that it never happens. Atom is a stable system. Therefore Rutherford model failed in
explaining the stability of an atomic system.
(iii) If an electron moving around the nucleus continuously emits energy, then the atomic spectrum must be
continuous, i.e. the spectrum should not have lines of definite frequency. However, the atomic spectrum is
actually not continuous and possesses so many lines of definite frequency. Therefore, Rutherford model failed to
explain the line spectrum of an atom.
 ATOMIC STRUCTURE

18.3 Bohr’s Model of an Atom

Neil Bohr in 1913 presented a quantum mechanical model of atomic structure.
(i) An electron moves around the nucleus in constant circular orbits.

Number of orbits
4
3 Electrons are absent
between two
2 successive orbits
1
Electron in
circular orbits
+
Nucleus

Electrons moving around in circular orbits

(ii) The electrons moving around the nucleus in only those circular orbits for which their angular momentum (mvr) is

h
integral multiple of . This is called the condition of quantization. The angular momentum (mvr) of an electron
2π

nh
is where m is the mass of electron. r is radius of its circular orbit, v is the velocity of electron, h is Planck’s
2π

constant; n is a whole number whose value may be 1, 2, 3, 4 etc, : n is called principal quantum number.
(iii) When energy is provided to an atom, its electrons get excited by absorption of energy and jumps to the orbits
of higher energy.
(iv) When an electron in an atom falls from higher energy level to lower energy level, spectral lines are formed.

Decrease in energy by
Increase in energy by emission of photons
absorption of photons

+ +
1 1
2 2
3 3
4 4
(a) Electron jumping from lower to higher energy level by absorption of energy
(b) Electron jumping from higher to lower energy level by emission of energy

(v) The force of attraction on electron by the nucleus is equal to the centrifugal force of that electron.

mv 2
r
e Force of attraction
v
r

+ Ze

The electron moving in an orbit by various forces

 ATOMIC STRUCTURE

nh mv 2 Ze2
Note : (a) mvr = ........[1] (b) = 2 ........[2] (c) En2 – En1 = hν...........[3]
2π r r

Ex.18 An electron has been excited from the first to the fourth energy state in an atom. Which of the following
transitions are possible when the electron comes back to the ground state ?
[1] 4 → 1 [2] 4 → 2, 2 → 1 [3] 4 → 3, 3 → 2m 2 → 1[4] All of the above Ans. [4]
Sol. Electron can undergo transition from higher state to all lower states by loss of energy.
Ex.19 How much total energy will be released when an electron present in hydrogen atom undergoes the following
sequence of transition ?
n=4→n=2→n=1
[1] One quantum [2] Two quantums [3] Three quantums [4] Four quantums Ans. [2]
Sol. One quantum of energy is released in each transition, i.e. one quantum in n = 4 to n = 2 and one quantum in
n = 2 to n = 1 transition.
Ex.20 Which of the following is a fundamental particle
[1] Nucleus of He [2] Nucleus of H [3] A positive atom [4] None of these Ans. [2]
+
Sol. Fundamental particle H is the nucleus of H

19. CALCULATION OF VELOCITY OF THE ELECTRON OF BOHR’S ORBIT

mv 2 Ze2
= 2 .............[1]
r r

From Bohr’s postulate

nh
mvr = ...............[2]
2π

Eq. [1] divided by [2]

2πZe 2 z
v= or v=K
nh n

Here π , e and h are constants, therefore

2πe 2 8
Here K = = 2.188 × 10 cm/second
h

Z
or v= × 2.188 ×108 cm / sec ond
n

(a) If Z is a constant, then

1
v∝
n
 ATOMIC STRUCTURE

Therefore, velocity goes on decreasing with increase in the number of orbits.

Thus

v1 n 2
=
v2 n1

(b) If n is a constant, then

v∝ Z
Therefore, velocity goes on increasing with increase in the atomic number.

v1 z1
=
v 2 z2

2πr
(c) Time period T =
V

2π × n2 h2 nh
= ×
4π2mZe2 2πZe2

n3h3
=
4π2mZ 2 e4

1 V
(d) Frequency =
T 2πr

Ex.21 The expression for calculation of velocity is

1
 Ze2  2 2πZe2 nh
[1] v =   [2] v = [3] v = [4] all of the above are correct
 mr  nh 2πmr

Ans. [4]

2 Ze2  Ze2  2
Sol. [1] v = v=  
mr  mr 

2πZe2
[2] v =
nh

nh nh
[3] mvr = v=
2π 2πmr
 ATOMIC STRUCTURE

Ex. 22 If the velocities of first, second, third and fourth orbits of hydrogen atom are v1 , v2 , v3 and v4 respectively, then
which of the following should be their increasing order
[1] v1 > v2 > v3 > v4 [2] v4 < v3 < v2 < v1 [3] v1 > v2 < v3 > v4 [4] Equal for all Ans. [2]

1
Sol. Z is a constant, therefore v ∝
n

i.e. v4 < v3 < v2 < v1

+10
Ex.23 The ratio of velocities of electrons present in Na and H should be
[1] 11 : 1 [2] 11:3 [3] 1 : 11 [4] 4 : 11
11 +10 1
Sol. Na → Na → Is
Thus, n is a constant

v1 Z1 11
Therefore v = Z = 1
2 2

Ex.24 What should be the velocity of the electron present in the fourth orbit of hydrogen atom, if the velocity of the
7
electron present in the third orbit is 7.29 × 10 cm per second ?

v 3 n4
Sol. =
v 4 n3

7.29 × 107 4
=
v4 3

7.29 × 107 × 3 7
v4 = = 5.46 × 10 cm per second
4

th
20. RADIUS OF n BOHR’S ORBIT
According to Bohr’s hypothesis

nh
put the value of v in mvr =
2π

n2h2 n2
r= or r =K
4π2 mZe2 z

In the above expression h, π, m and e, all are constants. therefore

 h2 
K = 2 2 = constant = 0.529Å 
 4π me 

n2
or r= × 0.529 Å
Z
 ATOMIC STRUCTURE

–8
Note : (a) 1Å = 10 cm
–10
(b) 1Å = 10 m
–9
(c) 1 nm = 10 m
–10
(d) 1 pm (picometer) = 10 cm
If Z is a constant, then

r ∝ n2

Thus, the radius of atoms goes on increasing as the number (n) of energy levels in the atoms goes on increasing
as shown below.

r1 n12
=
r2 n22

(b) If n is a constant, then

r1 Z 2
=
r2 Z1
1/z

Ex.25 If the radius of first, second, third and fourth orbits of hydrogen atom are r1, r2, r3 and r4 respectively, then their
correct increasing order will be
[1] r4 < r3 < r2 < r1 [2] r1 < r2 < r3 < r4 [3] r1 > r2 > r3 > r4 [4] Equal in all Ans. [2]
2
Sol. r∝ n

r1 < r2 < r3 < r4

+ +
Ex. 26 The ratio of radius of the fifth orbits of He and Li will be
[1] 2 : 3 [2] 3 : 2 [3] 4 : 1 [4] 5 : 3 Ans. [2]
Sol. Here n is a constant, therefore

r1 Z2 3
= = = 3:2
r2 Z1 2

Ex. 27 Which of the following orbits of hydrogen atom should have the values of their radii in the ratio of 1 : 4 ?
[1] K and L [2] L and N [3] M and N [4] 1 and 2 both are correct
Ans. [4]
Sol. [1] Ratio of radii of orbits K and L

2
r1 n1 12
= 2 = 2 = 1:4
r2 n2 2

[2] Ratio of radii of orbits L and N

2
r1 n1 22
= 2 = 2 = 4 : 16 or 1 : 4
r2 n2 4
 ATOMIC STRUCTURE

h
Ex. 28 If a = , then the correct expression for calculation of the circumference of the first orbit of hydrogen
4π me2
2

atom should be

[1] 4h2 πa [2] 2πr [3] 4 πha [4] 1 and 3 both are correct

Ans. [4]
Sol. Circumference = 2πr

n2 h2 h
2×π × 2 , n = 1 , Z = 1 and =a
4π mZe
2
4π me2
2

Thus 2 × π × h × a or 4πha or 4h2 πa

th
21. ENERGY OF ELECTRON IN BOHR’S n ORBIT
(a) The energy of an electron is negative because according to Bohr’s hypothesis, the maximum energy of an
electron at infinity is zero. Therefore, value of energy should be negative on moving towards lower side from
infinity.
(b) The energy of electron at infinity is zero because attractive force between electron and the nucleus is minimum.
(c) Stability would increase as the electron in an atom moves from the infinity distance to a distance r from the
nucleus, resulting in the value of the potential energy becoming negative. This is because of the fact that when

Ze2
two opposite charges attract each other, there is a decrease in the potential energy, as attractive forces =
r2

(d) Potential energy of electron is negative while kinetic energy is positive.

