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INORGANIC CHEMISTRYATOMIC STRUCTURE

FUNDAMENTALS OF ATOMIC STRUCTURE

RADIOACTIVITY

The spontaneous emission of some definite type of particles from the nucleus of an atom is called

radioactivity. The nuclei of all radioactive substances are unstable and in order to acquire stability,
they disintegrate into smaller nuclei which are more stable. Radioactivity prooves that atom is divisible
in nature.

ELECTRON

Electron was discovered by J J Thomson from cathode rays. Cathode rays dovelops from cathode in

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C h arg e
discharged tube. The specific charge
of chathode ray is a universal constant. The charge of an
M ass

electron is equal to 1 unit or 1.6 10 19 C . The mass of one electron is 0.000549 amu or 9.110 31 Kg .

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E

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a

a
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m
u

THOMSONS MODEL

This model is also known as plum pudding model or watermelon type model.

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A

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PROTON

Proton was discovered by Goldstein from anode rays (Electron as an particle was discovered by
Rutherford). Anode rays does not dovelop from anode. They are doveloped by the ionization of gas
Ch arg e

filled inside the discharged tube. The specific charge Mass of anode rays is not a universal constant.

The specific charge of anode rays depends upon the gas used. The charge of a proton is equal to 1 unit or
+ 1.6 10 19 C . The mass of one proton is 1.0072 amu or 1.672 10 27 Kg .

Chemistry By Arun Kumar Saini

INORGANIC CHEMISTRYATOMIC STRUCTURE

NEUTRON

Neutron was discovered by Chadwick. The cause of late discovery of neutron is its neutral nature. It
was discovered during radioactive disintegration ( 49 Be 24 He 126 C 01 n ). The mass of neutron
( 1.675 10 27 Kg ) is slightly higher than proton.

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MILLIKAN EXPERIMENT

The first precise measurement of the charge on the electron was made by Robert Millikan in 1909 by
oil drop experiment.
Mass of electron

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e
e
9.6 10 31 kg
Mass of proton
1.67 10 27 kg
&
e
e
m
m

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Millikan experiment can not be used for neutron, because it is chargeless particle.

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RUTHERFORD MODEL

This model is also known as solar model or planetary model.

Observations of particles scattering experiment
# Most of the particles (about 90 %) went straight without suffering any deflection.

# A few of them got deflected through small angles.

# A very few (About one in 20000) did not pass through the foil at all and are deflected through 180 0.
# The number of particles scattering at an angle is given by

Number of particles

1

sin 4
2

Chemistry By Arun Kumar Saini

INORGANIC CHEMISTRYATOMIC STRUCTURE

Fluorescence of
light

Gold foil

ZnS screen
Slit
Source of particles

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Rutherford's particle scattering experiment

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Conclusion of particles scattering experiment

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# The atom is extraordinarily empty.

# Whole of the positive charge is concentrated and the space occupied by this positive charge is very
small (Nucleus).
# The nucleus is very rigid.
Electrons revolve around the nucleus in the circular orbits and the necessary centripetal force for
revolution is provided by the electrostatic attraction between the nucleus and the electron.
According to Rutherford model the spectrum of the atom should be continuous, but it is line spectrum.
The stability of the atom cannot be explained on the basis of Rutherfods Model.
According to electromagnetic theory of radiation, when e may be accelerated, it would be emit energy.
So the energy of electron would be decrease continuously and hence electron would be fall down into
the nucleus i.e., atom should be unstable, but atom is stable.

Chemistry By Arun Kumar Saini

INORGANIC CHEMISTRYATOMIC STRUCTURE

ELECTROMAGNETIC RADIATION

Electromagnetic radiations are a form of energy transported in the forms of waves from any source

continuously with the velocity of light and consists of electric and magnetic fields oscillating
perpendicular to each other and to the direction of propagation.
These are energy radiations, which do not need any medium for propagation.
An electromagnetic radiation is generated by oscillations of a charged body in a magnetic field or
a magnet in an electric field.
These radiations or waves have electrical and magnetic field associated with them and travel at right
angle to these fields.
The rest mass of photon is zero.
All electromagnetic radiations travel with the velocity of light (3 108 m s1).