(e) Total energy is negative and the negative value shows that attractive forces are working between electron and
nucleus. Therefore, work is to be done to remove the electron from this equilibrium state.
(f) Energies are of two types.
21.1 Kinetic Energy (EK)
This energy is produced due to the velocity of electron. If mass is m, velocity is v and radius is r then

1 1 Ze2
Kinetic energy = mv 2 =
2 2 r

21.2 Potential Energy (EP)

This energy is produced due to electrostatic attractive forces between electron and proton, and its value is
negative. If atomic number is Z. charge is e and radius is r, then

−Ze2
Potential energy =
r

21.3 Total Energy (ET)

1 − Ze 2
Total energy = Kinetic energy + potential energy ET = EK + EP mv 2 +
2 r
 ATOMIC STRUCTURE

1 Ze2
Total energy E = –
2 r

Formula
(i) Total energy = – Kinetic energy (ET = – EK)
(ii) Potential energy = 2 × Total energy) (EP = 2ET)
Ex. 29 What should be the kinetic energy and total energy of the electron present in hydrogen atom, if its potential
energy is –5.02 eV

Potential energy −5.02

Sol. (a) Total energy = =
2 2

Total energy = – 2.51 eV

(b) Kinetic energy = – Total energy
= – (–2.51 eV)
= + (2.51 eV)
21.4 Calculation of energy

1 Ze2
Formula :- Q E= − put the value of r
2 r

Z2 2π 2me 4 Z2
ET = − × or =–K
n2 h2 n2

2π2me 4
where K = = A constant, whose values can be depicted as follows
h2

(a) = 13.60 eV per atom

–11
(b) = 2.179 × 10 ergs per atom
(c) = 313.6 kilocalories per mole
–19
(d) = 21.79 × 10 joules per atom
(e) = 1312.1 kilojoules per atom
–7
Note : Units – (a) 1 erg = 10 joule
11
(b) 1 erg = 6.2419 × 10 eV
(c) 1 eV = 23.06 kilocalories
–12
(d) 1 eV = 1.602 × 10 ergs
18
(e) 1 joule = 6.2419 × 10 eV
(f) 1 kilocalorie = 4.184 kilojoule

Z2
(i) E = – × 13.6 eV
n2

1
If Z is a constant, then E ∝ –
n2
 ATOMIC STRUCTURE

Therefore, the energy of electron goes on increasing as the number of orbits increases.

2
E1 n2
E2 = n12

3
(ii) If n is a constant, then E ∝ – Z

2
E1 Z1
E2 = 2
Z2

Z2
E= × Rhc
n2

Z2  Z2 
[1] Kinetic energy = × Rhc [2] Potential energy = 2  − 2 × Rhc 
n2  n 

Ex.30 What should be the order E1, E2, E3 and E4, if these are the respective energies of the first, second, third and
fourth orbits of hydrogen atom ?
[1] E1 = E2 = E3 = E4 [2] E4 < E3 < E2 < E1 [3] E1 < E2 < E3 < E4 [4] E2 > E3 < E4 < E1 Ans. [3]

1
Sol. E∝–
n2

Ex.31 What should be kinetic energy and potential energy, respectively, of the electron in the third orbit of hydrogen
atom ?
[1] – 1.5 eV, 3.0 eV [2] 1.5 eV, – 3.0 eV [3] 1.5 eV, 3.0 eV [4] 3.0 eV, – 3.0 eV Ans. [2]
Sol. Total energy of the third orbit of H atom

Z2
E=– × 13.6
n2

1
=– × 13.6 = – 1.5eV
9

[1] Kinetic energy = – Total energy

= – (–1.5) = + 1.5 eV
[2] Potential energy = 2 × Total energy
= 2 × –1.5 = –3.0 eV
+10
Ex.32 What should be the ratio of energies of the electrons of the first orbits of Na and H ?
[1] 11:1 [2] 121 : 1 [3] 1 : 121 [4] 1 : 11 Ans. [2]
Sol. Here n is a constant, therefore

2
E1 Z1 (11)2
E2 = Z12 = (1)2 = 121 : 1
 ATOMIC STRUCTURE

21.5 Quantization of electronic energy Levels

Quantum State Energy Separation Energy Excitation Energy

n=∞ 0 0 13.6
2
n=5 -13.6/5 = -0.54 0.54 13.05
2
n=4 -13.6/4 = -0.65 0.85 12.75
n=3 2nd Excited State -13.6/32 = 1.51 1.51 12.1

n=2 1st Excited State -13.6/22 = -3.4 3.4 10.2

n=1 Ground State –13.6 eV 13.6 eV 0 eV

Electronic energy levels of hydrogen atoms

21.6 Ground state

Ans atom in its lowest energy state or initial state is said to be in ground state. This is the most stable of an
atom.

Ex.33 Which of the following should be the energy of an electron present in ground state of hydrogen atom ?

[1] – 13.6 eV [2] – 3.4 eV [3] – 1.5 eV [4] – 0.85 eV Ans. [1]

Sol. An electron in ground state is in n = 1 orbit. Therefore the energy of the electron = – 13.6 eV

21.7 Excited State

The states of higher energy than the ground state are said to be in excited state. For example, the electron of
hydrogen atom in ground state is present in n = 1 orbit.

(a) Electron in n = 2 orbit is in first excited state

(b) Electron in n = 3 orbit is in second excited state

(c) Electron in n = 4 orbit is in third excited state

This means that the energy of n + 1 orbit is in first excited state, of n + 2 orbit in second excited state
and of n + 3 orbit in third excited state, where n = the energy in ground state.
+2
Ex.34 What should be the energy of the second excited state of Li ?
[1] – 13.6 eV [2] – 30.6 eV [3] – 3.4 eV [4] – 1.5 eV Ans. [1]
Sol. Second excited state n = 3

Z2
En = – 13.6 ×
n2

32
= – 13.6 ×
32

= – 13.6 eV
 ATOMIC STRUCTURE

21.8 Excitation Potential

(a) The energy required to excite an electron from ground sate to any excited state is known as excitation potential.
(b) Excitation potential has a positive value. For example,
First excitation potential of hydrogen atom = E2 – E1
Second excitation potential of hydrogen atom = E3 – E1
Third excitation potential of hydrogen atom = E4 – E1
Ex.35 How much minimum energy should be absorbed by a hydrogen atom in ground state to reach excites state ?
[1] + 10.2 eV [2] + 13.4 eV [3] + 3.4 eV [4] + 1.5 eV Ans. [1]
Sol. The electron has to go to the second orbit E2 on excitation. Therefore
E2 – E1 = – 3.4 – ( – 13.6) = 13.6 – 3.4 = 10.2 eV
21.9 Ionisation Energy or Ionisation Potential
The energy required to remove an electron from the outermost orbit of a gaseous atom in ground state is called
ionisation energy or ionisation potential. Its value is positive.
Ex.36 The maximum energy absorbed by hydrogen atom in its ground state will be
[1] 13.6 eV [2] 3.4 eV [3] 10.2 eV [4] 0 eV Ans. [1]
Sol. E∞ – E1
0 – (–13.6) = 13.6 eV
+2 +3
Ex.37 The energy required in the process He → He will be
[1] 0 eV [2] + 13.6 eV [3] + 3.4 eV [4] + 1.5 eV Ans. [1]
+2
Sol. He does not have any electron, therefore the ionisation energy will be 0.
21.10 Separation Energy
The energy required to separate an electron from any excitation state of an atom is known as separation energy.
For example, the first separation energy, i.e. the energy required to remove an electron from the first excited
state in hydrogen is + 3.4 eV.

22. SPECTRAL EVIDENCE FOR QUANTIZATION IN BOHR’S THEORY

(a) When an electron undergoes transition from lower to higher orbit, there is absorption of energy and the spectrum
obtained thereby is called absorption spectrum.
(b) When an electron undergoes transition from higher to lower orbit, there is emission of energy and the spectrum
obtained thereby is called emission spectrum.
(c) A hydrogen atom has only one electron, yet a very large number of lines are visible in its spectrum.
(d) The wave number of spectrum can be find out using the following expression.

1  1 1 
ν= = R × Z2  2 − 2 
λ  n1 n2 

1
where is wave number
λ

R = Rydberg constant,
n1 = Number of lower energy level
n2 = Number of higher energy level
 ATOMIC STRUCTURE

Calculation of formula
2
1 Ze
En1 = – (r1 = radius of the first orbit)
2 r1

2
1 Ze
En2 = – (r2 = radius of the second orbit)
2 r2

1 1 1
Ze  r − r 
2
En1 – En2 = –
2 1 2

According to Bohr hypothesis

En1 – En2 = hν
En1 – En2 = – hν

2π2mZ 2 e 4  1 1 
Therefore hν =  2 – 2 
h2  n1 n2 

2π2mZ 2 e 4  1 1 
ν=  2 – 2 
h3  n1 n2 

2π2mZ2 e4
Here is a constant, because for hydrogen atom Z = 1
ch3

2π2me4 –1
Thus R = Value of R = 109678 cm
ch3
–1
If calculation, this value is 109700 cm .

1  1 1 
Formula = = RZ
2  2 – 2 
λ  n1 n2 

Ex.38 What should be the value of wave number of emitted radiation with respect to R, when the electron present in
hydrogen atom jumps from M orbit to K orbit ?
8 5 3 5
[1] R × [2] R × [3] R × [4] R × Ans. [1]
9 8 4 16
Sol. The electron jumps from M orbit (n = 3) to K orbit (n = 1). Therefore

 1 1 
ν = R  − 2 
n2 
2
n1

1 1  1 1  9 − 1 8
=R  − 2 =R  −  =R   =R×
1 3  1 9   9  9

Ex.39 What should be the energy of a photon whose wavelength is 4000 Å ?

–19 –19 –12 –19
[1] 4.06 × 10 joule [2] 4.96 × 10 joule [3] 3.0 × 10 joule [4] 2.4 × 10 joule
Ans. [2]
–8 –7
Sol. λ = 4000 Å i.e. 4000 × 10 cm 4 × 10 meter

hc 6.62 × 10−34 × 3 × 108 –19

E = hν = = = 4.96 × 10 joule
λ 4 × 10 –7
 ATOMIC STRUCTURE

23. EMISSION SPECTRUM AND ABSORPTION SPECTRUM

When a beam of white light passes through a slit or an aperture and then falls on a prism, it gets spilt into many
coloured bands. The image of colours so obtained is known as a spectrum. A spectrum is of mainly three types viz.

(i) Emission spectrum

(ii) absorption spectrum

and (iii) molecular spectrum

23.1 Emission Spectrum

When energy is provided to any substance, it starts emitting radiations. These radiations are passed through a
spectroscope, they get split up into spectral lines producing emission spectrum. Normally a substance can be
excited by any of the following ways.

(a) By heating the substance at high temperature

(b) By passing electric current through a discharge tube having gaseous substance at very low
pressure.

(c) By passing electric discharge through a metallic filament.

Emission spectra are of the following two types.

(i) Continuous spectrum and (ii) line spectrum or atomic spectrum

23.1.1 Continuous Spectrum

When sunlight or a glowing heat fluorescent substance like tungsten wire present in an electric bulb, is
analysed with the help of a spectroscope, the spectrum obtained on a screen is observed as divided into bands
of seven colours, which are in a continuous sequence. Such a spectrum is called a continuous spectrum.

Ultraviolet
Violet
Indigo
Blue
Green
Yellow

Prism Orange
Red

Continuous spectrum

Continuous spectrum of white light

23.1.2 Line spectrum or Atomic spectrum

When atoms of a substance is excited, it emits radiations. These radiations are analyzed with the help of a
spectroscope, then many fine bright lines of specific colours in a sequence are seen in the spectrum, which is
not continuous, i.e. there is dark zone in between any two lines. Such a spectrum is called a line spectrum or
atomic spectrum. For example, neon single lamp, sodium vapour lamp, mercury vapour lamp, etc. emit light of
different colours and they give specific line spectra.
 ATOMIC STRUCTURE

23.2 Absorption Spectrum

When white light emitted by glowing heat fluorescent substance is passed through another substance lime
sodium substance. This results in appearance of some black lines in the spectrum. These are present at those
places where the line spectrum of the substance i.e. sodium vapour is formed. The spectrum so formed is
known as absorption spectrum.
23.3 Molecular Spectrum
Molecular spectrum is given by molecules and it is also known as band spectrum. Three types of energy
transitions are found in molecules. These are as follows.
(i) electronic transitions, (ii) vibrational transitions and (iii) rotational transitions.
Therefore, bands are obtained in the spectrum, which are actually groups of lines.

24. HYDROGEN SPECTRUM

Hydrogen atom gives line spectrum. When hydrogen gas is filled at low pressure in a discharge tube and electric
discharge is passed through it, a pink coloured is produced in the visible region due to the formation of hydrogen
atoms. On studying this light with the help of a spectroscope, series of lines of various wavelengths are obtained
in the spectrum.
The frequency of spectral lines in the form of wave number can be calculated with the help of the following
expression.

1  1 1 
ν or =R×  2 − 2 
λ  n1 n2 
24.1 Series of Lines in Hydrogen Spectrum
24.1.1 Lymen Series
When an electron undergoes transition from a higher energy level (n2), e.g. 2, 3, 4, 5, ..... ∞ to ground state or
lower energy level, the spectrum is said to belong to Lymen series. For this, n1 = 1 and n2 = 2, 3, 4, 5, 6, 7, 8
....... ∞.
24.1.2 Balmer Series
When an electron undergoes transition from a higher energy level (n2), e.g. 3, 4, 5, 6, 7, 8 ......... ∞ to the second
energy level n1 = 2, the spectrum is said to belong to Balmer series.

Regions of line spectrum of hydrogen atom Explanation of Balmer series (line spectrum)
on the basis of Bohr model
 ATOMIC STRUCTURE

24.1.3 Paschen Series

When an electron falls from a higher energy level to third orbit (n = 3). It gives a spectrum that is associated with
Paschen series. For this n1 = 3 and n2 = 4, 5, 6, 7, 8 ........ ∞.
24.1.4 Brackett Series
When an electron falls from a higher energy level to the fourth orbit (n = 4), the spectrum obtained is associated
with Brackett series. For this n1 = 4 and n2 = 5, 6, 7, 8 ..... ∞.
24.1.5 Pfund Series
When an electron falls from a higher energy level to the fifth orbit (n = 5), the spectrum obtained is associated
with Pfund series. For this n1 = 5 and n2 = 6, 7, 8, 9, 10 ........ ∞.
24.1.6 Humphry Series
When an electron falls from a higher energy level to the sixth orbit (n = 6), Humphrey series of the spectrum is
obtained. For this n1 = 6 and n2 = 7, 8, 9, 10, 11 .... ∞.

S.No. Series of lines n1 n2 Spectral region Wavelength

1. Lymen series 1 2, 3, 4, 5 ...... ∞ Ultraviolet < 4000Å

2. Balmer series 2 3, 4, 5, 6 ...... ∞ Visible 4000Å to 7000Å

3. Paschen series 3 4, 5, 6, 7 ...... ∞ Near infrared > 7000Å

4. Brackett series 4 5, 6, 7, 8 ..... ∞ Infrared > 7000Å

5. Pfund series 5 6, 7, 8, 9 ..... ∞ Far infrared > 7000Å

6. Humphrey series 6 7, 8, 9, 10 .... ∞ Far infrared > 7000Å

For the given value of n (principal quantum number), the total number of spectral lines can be calculate by the by

n(n − 1)
the expression .
2

Ex.40 How many emission spectral lines in all should be visible, if an electron is present in the third orbit of hydrogen
atom ?
[1] 6 [2] 3 [3] 5 [4] 15 Ans. [2]

n(n − 1) 3(3 − 1) 6
Sol. The expression of maximum number is = = =3
2 2 2

Ex.41 Which of the following should be the expression for the last line of Paschen series ?