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PROPERTIES OF WAVES

A wave is always characterised by the following five characteristics:

(i) Wavelength: The distance between two nearest crests or nearest troughs is called a wavelength. It is
denoted by (lambda) and is measured in terms of centimetre (cm) or angstrom ( A ) or micrometre
0

( m ) or nanometre (nm).
(ii)Frequency: It is defined as the number of waves which pass through a point in one second. It is denoted
by the symbol (nu) and is measured in terms of cycles (or waves ) per second (cps) or Hertz (Hz) units.

c
v

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(iii)
Velocity: It is defind as the distance covered in one second by the wave. It is generally denoted by
the letter c. All electromagnetic waves travel with same velocity, i.e, 3 1010 cm / sec .
(iv) Wave number: This is reciprocal of wavelength, i,e., number of wavelengths per centimetre. It is
denoted by the symbol

H
C

m
u

(nu bar).

1
(It is expressed in cm 1 or m 1 )

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(v) Amplitude: It is defined as the height of the crest or depth of the trough of wave. It is denoted by the
litter a. It determines the intensity of the radiation.
(vi)

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Intensity a 2
Time period (T): Time taken by the wave to complete one cycle or one vibration.
T

1
v

LIMITATIONS OF ELECTROMAGNETIC WAVES

Electromagnetic wave theory was successful in explaining the properties of light such as interference,

diffraction etc. but it could not explain the phenomena of Black body radiation, and Photoelectric
effect.

Chemistry By Arun Kumar Saini

INORGANIC CHEMISTRYATOMIC STRUCTURE

PLANCKS QUANTUM THEORY

This theory was proposed by Max Planck to explain black body radiations and photoelectric effect.
According to this theory,

Radiant energy is emitted or absorbed only in discrete units or packets of energy called photon
(quantum). the energy E associated with a quantum is given by E h , where h is Plancks constant
and v is frequency of radiations.

E h

hc

hc

h is Plancks constant = 6.625 10 34 J sec. 6.625 10 27 erg sec

c is velocity of light = 3.0 10 8 m sec 1 = 3.0 10 10 cm sec 1
Energy E associated with a photon can also be written as

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12375
E
eV. where E is energy in eV and is wavelength of light in .

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PHOTOELECTRIC EFFECT

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The phenomenon of ejection of electrons from the surface of a metal when light of suitable frequency
strikes on it, is called as photoelectric effect. The emitted electrons are called photoelectrons.
Threshold energy is a character of a particular metal, therefore

h x

1
m 2
2

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r
a

m
u

If the threshold frequency is 0 , then Threshold energy, x h 0 , so that

1
1
h h 0 m 2 or m 2 h h 0
2
2

H
C

K
n

Therefore kinetic energy of ejected electron

K . E. h h 0

1
( m 2)
2

In this equation h energy of incidental photon and h 0 minimum value of energy required to eject
the electron.

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Chemistry By Arun Kumar Saini

INORGANIC CHEMISTRYATOMIC STRUCTURE

EXERCISE-I
FUNDAMENTALS OF ATOMIC STRUCTURE
REVISE SOME IMPORTANT FACTS:
(1) Electron: Specific charge

C h a rg e

M ass

of chathode ray is a universal constant. Charge of an electron

is 1 unit or 1 .6 1 0 1 9 C . The mass of one electron is 0.000549 amu or 9 .1 1 0 3 1 K g .

(2) Proton: The specific charge of anode rays is not a universal constant. The charge of a proton is

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1 unit or + 1.6 10 19 C . The mass of one proton is 1.0072 amu or

1 .6 7 2 1 0

27

Kg

(3) Neutron: It was discovered during radioactive disintegration ( 49 Be 24 He 126 C 01n ). The mass of
neutron ( 1.675 10 27 Kg ) is slightly higher than proton.
(4) Isosters: Species with same number of atoms & isoelectronic.
(5) Isodiaphers: Same isotopic number.

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(6) Rutherford Model: Number of particles at an angle

(7) Plank,s Quantum Theory: E h

1

sin4
2

hc
hc
[h= 6.626 10 34 J s ].

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r
a

Energy E associated with a photon can also be written as

12375
E
eV .

a
S

[E is energy in eV and is wavelength of light in .

m
u

1
2

(8) Photoelectric Effect: h h 0 m 2

H
C

SOLVE THESE QUESTIONS:

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01. The mass number of an element is A. If number of neutrons are x % extra than the number of protons,
what is the atomic number of the element:
200 x

(a) 100 A

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100 x

100 A

200 A

(b) 200 A
(c) 200 x
(d) 100 x
02. Atoms may be regarded as comprising of protons, neutrons and electrosns. If the mass attributed by
electrons was doubled and that attributed by neutrons was halved, the atomic mass of 12C would be:
(a) Reduced approx 25 %
(b) Doubled
(c) Approximately the same
(d) Approx halved
03. Three isotopes of an element have mass numbers M, (M + 1) & (M + 2). If the mean mass number is (M +
0.5), then which of the following ratios may be accepted for M, (M + 1), (M + 2) in that order:
(a) 1 : 1 : 1
(b) 4 : 1 : 1
(c) 3 : 2 : 1
(d) 2 : 1 : 1
04. The specific charge of a proton is 9.6 10 7 C kg1, then find the specific charge for an particle.
05. The number of quanta of radiations of frequency 4.67 10 12 s1 that must be absorbed in order to melt 5
g of ice is 54 1011x. Find the value of x. The energy required to melt 1 g of ice is 333 J.
06. A bulb emits light of wavelength 4500 . The bulb rated as 150 watts and 8 % of energy is emitted as
light. The number of photons emitted by the bulb per sec is 13.63 10 2x. What is the value of x.

Chemistry By Arun Kumar Saini

INORGANIC CHEMISTRYATOMIC STRUCTURE

07. A 1-kW radio transmitter operates at a frequency of 880 Hz. How many photons per second does it emit?
08. A photosensitive material would emit electrons if excited by photons beyond a threshold, to overcome
the threshold, one would increase:
(a) The intensity of light
(b) The wavelength of light
(c) The frequency of light
(d) All
09. In an experiment of photoelectric effect the stopping potential was measured to be V 1 & V2 volts, with

respectively. The relation between V1 & V2 may be:

2
(b) V1 V2 2 V1
(c) V2 = 2 V1
(d) V2 2 V1

incident light of wavelength &

(a) V2 2 V1 V1

10. Photoelectric emission is observed from a surface for frequencies 1 and 2 of the incident radiation

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( 1 > 2 ). If the maximum K.E. of the photoelectrons in two cases are in ratio 1 : K, then the threshold
frequency 0 is given by

2 1
2 1
K1 2
K2 1
(B)
(C)
(D)
K 1
K 1
K 1
K
11. In photoelectric effect work function of any metal is 2.5 eV. The most energetic emitted electrons are
stopped by the potential of 1.5 volt then
(A) Energy of incident photons is 4 eV
(B) Energy of incident photons is 1 eV
(C) Photoelectric current increases when we use photons of high frequency
(D) None of the above
12. With the help of following graph calculate K.E. corresponding to = 2000 .

(A)

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13. If 32 -particles scattered by an angle 60 in Rutherford's experiment, then how many -particles
scattered by an angle of 90?

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14. In a photoelectric experiment the collector plate is 2.0 V with respect to emitter plate of Cu (W =
0.5 eV). The emitter is illuminated by source of chromatic light of wavelength 200 nm. Find the
minimum & maximum KE of photoelectron reaching the collector.

15. A light of wavelength 4500 A is striked on metal surface. Kinetic energy of photoelectrons is half
of the energy of incident radiation. The threshold frequency of metal is:
(A)

1
1015 Hz
3

(B)

4
1015 Hz
3

(C)

2
1015 Hz
3

Chemistry By Arun Kumar Saini

(D)

4
1012 Hz
3

INORGANIC CHEMISTRYATOMIC STRUCTURE

BOHRS ATOMIC MODEL

BOHRS ATOMIC MODEL

Bohrs theory was based on application of Plancks quantum theory on the atomic spectra of hydrogen
atom.
The electrons revolve around the nucleus in a certain orbits without losing energy because the energy
in a fraction of a quantum can neither be lost nor gained.
Energy is absorbed or emitted only when an electron in an atom jumps from one orbit to another.
The necessary centripetal force is provided by the electrostatic attraction of protons in the nucleus.
Bohrs model is applicable only to one-electron atoms like, H, He +, Li++ etc.