1 1 1  1  1 1 1 1 1  1  1 1
[1] =R  – 2  [2] =R  –  [3] =R  –  [4] =R  –  Ans. [1]
λ 9 ∞  λ 4 9 λ  9 16  λ  16 ∞ 

1 1 1
Sol. ν = =R  – 
λ 9 ∞

25. FAILURES OF BOHR’S ATOMIC MODEL

(a) Bohr model cannot explain the elements having more than one electron. Only one-electron species, like
hydrogen atom, He+1 ion, Li+2 ion, Be+3 ion, etc. can be explained with the help of Bohr model.
 ATOMIC STRUCTURE

(b) Bohr model can explain only circular orbits in the atom and not the elliptical ones.
(c) Bohr model cannot explain splitting of spectral lines into finer lines in a magnetic field, which is known as
Zeeman effect.

No magnetic
field

Weak
magnetic field

Representation of Zeeman effect

(d) Bohr model fails to explain the splitting of spectral lines into finer lines in an electric field, which is known as
Stark effect.
(e) Bohr model fails to explain Hiesenberg uncertainty principle and it cannot be applied for giving any basis to
classification of elements and periodicity in their properties.
(f) Bohr model cannot be used for explaining finer structure of spectrum and calculating intensity of spectral lines.

26. SOMMERFELD’S EXPANSION OF BOHR’S MODEL

(a) The aforesaid discovery proved that each principal quantum number (n) is composed of many suborbits.
(b) Sommerfeld suggested that electrons moves around the nucleus not only in circular orbits but also in elliptical
orbits.
(c) When an electron travels in an elliptical orbit, its distance (r) from the nucleus and its angle of rotation both will
change.
–
e
–
e
– e –
e
θ' r θ' r
r' θ r' θ

(d) In circular orbit, the distance r remains constant but angle of rotation will change. In elliptical orbit, the nucleus
is regarded as situated at the focal point.
(e) A circular orbit is a particular situation of an elliptical orbit, in which the lengths of major axis is equal to that of
the minor axis.
(f) In elliptical orbits, the orbital angular momentum is a sum of the following two vector number.
(i) towards the radius, which is called radial component Pr, and
(ii) in the perpendicular direction to radius, which is called azimuthal component Pk.

h
(g) The above two momenta are separately quantized, i.e. both are multiple of .
2π

(h) Sommerfeld suggested that Bohr quantum number n is a sum of two quantum numbers, of which one is radial
quantum number nr and the other is azimuthal quantum number K, i.e.
n = nr + K
 ATOMIC STRUCTURE

27. THE WAVE THEORY OF LIGHT

Light, X-rays and radiation produced by a radioactive substance are some of the examples of radiation energy.
In 1856 Clark Maxwell showed that energy of radiation is of wave nature, i.e. the energy is emitted in the form of
a wave. Therefore, he called the emitted energy as electromagnetic wave or electromagnetic radiation. Since
energy is a sort of wave, it is explained as wave motion. Following are the salient features of this wave motion.
[1] Wavelength (λ)
[2] Period (T)
[3] Fequcney (ν)
[4] Amplitude (A)
(5) Wave velocity (c or v)
The aforesaid properties of a wave have the following relationship

1 λ
ν= and c = or c = νλ
T T
27.1 Wave Length
The distance between any two successive crests (or troughs) is known as wavelength. This is
expressed as λ (Lambda). The range of the wavelength associated with spectrum line is 108 to 106 cm. Its
common units are as follows. Angstrom (Å).
27.2 Frequency
The number of vibrations produced in a unit time is called frequency. Here, the time is taken in seconds. The
number of wavelengths passing forward in one second from a fixed point is called frequency.
27.3 Velocity of Light
The distance traveled by a light wave in a unit time (second) is called the velocity of that wave. It is represented
by c and its unit is normally cm/second or m/second. Its value is definite. For example, for a light wave, the
velocity c = 3 × 108 m/second or 3 × 1010 cm/second.
27.4 Amplitude
The maximum deviation of a wave from its equilibrium point is known as its amplitude.
27.5 Wave Number
The reciprocal of wavelength is called wave number. It is represented by υ .

1
υ =
λ

Therefore, the unit of wave number is cm–1 or m–1

c c υ
Q c = υλ or λ = or υ = or υ = c υ or υ =
υ λ c

Ex.42 What should be the wavelength of an ultraviolet wave, if its frequency is 12 × 1016 cycles per seond and
c = 3 × 108 m/second ?
[1] 25 Å [2] 2.5 Å [3] 0.25 Å [4] 0.025 Å Ans. [1]
Sol. Q c = νλ

c 3 × 108
Therefore λ = = = 0.25 × 10–8 m
ν 12 × 1016

or λ = 2.5 × 10–9 m or 25 × 10–10 m

λ = 25 Å
 ATOMIC STRUCTURE

28. PLANCK’S QUANTUM THEORY

If a substance emits or absorbs energy, it does not do so continuously but does but does it in the form of
discrete series of small packet or bundles, called quanta. This energy could be any of the quantum numbers 1,
2, 3, 4, 5 ....... n but not in the form of fractional quantum number.

c c
Qν= Therefore E = h ×
λ λ

29. THE DUEL NATURE OF MATTER (THE WAVE NATURE OF ELECTRON)

(a) In 1924, a French physicist, Luis De Breoglie suggested that if the nature of light is both that of a particle and of
a wave, then this dual behaviour should be true for the matter also.
(b) The wave nature of light rays and X-rays is provided on the basis of their interference and diffraction and, many
facts related to radiations can only be explained when the beam of light rays is regarded as composed of energy
corpuscles or photons whose velocity is 3 × 1010 cm/second.
(c) According to De Broglie, the wavelength λ of an electron is inversely proportional to its momentum p.

1 h
λ∝ or λ = Here h = Planck’s constant
p p

p = Momentum of electron
∴ Momentum (p) = Mass (m) × Velocity (c)

h
Therefore λ = This is called De-Broglie equation
mc

(d) The above relation can be confirmed as follows by using Einstein’s equation, Planck’s quantum theory and wave
theory of light.
But according to Einstein’s equation

c h h h
E = mc2 = h × or mc = or p = or λ =
λ λ λ p

30. BOHR’S THEORY AND DE BROGLIE CONCEPT

(a) According to De Broglie, the nature of an electron moving around the nucleus is like a wave that flows in circular
orbits around the nucleus.
(b) If an electron is regarded as a wave, the quantum condition as given by Bohr in his theory is readily fulfilled.
(c) If the radius of a circular orbit is r, its circumference will be 2πr.

nh
(d) We known that according to Bohr theory, mvr =
2π

nh nh h
or 2πr = (Q mv = p momentum) or 2πr = (Q = λ De Broglie equation)
mv p p
 ATOMIC STRUCTURE

nh
(e) Q 2πr =
mv

nh
or mvr = Q mvr = Angular momentum
2π

h
Thus mvr = Angular momentum, which is a integral multiple of
2π

(f) It is clear from the above description that according to De Broglie there is similarity between wave theory and
Bohr theory.
Ex.43 What should be the mass of the photon of sodium light if its wavelength is 5894 Å, 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 Ans. [4]

h h
Sol. λ= or
m×c cλ

(Q λ = 5894 Å or 5894 × 10–10 m)