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The electron is restricted to those orbits in which its angular momentum is an integral multiple of

(1)

SOME IMPORTANT RELATIONS

Angular momentum for a shell is given by

J = mvr =

(2)

nh
2

or J n

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a
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The necessary centripetal force for uniform circular motion is balanced by electrostatic force of
attraction between electron and the nucleus
1 Ze 2 mv 2

4 0 r 2
r

(3)

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r
a

Velocity of an electron in an orbit: Combining relation (1) & (2)

2

m
u

1 Ze mv
1 Ze mv r
1 Ze2
1 Ze2
Ze2
=
or
=
or v =
or v =
or v =
2
4 0 r
r
4 0
4 0 mvr
4 0 nh
2 0nh
2

H
C

v 2.188108
(4)

K
n

Z
Z
cm s 1 or v n v 1
n
n

Radius of orbit:

or r 0.529

u
r

or v

Z
n

1 Ze 2 mv 2
1 Ze 2 r
=
or
= or r =
2
4 0 r
r
4 0 mv 2

n2 .
n2
A or rn r1
Z
Z

or r

Ze 2
Ze 2
4 0 m

2 0 nh

or r =

n2h2 0
mZe 2

n2
Z

Z c

c is velocity of light
n 137
The relation of time period & frequency of revolution of an electron is given by
vn

(5)

h
.
2

2 rn 1
n3
Z2

&
f

vn
f or
Z2
n3

Chemistry By Arun Kumar Saini

(6)

INORGANIC CHEMISTRYATOMIC STRUCTURE

The kinetic energy of an electron in an orbit is given by

2
Ze 2
2 2 Z 2 me 4
Z2
( )
() (13.6) 2 eV per atom ( ) ( E n ) or KE () Z
KE ( ) ( k )
2 2
n2
2r
n h

(7)

The potential energy of an electron in an orbit is given by

Ze 2
PE ( ) ( k )
r

(8)

4 2 Z 2 me 4
( )
2 2

n h

Z2
() (2 13.6) 2

eV per atom ( 2 ) ( E n ) or PE ( ) Z
n2

The total energy of an electron in an orbit is given by

Ze 2
2 2 Z 2 me 4
Z2
Z2
( )

En ( ) ( k )

)
(
13
.
6
)
eV
per
atom
E

)
or
2 2

n2
n
n2
2r
n h

Potential Energy
2
(10) Time period of revolution is given by
(9)

Kinetic Energy () Total Energy ()

T1 r1 n1
n1

T 2 r2 n 2 = n
2

(11) Moment if inertia = mr2

I n

(12) Ionization energy of an electron

I.E = E E(ground state) = + E(ground state)
(13) For Bohr energies
E1 < E2 < E3 < E4
(E2 E1) > (E3 E2) > (E4 E3).

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r
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(E = Zero)

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FAILURE OF BOHRS MODEL

It does not explain the spectra of species having more than one electron.
It does not explain the fine spectral lines obtained under a spectroscope of strong resolution. (Fine

structures are related to subshells)

It can not explain Zeeman effect (splitting of spectral lines under magnetic filed) and Stark effect
(splitting of spectral lines under electric field). (It is the spliting of energies of different orbitals
for a given subshell)

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SOMMERFELD ATOMIC MODEL

According to Summerfield shell are divided into subshells.

Subshell may be s (spherical), p (dumble shaped), d (double dumble shaped) or f (complex).
Radial (spherical) nodes = nl1
ns subshell have (n1) radial nodes and np subshell have (n2) nodes and so on.

Chemistry By Arun Kumar Saini

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INORGANIC CHEMISTRYATOMIC STRUCTURE

EXERCISE-II
BOHRS ATOMIC MODEL
REVISE SOME IMPORTANT FACTS:

n2 0
1. Radius of Bohr Orbit: rn (0.529) A
Z
Z 1
ms
n

6
2. Velocity of Bohr orbit: vn (2.19 10 )

3.