6.652 × 10 –34 6.652

m= or × 10–32
3 × 108 × 5894 × 10 –10 17682

= 3.746 × 10–36 Kg

31. QUANTUM MECHANICAL THEORY OF ATOM

(a) The dual nature (particle and wave) of electron led to the use of a new system of mechanics called quantum
mechanics. This system was first put forward by an Austrian physicist E. Schrodinger and a German physicist
W. Heisenberg.
(b) The two fundamental principles of quantum mechanics are given below :
(i) Heisenberg’s uncertainty principal and
(ii) Schrodinger’s wave equation
31.1 Heisenberg’s Uncertainty Principle
(a) According to this principle, it is impossible to experimentally determine together both exact position and actual
momentum of a minute particle like an electron.
(b) This principal can be depicted mathematically as follows.

h h
∆x × ∆p ≥ or ∆x × m × ∆v ≥
4π 4π

Here ∆x is uncertainty of position,

∆p is uncertainty of momentum and
h is Planck’s constant
Ex.44 What should be the uncertainty in position if uncertainty in momentum is 1 × 10–2 gm cm/sec and value of h is
6.6253 × 10–34 Js ?
[1] 1.054 × 10–22m [2] 1.054 × 10–25m [3] 1.054 × 10–27 m [4] 1.054 × 10 –32 m Ans. [3]
 ATOMIC STRUCTURE

Sol. Given that

∆p = 1 × 10–2 gm cm/sec. = 1 × 10–7 Kg m/sec.
h = 6.6252 × 10–34 Js

h h
∆x × ∆p = ∴ ∆x =
2π 2π × ∆p

6.6252 × 10 –34
or ∆x = m = 1.054 × 10–27m
2 × 3.14 × 10 –7

31.2 Schrondinger’s Wave Equation

Schrondinger regarded electron as having wave nature and put forward the following complex
differential equation.

8π 2m
∇2 ψ + (E – v) φ = 0
h2

d2 d2 d2
∇2 = + +
dx 2 dy 2 dz 2

where m = Mass of electron, h = Planck constant,

E = Total energy of electron, v = Potential energy of electron,

ψ = Wave function, ∇ = Laplacian Operator

32. QUANTUM NUMBERS

(a) The position of any electron in any atom can be ascertained with the help of quantum numbers.
(b) In an atom, the shell consists of sub-shells and the sub-shell consists of orbital can accommodate only two
electrons, which are in opposite spins.
32.1 Principal Quantum Number (n)
(a) Principal quantum number indicates the shell or energy level or orbit.
(b) An atoms has K, L, M, N, O, P, Q, etc. shells.
(c) Principal quantum number also gives information about the radius of size.
(d) Principal quantum number also gives information about the distance of an electron from the nucleus in an atom
(e) Principal quantum number also given information about the energy of an electron.
(f) Principal quantum number also gives information about the velocity of an electron.
(g) In any orbit, the number of orbitals is given by n 2 and number of electrons is given by 2n 2 .
This is called Bohr-Bury rule.
Ex.45 Which of the following is the principal quantum number for the last electron of 11Na ?
[1] 3 [2] 2 [3] 4 [4] 1 Ans. [1]
Sol. 11Na = 1s2, 2s2, 2p6, 3s1
n=3
Ex.46 Which of the following should have greater size ?
[1] 1s [2] 2s [3] 3s [4] 4s Ans. [4]
Sol. n = 4 for 4s
 ATOMIC STRUCTURE

32.2 Azimuthal Quantum Number (l)

(a) Azimuthal quantum number gives information that a particular electron belongs to which sub-shell.
(b) In an atom the shells consist or sub-shells, which are indicated as s, p, d and f.
(c) Azimuthal quantum number determines the shape of an orbital.
(d) The value of n starts from 1, while that of l starts from 0. Therefore, the maximum value of l is n – 1.
(e) The values of n and l can never be equal.
Sub shell s p d f
l 0 1 2 3
(f) The number of orbitals in any sub orbit is determined by the expression 2l + 1 and the number of electrons is
determined by the expression 2(2l + 1).
(g) l=0 → s Sub-shell → Spherical
l= 1 → p Sub-shell → Dumb-bell
l=2 → d Sub-shell → Double dumb-bell
l=3 → f Sub-shell → Complex
(h) The order of energy of various sub-shells present in any shell is s < p < d < f < g ........... and so on.
(i) The value of orbital angular momentum, µi, of an electron can be determined with the help of azimuthal quantum
number

h
µi = l(l + 1) ×
2π
Here l = Azimuthal quantum number and h = Planck’s constant
Ex.47 Which of the following should be the possible sub-shells, for n + l = 7 ?
[1] 7s, 6p, 5d, 4f [2] 4f, 5p, 6s, 4d [3] 7s, 6p, 5d, 6d [4] 4s, 5d, 6p, 7s Ans. [1]
Sol. n+l=7
7 + 0 = 7s ; 6 + 1 = 6p ; 5 + 2 = 5d ; 4 + 3 = 4f
Ex.48 What should be the maximum number of electron in the possible sub-shells, for n + l = 4 ?
[1] 8 [2] 6 [3] 12 [4] 16 Ans. [1]
Sol. n+l=4 Maximum number of electrons
4 + 0 = 4s →2
3 + 1 = 3p →6
8
Ex.49 The sub-shell 2d is not possible because
[1] n ≠ l [2] l > n [3] n < l [4] None of these Ans. [1]
Sol. For sub-shell 2d, n = 2 and l = 2 and the values of n and l can never be equal.
Ex.50 What should be the maximum number of elements, if the elements above n = 4 do not exist in nature ?
[1] 40 [2] 60 [3] 44 [4] 108 Ans. [2]
Sol. Since, n = 1, 2, 3 and 4, therefore

1s 2s,2p 3s,3p,3d 4s,4p,4d,4f

, , , Thus, total number of existent elements = 2 + 8 + 18 + 32 = 60
2 8 18 32

Ex.51 Which of the following orbitals should be nearest to the nucleus ?

[1] 5s [2] 6p [3] 3d [4] 4d Ans. [3]
Sol. n = 3 will be nearest to the nucleus.
 ATOMIC STRUCTURE

32.3 Magnetic Quantum Number (m)

(a) Magnetic quantum number gives information about an orbital. It is depicted by the symbol m.
(b) Magnetic quantum number gives information about orientation of orbitals.
(c) The value of m ranges from – l to + l.
(d) The total number of orbitals present in a sublevel is equal to the total values of magnetic quantum number.
This can be find out by the following expression.
m = 2l = 1
where m is total value of magnetic quantum number and l is the value of azimuthal quantum number.
(i) For s sub-shell, l = 0. Thus, m = 2 × 0 + 1 = 1 and therefore s sub-shell consists of only one orbital called s
orbital.
(ii) For p sub-shell, l = 1. Thus, m = 2 × 1 + 1 = 3 and therefore p sub-shell consists of three orbitals called px,
py and pz orbitals.
(iii) For d sub-shell, l = 2. Thus, m = 2 × 2 + 1 = 5 and therefore d sub-shell consists of five orbitals called dxy,
dyz, dz2, dxz and d 2 2 orbitals.
x −y

(i) For s sublevel, l = 0. Thus, for s orbital, the value of m is 0.

s
m=0
(ii) For p sub-level, l = 1. Thus, the values of m for p orbitals are as follows.

px/py pz pz/py

–1 0 +1

(iii) For d sub-level, l = 2. Thus, the values of m for d orbitals are as follows.
2
dxy dyz dz dxz dx2 − y2

–2 –1 0 +1 +2

(iv) For f sub-level, l = 3. Thus, the values of m for f orbitals are as follows.

–3 –2 –1 0 +1 +2 +3

(e) The total number of orbitals present in an energy level is determined by the formula n2 where n is principal
quantum number.
Ex.52 What should be the total numbers of orbitals and electrons for m = 0, if there are 30 protons in an atom ?
[1] 7 orbitals, 14 electrons [2] 6 orbitals, 12 electrons
[3] 5 orbitals, 10 electrons [4] 3 orbitals, 6 electrons Ans. [1]
Sol. The configuration of the atom of atomic number 30 is 1s2, 2s2, 2p6, 3s2, 3p6, 3d10, 4s 2. This will have 7 orbitals
of m = 0.
Ex.53 The orbital having n = 6, l = 2 and m = 0 will be designated as

[1] 6 dz2 [2] 6 d [3] 6dxy [4] 6pz Ans. [1]

x2 – y2

Sol. For 6th of P energy level, l = 2 is for d sub-level, and m = 0 for dz2 orbital

Ex.54 The orbital having n = 2, l = 1 and m = 0 is designated as

[1] 2pz [2] 2px [3] 2py [4] 3 dz2 Ans. [1]

Sol. In the second or L energy level (n = 2) , l = 1 for p orbital, m = 0 for z axis, Hence, the orbital will be designated
as 2pz.
 ATOMIC STRUCTURE

32.4 Spin Quantum Number (s)

(a) Spin quantum number gives information about the spin of an electron.
(b) The value of s is 1/2 which depicts the direction of spin of the electron.