&

Z2
E

)(13.6)
4. Energy of Bohr Orbit: n
n2 eV

1

5. Rydberg's Constant: [R = 109,677 cm ].

SOLVE THESE QUESTIONS:

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n3
Z2
&
f

Z2
n3

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1. For which of the following species, Bohr theory does not apply:
(a) H
(b) H
(c) He +

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(d) Li2+

2. The ratio of the radius of Bohr first orbit for the electron orbiting the hydrogen nucleus to that
of the electron orbiting the deuterium nucleus (Mass nearyl twice that of H nucleus) is approximately:
(a) 1 : 1

(b) 1 : 2

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C

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(c) 2 : 1

(d) 1 : 4

3. For an electron, the product (velocity principle quantum number) will be indepedent of the
(a) Principal quantum number
(b) Velocity of the electron
(c) Energy of the electron
(d) Frequency of its revolution

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4. In two Hatoms A and B the electrons move around the nucleus in circular orbits of radius r
and 4r respectively. The ratio of the time taken by them to complete one revolution is:
(a) 1 : 4

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(b) 1 : 2

(c) 1 : 8

(d) 2 : 1

5. For which of the following, the radius will be same as for hydrogen atom having n = 1?
(a) He+, n = 2
(b) Li2+, n = 2
(c) Be3+, n = 2
(d) Li2+, n = 3

6. In hydrogen atom, energy of first excited state is 3.4 eV. Then find out the KE of the same orbit
of hydrogen atom.
7. The energy of an electron in the first Bohr orbit of Hatom is 13.6 eV. The possible energy value
of the excited state(s) for electrons in Bohr orbits of hydrogen is (are):
(a) 3.4 eV
(b) 4.2 eV
(c) 6.8 eV
(d) +6.8 eV
8. The radii of two of the first four Bohr orbits of the hydrogen atom are in the ratio 1 : 4. The energy
difference between them may be:
(a) Either 12.09 eV or 3.4 eV
(b) Either 2.55 eV or 10.2 eV
(c) Either 13.6 eV or 3.4 eV
(d) Either 3.4 eV or 0.85 eV

Chemistry By Arun Kumar Saini

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INORGANIC CHEMISTRYATOMIC STRUCTURE

9. What is the potential energy of an electron present in I st shell of hydrogen species?

e2
(A)
4 0 r

(B) 2 Total energy

e2
(C)
8 0 r

(D) +13.6 eV

10. The one electron species having ionization energy of 54.4 eV is:
(a) H
(b) He +
(c) B4+
(d) Li2+
11. The ratio of force of attraction on electron in first orbit and second orbit of H atom is 2x. The
value of x is--------.
12. Match the following
Column I

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Column II

(A) Energy of orbit

(p) Directly proportional to Z 2

(B) Time of revolution

(q) Directly proportional to Z 3

(C) Radius of orbit

(r) Directly proportional to n 2

(D) Force of attraction

(s) Directly proportional to n 2

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(t) Dependent on mass of electron

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13. The binding energy of an electron in the ground state of the He atom is equal to 24 eV. Calculate
the energy required to remove both the electrons from the atom.

r
a

14. 1.8 g hydrogen atoms are excited to radiations. The study of spectra indicates that 27% of the
atoms are in 3rd energy level and 15 % of atoms in 2nd energy level and the rest in ground state.
IP of H is 13.6 eV. Calculate

M
E

(i) Number of atoms present in III and II energy level

m
u

(ii) Total energy evolved when all the atoms return to ground state

H
C

15. An ion M n is one electron system and radius of its third orbit is
125

K
n

times that of fifth orbit

of H-atom. The amount of energy required to remove single electron from M n ion is:
(A) 122.4 eV

(B) 217.6 eV

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(C) 340 eV

Chemistry By Arun Kumar Saini

(D) 489.6 eV

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INORGANIC CHEMISTRYATOMIC STRUCTURE

SPECTRUM OF ATOM
SPECTRUM OF HYDROGEN ATOM

When an electron jumps from a higher energy state to a lower energy state, the radiation is emitted in
from of photons.
Spectral lines are regarded as the finger prints of the elements.
The radiation emitted in a transition corresponds to the spectral line in the atomic spectra of H-atom.
* The difference of energies between two successive shells is given by:
2


1
1 13.6 1
En E( n 1) En 13.6 2
2 1

2
n (n 1) n 1 1
n

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RYDBERGS FORMULA

1 1
1
RZ 2 2 2 (R = 109,677
cm 1 )

n1 n2

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HYDROGEN SPECTRAL LINES

H
C
A
Lines
Lyman
Balmer
Paschen
Brackett
Pfund
Humphrey

n1
1
2
3
4
5
6

M
E

u
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m
u

K
n

n2
2, 3, 4..
3, 4, 5
4, 5, 6,..
5, 6, 7,..
6, 7, 8,
7, 8, 9.