1
(c) If the electron spins in clockwise direction, s is denoted by + or a sign [↑]. Anticlockwise spin of the electron
2

1
is denoted by s = – or [↓].
2

(d) One orbital can accommodate only two electrons, with opposite spins.
(e) One orbital can accommodate only two electrons, with opposite spins.
(f) The angular momentum of an electron is not only due its motion around the nucleus in an energy level but also
due to its rotation along its own axis. The angular momentum that arises due to rotation of an electron along its
axis, is called spin angular momentum and is depicted by the symbol µs. The value of µs can be found out with
the help of the following expression.

h 1
µs = s(s + 1) × where s is spin quantum number. In this expression the value of s is always taken as
2π 2

1
and not – .
2

Ex.55 If x is the number of electron in an atom, the configuration should be expressed as :

[1] lx [2] nlx [3] nmx [4] None of these Ans. [2]
Sol. The electronic configuration of an atom is expressed by first writing principal quantum number (n), followed by
azimuthal quantum number (l) and then writing number of electrons (x) as superscript.
Ex.56 What should be the atomic number of an element, if the quantum numbers of the highest energy electron of the

1
element in ground state are n = 4, l = 1, m = – 1 s = + ?
2

[1] 31 [2] 35 [3] 30 [4] 32 Ans. [1]

Sol. The electronic configuration of the element will be 1s2, 2s2, 2p6, 3s2, 3p6, 4s2, 3d10, 4p1. Thus, the total number
of electrons is 31 and hence the atomic number will be 31.
Ex.57 The orbital having m = – 2 should not be present in the following sub-shell
[1] d [2] f [3] g [4] p Ans. [4]
Sol. For p sub-shell, m = – 1, 0, + 1. Therefore, m = – 2 orbital will not be present in p sub-shell.
Ex.58 What should be the value of spin quantum number of the last electron for d9 configuration ?

1 1
[1] 0 [2] – [3] [4] 1 Ans. [2]
2 2

1 1
Sol. The value of spin quantum number (s) can be + or – , because an electron can rotate along its axis either
2 2
in clockwise or in anticlockwise direction. But one quantum number depicts one electrons and thus its value will
1
be – for d9 configuration.
2
Ex.59 The all energy levels are called excited states when the value of principal quantum number is :
[1] n = 1 [2] n > 1 [3] n < 1 [4] n > – 1 Ans. [2]
Sol. All the energy states in which n is greater than 1 are called excited states.
 ATOMIC STRUCTURE

33. AUFBAU PRINCIPLE

Aufbau is a German word that means to build up. Therefore, electrons are filled up in accordance with this
principle.
(a) Pauli’s exclusion principle should be followed during filling up of electrons, i.e. no two electrons should have
same set of four quantum numbers. This means that maximum number of electrons to be filled in various
sub-shells are 2 in s, 6 in p, 10 in d and 14 in f.
(b) Hund’s rule should be followed during filling up of electrons i.e. the electrons are to be filled in the degenerate
orbitals first in unpaired state.
(c) The electrons are filled in a sub-shell according in n + l rule.
33.1 Pauli’s Exclusion Principle
(i) According to Pauli exclusion principle, any two electron cannot have same set of four quantum numbers.
For example :
(a) 6s1 and 6s2
n=6 n=6
l=0 l=0
m=0 m=0

1 1
s=+ s=–
2 2
(b) 4p2 and 4p5
n=4 n=4
l=1 l=1
m=0 m=0

1 1
s=+ s=–
2 2

In the above illustrations, the respectively values of n, l and m are same but that of s is different.
(ii) Pauli exclusion principle can be stated in other words as that “only two electrons can be accommodated in
the same orbital only when their spin quantum number is different”.
(iii) If the third electron enters in an orbital, the set of four quantum numbers becomes same for any two electron.
(iv) According to this rule, for any two electrons, a set of maximum three quantum numbers can be same, but the
fourth has to be different. For example, two electrons can have same (n, l and m) or (l, m or s) or (n, m or s)
Example 1s1 and 1s2
n=1 n=1
l=0 l=0
m=0 m=0

1 1
s=+ s=–
2 2

(v) This rule does not apply for hydrogen atom because it contains only one electron.
Ex.60 Pauli exclusion principle applies to
[1] H [2] H+ [3] H– [4] None of the above Ans. [3]
Sol. Since, H has one electron and H+ has no electron, therefore Paulie principal does not apply to them. However,
H– has two electrons, hence this principle applies on it.
 ATOMIC STRUCTURE

Ex.61 Which of the following statements is true ?

[1] One orbit can accommodate a maximum of two electrons
[2] One sub-shell can accommodate a maximum of two electrons
[3] One orbital can accommodate a maximum of two electrons
[4] None of the above Ans. [3]
Sol. It is an orbital that can accommodate a maximum of two electrons having opposite spins
Ex.62 Which of the following is not according to Pauli exclusion principle ?

[1] ↑↑ [2] ↑↓↑ [3] ↑↓ ↑ [4] 1 and 2 both Ans. [4]

Sol. The set of four quantum numbers are not same for the three electrons in answer 3. In answer 1 both of the
electrons have same set of quantum numbers, while in answer 2 the first and third electrons have same set of
quantum numbers.
Ex.63 Supposing that Pauli exclusion principle is not correct, if one orbital can accommodate three electrons, what
should be the respective atomic number of the second member of alkali metal family and the first member of
halogen family
[1] 16, 14 [2] 11, 9 [3] 16, 9 [4] 34, 17 Ans. [1]
Sol. (a) Sodium is the second member of alkali metal family
Na11 = 1s2, 2s2, 2p6, 3s1
We know that the inner orbitals of sodium are fully filled and the outer most orbit has one electron. If inner
orbitals can accommodate three electrons each, the configuration will be as follows.
1s3, 2s3, 2p9, 3s1
Therefore, three will be 16 electrons in all. Hence the atomic number will be 16.
(b) The first member of halogen family is fluorine, F9 whose configuration is 1s2, 2s2, 2p5
Halogen has one electron less than the next inert of noble gas. If inner orbitals can accommodate three electron
each, the configuration will be as fallows.
1s3, 2s3, 2p8
Therefore, total number of electrons will be 14 and thus the atomic number will also be 14.
Ex.64 Supposing that Pauli exclusion principle is nonexistent, which of the following should be the most unacceptable
configuration of Li in ground state ?
[1] 1s2, 2s1 [2] 1s3 [3] 1s1, 2s2 [4] 1s1, 2s1, 2p1 Ans. [4]
Sol. As a matter of fact, the configuration given in 2, 3 and 4 are wrong, but configuration given in 4 is most unaccept-
able because there is one electron in each of the three orbitals and according to Paulis exclusion principle
maximum two electrons can be occupier in a orbital.
33.2 Hund’s Rule of Maximum Multiplicity
(a) Degenerate orbitals
The orbitals having same energy are called degenerate orbitals.
(b) s sub-shell consists of only one orbital. Thus, it cannot have degenerate orbital.
(c) According to Hund’s rule, the degenerate orbitals get filled by electrons having parallel spin one by one to give
an unpaired state.
(d) According to this rule, the degenerate orbitals are filled in such a way that there is a maximum number of
unpaired electrons. For example, C6 can possibly have the following two configurations of 2s2 2p2.
2p
[1] ↑↓ ↑↓

[2] ↑↓ ↑ ↑
 ATOMIC STRUCTURE

(e) The following two conditions have to be fulfilled for Hund’s rule.
[1] The orbitals should be degenerate
[2] The member of electrons and the degenerate orbitals should be more than one
(f) Hund’s rule is not applicable for H, He, Li and Be, because electrons in them go to s sub-shell, which does not
have any degenerate orbital.
(g) Hund’s rule is not applicable for B5 also, because there is only one electrons in p orbital. Therefore, this rule is
applicable from C6 onwards.
(h) Hund’s rule is not important for elements belonging to groups IA, IIA and IIIA.
Ex.65 Which of the following should be correct according to Hund’s rule ?

[1] C6 = 1s2, 2s2 ↑↑ [2] O8 = 1s2, 2s2 ↑↓ ↑ ↓

[3] N7 = 1s2, 2s2, ↑↓ ↑ [4] F9 = 1s2, 2s2 ↑↓ ↑↓ ↑ Ans. [4]

Sol. Configuration of C6 should be 2px1 2py1 instead of 2px2

Configuration of O8 should be 2px2 2py1 2pz1 instead of 2px2 2py2
Configuration of N7 should be 2px1 2py1 2pz1 instead of 2px2 2py1
Configuration of F9 2px2 2py2 2pz1 is correct because two out of the three degenerate p orbtials are fully-filled, one
is half-filled and there is no unfilled p orbital.
33.3 n + l Rule
(a) n + l Rule gives information about the energy of various sub-shells.
(b) According to this rule, the sub-shells having higher value of n + l have higher energy.
(c) The sub-shells having lower value of n + l have lower energy.
(d) It two sub-shells have same value of n + l, then that sub-shell will have higher energy which has higher value of n.
Ex.66 If the value of n + l = 7, then what should be the increasing order of energy of the possible sub-shells ?
[1] 4f < 5d < 6p < 7s [2] 7s < 6p < 5d < 4f [3] 7s > 6p < 5d < 4p [4] 4f < 5d < 6p > 7s Ans. [1]
Sol. n+l=7
7 + 0 = 7s Order of energy
6 + 1 = 6p 4f < 5d < 6p < 7s
5 + 2 = 5d
4 + 3 = 4f
Ex.67 Which of the following sub-shells will be filled by the electron after complete filling up of the orbital of the third
principal shell ?
[1] 4s [2] 4f [3] 4d [4] 4p Ans. [4]
Sol. The electron goes to 4p after filling up to 3d.
Ex.68 Which of the following should be the basis of entry of an electron in 4s orbital before 3d orbital ?
[1] Energy level diagram [2] Hund’s rule [3] Pauli’s principle [4] Shielding constant Ans. [1]
Sol. n + l of 4s = 4 + 0 = 4 and that of 3d is 3 + 2 = 5. Therefore, energy of 4s is lower than that of 3d.
Increasing order of energy
1s < 2s < 2p < 3s < 3p < 4s < 3d < 4p < 5s < 4d < 5p < 6s < 4f < 5d < 6p < 7s < 5f < 6d < 7p
The maximum number of electrons that can be accommodated in s orbital is 2, that in p orbital is 6, that in d
orbital is 10 and that in f orbital is 14.
 ATOMIC STRUCTURE

Exceptions to n + l Rule

There are mainly two exceptions of n + l rule.

(a) La57 – 1s2, 2s2, 2p6, 3s2, 3p6, 4s2, 3d10, 4p6, 5s2, 4d10, 5p6, 6s2, 5d1
(b) Ac89 – 1s2, 2s2, 2p6, 3s2, 3p6, 4s2, 3d10, 4p6, 5s2, 4d10, 5p6, 6s2, 4f14, 5d10, 6s2, 7s2, 6d1
Specific Electronic Configuration

Element Atomic number Expected Atcual

configruation configration

1. Cr 24 [Ar]18 3d4 4s2 [Ar]18 3d5 4s1

2. Cu 29 [Ar]18 3d9 4s2 [Ar]18 3d10 4s1

3. Mo 42 [Kr]36 4d4 5s2 [Kr]36 4d5 5s1

4. Pd 46 [Kr]36 4d8 5s2 [Kr]36 4d10 5s0

5. Ag 47 [Kr]36 4d9 5s2 [Kr]36 4d10 5s1

6. W 74 [Xe]54 4f14 5d4 6s2 [Xe]54 4f14 5d5 6s1

7. Pt 78 [Xe]54 4f14 5d8 6s2 [Xe]54 4f14 5d9 6s1

8. Au 79 [Xe]54 4f14 5d9 6s2 [Xe]54 4f14 5d10 6s1

Due to greater stability of half-filled and fully-filled orbitals, the configurations d5 ns1 and d10 ns1 are written in
place of d4 ns2 and d9 ns2 respectively.
33.4 Stability of Half-filled and Fully-Filled orbitals
The stability of half-filled orbitals (p3, d5 and f7) and fully-filled orbitals (p6, d10 and f14) is higher than that in other
states. This is due the following reasons.
(a) When a sub-shell is half–filled or fully-filled, it means that the distribution of electrons is symmetrical in the
orbitals of equal energy. Unsymmetrical distribution of electrons results in lower stability.
(b) The electrons present in orbtials of equal energy in an atom can interchange their position, in this process
energy is released, resulting stable system. The possibility of interchange of positions is highest in half filled
and fully-filled states. This provides greater stability to the system.
(c) The exchange energy for half-filled and fully-filled orbitals is maximum. As the number of electrons increases,
electron start pairing resulting in spin coupling. The energy liberated in the process of coupling is called coupling
energy.
(d) The spin of electrons in a fully-filled orbital are opposite to each other or antiparallel. The energy of the system
decreases due to neutralization of opposite spins. So fully-filled orbitals are more stable.

34. MODE OF FILLING UP TO ELECTRONS

Writing the configuration of ions
First of all, the configuration of the atom is written. Then, appropriate number of electrons are deducted from the
outermost shell for the configuration of the cation. Similarly, appropriate number of electrons are added to the
outermost shell for the configuration of the anion.
 ATOMIC STRUCTURE

Ex.69 Which of the following should be the atomic number of an atom if its electronic configuration is
(n – 2)s2, (n – 1) sa pb nsa p2 where n = 3, a = 2 and b = 6 ?
[1] 14 [2] 12 [3] 16 [4] 15 Ans. [1]
Sol. (3 – 2)s2 (3 – 1)s2 p6 3s2 3p2 ; 1s2, 2s2 2p6, 3s2, 3p2 = 14
The atomic number of the atom is 14
Ex.70 Which of the following should be the number of electrons present in X+2 on the basis of electronic configuration,
if the ion X–3 has 14 protons ?
[1] 12 [2] 14 [3] 16 [4] 18 Ans. [1]
Sol. X–3 has 14 protons, i.e. X also has 14 protons and therefore 14 electrons.
X = 14 = 1s2, 2s2 2p6, 3s3 3p2
X+2 = 1s2, 2s2 2p6, 3s2 = 12 electrons
Ex.71 Which of the following should be the electronic configuration of an atom in its first excited state if that atom is
isoelectronic with O2 ?
[1] [Ne] 3s2 3p4 [2] [Ne] 3s2 3p3 3d1 [3] [Ne] 3s1 3p5 [4] None of the above Ans. [2]
Sol. 16 electrons = 1s2, 2s2 2p6, 3s2 3p4 (Two unpaired electrons)
Excited state = [ Ne] 3s2, 3p3, 3d1 (Four unpaired electrons)
Ex.72 Which of the following should be the electronic configuration of P in H3PO4 ?
[1] [Ne] [2] [Ne] 3s2 3p6 [3] [Ne] 3s2 [4] [Ne] 3s2 3p1 Ans. [2]

35. DIFFERENCE BETWEEN ORBIT AND ORBITAL

S.No. Orbit Orbital
1. It is depicted by n. It is depicted by m
2. It has maximum electron It has maximum electron
capacity of 2n2 capacity of 2 in accordance
with Pauli’s principle
3. It is bigger in size It is smaller in size
4. Orbit consist of suborbits Sub-orbit consists of orbitals
5. The path of an electron The space around the nucleus
around the nucleus is where probability of finding an
called an orbit electron is maximum, is called
an orbital

36. ORBITAL
(a) The space around the nucleus where probability of finding an electron is maximum, is called an orbital.
(b) An electron cloud is negatively charged and the nucleus is positively charged. Therefore, the probability of
finding an electron is maximum around the nucleus.
(c) The probability of finding an electron is an orbital is 95% to 98%.
36.1 s-Orbital
(a) Only one s-orbital is possible in an orbit because l = 0 and m = 0 for it.
(b) It is spherical in shape and thus the electron density is uniform in all directions.
 ATOMIC STRUCTURE

(c) The size increases with increase in the value of n. There is vacant space between 1s orbital and 2s orbital, where
the probability of finding electron is minimum, it is known as nodal surface.
(d) The nodal surface is missing inside 1s orbital because of its proximity with the nucleus.
(e) The number of nodel surfaces in an orbit is equal to (n – 1)
z z

y y

x + x +

1s Orbital 2s Orbital
(a) (b)
The shapes of s-orbital
36.2 p-Orbital

(a) For p orbitals, l = 1 and m = – 1, 0, + 1. Thus, it can have three configurations, which are distributed in x, y and
z axes. Therefore, there are three p-orbitals, which are dumbbell, shaped.
(b) Each p-orbital has two lobes and the probability of finding electron inside these two lobes is equal. The plane
perpendicular to the axis two lobes and passing through the point where these two lobes join, is the nodal plane
of p-orbital, because the probability of finding electron in this plane is negligible or minimum.
(c) The value of nodal planes for each of the px, py and pz orbitals is same and these nodal planes are present in xy,
yz and xz planes, respectively.
(d) The three p-orbitals of a particular orbit (px, py and pz) have equal energy and therefore these are called degen-
erated orbitals.
x
+

px Orbitals
+ y +

+
z
z
y
px–py–pz Orbitals py Orbitals pz Orbitals

Shape of p orbitals
36.3 d-Orbitals
(a) For d orbitals, l = 2 and m = – 2, – 1, 0, +1, + 2. Therefore, there are five orientations and thus five d-orbitals.
(b) Its shape is like a double dumbbell.
(c) The five orientations of d-orbitals are as follows :
(i) The double dumbbell of dxy orbital are situated between x and y axes.
(ii) The double dumbbell of dyz orbital are situated between y and z axes
(iii) The double dumbbell of dxz orbital are situated between x and z axes.

(iv) The double dumbbell of d 2 2 orbital are directed on x and y axes

x –y

(v) dz2 orbital is composed of one dumbbell and one ring. The dumbbell is situated on z axis and the ring is present
on its middle part.
The aforesaid five d orbtials can be classified into the following two categories.
 ATOMIC STRUCTURE

(i) t2g Orbitals (dxy, dxz and dyz) – In these, the electron density is concentrated in-between the axes. These are
also called grade orbitals.
(ii) eg Orbitals ( dx2 − y2 and dz2 ) – In these, the electron density is concentrated on the axes.

Shape of d Orbitals
36.4 f-orbitals
(i) They have complex shapes,
(ii) For these, l = 3 and m = – 3, –2, –1, 0, +1, +2, +3
(iii) These have seven orientations.

37. CONTRIBUTION OF SOME SCIENTISTS

[1] Atom
John Dalton in 1880 said that matter is composed of very minute and indivisible particles, called atoms.
[2] Electrons
(a) Discoverer – J.J. Thomoson

1
(b) Weight – th of the weight of H atom
1837
(c) Mass – 9.1 × 10–28 gram
(d) Amount of charge – (a) 4.8 × 10–10 e.s.u. (electrostatic unit) (b) 1.6012 × 10–19 coulomb
(e) Rest mass – Mass of electron = 9.1 × 10–28 grams
1 a.m.u. = 1.6 × 10–24 gm

9.1× 10 −28
Rest mass = = 5.51 × 10–4 a.m.u.
1.6 × 10 −24
The mass of an electron 9.1 × 10–28 gram is also called its rest mass.
(f) Discovery – With the help of cathode rays.
[3] Proton
(a) Discoverer – Goldstein
(b) Discovery – With the help of anode rays
(c) Mass – 1.6748 × 10–24 gram or 1.00757 a.m.u.
(d) Charge – Unit positive charge
 ATOMIC STRUCTURE

[4] Neutron
(a) Discoverer – James Chadwick (1932)
(b) Charge – Zero (i.e. a neutral particle)
(c) Mass – 1.67 × 10–24 gram or 1.6 × 10–27 Kg
(d) Density – 10–12 Kg/cm3
(5) Nucleus
(a) Discoverer – Rutherford
(b) Size of nucleus – 10–13 to 10–12 cm i.e. 10–15 to 10–14 metre
(c) Size of atoms – 10–8 cm
(d) Atomic radius – 105 × Radius of the nucleus
(6) Positron
(a) Discoverer – C.D. Anderson (1932)
(b) Symbol – e+1
(c) Charge – Unit positive charge
(d) Mass – Negligible (like electron)
(e) Stable particle
(7) Meson
(a) Predicted by — Yukawa
(b) Discoverer – Neddermeyer and Anderson
(c) Charge – Positive, negative or zero
(d) Mass – In between proton and electron
(e) Unstable particle
(8) Neutrino
(a) Discoverer – Pauling
(b) Charge – Zero
(c) Mass – Negligible (less than that of electron)
(d) Stable particle
(9) Antiproton
(a) Discoverer – Segre
(b) Charge – Unit negative charge
(c) Mass – Equal to that of proton
(d) Stable particle
4 3 4
(10) Volume of atom = πr = π 10–24 cm
3 3

4 3 4 10 −39
(11) Volume of nucleus = πr = π 10–39 cm = = 10–15 cm
3 3 10 − 24
Thus, the nucleus of an atom occupies 10–15 part of an atom
(12) Some discoverers
(a) Positive rays – Goldstein
(b) Cathode rays – William Crookes
(c) Atomic number – Mosley
(d) e/m of proton – J.J. Thomson
(e) chanrge on electron – Milliken
(f) e/m of electron – J.J. Thomson
(f) Radioactivity – Henry Becquerel
 ATOMIC STRUCTURE

38. IMPORTANT POINTS

(a) Number of sub-shells in the shell = n
(b) Number of orbitals in the shell = n2
(c) Number of electrons in the shell = 2n2
(d) No. of orbitals in the sub-shell = 2l + 1
(e) Number of elliptical orbits according to Sommerfeld = n – 1

n(n − 1)
(f) Maximum number of spectral lines =
2
(g) Number of nodal surfaces = n – 1
(h) K. E. = – T.E.
(i) T.E. = P.E./2
(j) Nodal Point : The nucleus of an atom called Nodal Point.
(k) Isodiapheres : The elements which have same value of (n – p) is called isodiapheres.
(l) Isomorphous : The two different type of compound which contain same crystalline structure called
isomorphous and this property called isomorphism.
(m) Substance which have same number of electron and atoms called Isosteres.
(n) Core : The outer most shell of an atom called Core and the number of electron present to that shell is called
Core electron.
(o) Promotion : The transfer of electron between subshells in an orbit is called promotion. While the transfer of
one energy level to another is called transition. After the completion of promotion the transition process is
occurred.

S.No. Radius Velocity Energy Wavelength

n 2h 2 2πZe2 Ze 2 2π 2me 4
1. r= V= E=– R=
4π 2mZe 2 nh 2r Ch 3

1/ 2
n2  Ze 2  2π 2mZ 2 e 4 1 1 1
2. r= × 0.529Å V =  
 E=– = R × Z2  2 – 2
Z  rm 
2 2
n h λ  n1 n2 

n2 nh z2
3. r= × 0.0529 nm V= E = – Rch × E = hυ
Z 2πmr n2

1 z2 h
4. r ∝ n2 (Z const) V∝ (Z const) E=– 2
× 313.6 Kcal λ =
n n mc

r1 n12 V1 n2
5. r2 = n 22 (Z const) V2 = n1 (Z const) E ∝ – Z2 (n const) c = v/t

2πr E1 Z12
6. r ∝ 1/Z (n const) Time period T = = E = mc2
V E 2 Z 22 (n const)