Spectral regions
Ultraviolet
Visible
Infrared
Infrared
Infrared
Infrared

Chemistry By Arun Kumar Saini

a
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INORGANIC CHEMISTRYATOMIC STRUCTURE

The maximum number of emission lines noticed when the electron jumps from the nth shell to the
ground stage due to all possible jumps is

The maximum number of emission lines noticed when the electron jumps from the n 2 shell to the n1
stage due to all possible jumps is

n (n 1)
.
2

(n2 n1 )(n2 n1 +1)

.
2

Adsorption spectrum of hydrogen has only Lyman series wavelengths, because electron can not remain
at higher energy levels.

H
C
A

M
E

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r
a

m
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Chemistry By Arun Kumar Saini

a
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INORGANIC CHEMISTRYATOMIC STRUCTURE

EXERCISE-III
SPECTRUM OF ATOM
1. Transition Energy of Bohr Orbits & Spectrum of Radiation:
2. Number of Spectral Lines of Transitions:

1 1
1
RZ 2 2 2

n1 n2

(n 2 n 1 ) (n 2 n1 +1)
n(n 1)
&
.
2
2

3. Rydberg's Constant: [R = 109,677 cm ].

SOLVE THESE QUESTIONS:

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1. An electron in the hydrogen atom jumps from some higher level to third energy level. If three
spectral lines are possible for the transition, find the initial orbit of electron.
2. Calculate the number of spectral lines that can be possible when electrons in 7 th shell in different
hydrogen atoms return to the 2nd shell.
3. Whenever a hydrogen atom emits a photon in the Balmer series
(A) It may emit another photon in the Balmer series
(B) It may emit another photon in the Lyman series
(C) The second photon, if emitted will have a wavelength of about 122 nm
(D) It may emit a second photon, but the wavelength of this photon cannot be predicted
4. Energy levels A, B, C of a certain atom corresponds to increasing values of energy, i.e., E A < EB < EC.

M
E

S
I

r
a

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m
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If 1 , 2 and 3 are the wavelengths of radiations corresponding to the transitions C to B, B to A

anc C to A respectively, which of the following statements is correct?

H
C
2

C
B

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K
n

12
(b) 3
1
2

(a) 3 1 2

(c) 1 2 3 0

(d) 32 12 22

5. Calculate the wavelength of the spectral line obtained in the spectrum of Li 2+ ion when the
transition takes place between two levels whose sum is 4 and difference is 2.
6. Two hydrogen atoms with electrons in ground state collide head on and ends up with zero kinetic
energy. Each then emits a photon of wavelength 121.6 nm. Which transition leads to this
wavelength? How fast were the hydrogen atoms traveling before collision?
7. An electron in a H-like species is in the excited state (n 2). The wavelength corresponding to
a transition to the second orbit is 48.24 nm. From the same orbit, wavelength corresponding
to a transition to third orbit is 142.46 nm. Find the value of (n 2 Z), where Z is the atomic
number of H-like species.

Chemistry By Arun Kumar Saini

15

INORGANIC CHEMISTRYATOMIC STRUCTURE

8. The wave number of first line of Balmer series of hydrogen is 15200 cm 1. Calculate the wave
number of the first Balmer line of Li 2+ ion.
9. The ratio of (E2 E1) to (E4 E3) for the hydrogen atom is approximately equal to:
(a) 10
(b) 15
(c) 17
(d) 12
10. The transition of an electron in the hydrogen atom that will emit maximum energy is:
(a) n5 to n4
(b) n4 to n3
(c) n3 to n2
(d) n2 to n1
11. A hydrogen atom in an excited state emits a photon which has the longest wavelength of the Paschen
series. Further emissions from the atom cannot include the
(A) longest wavelength of the Lyman series
(B) second longest wavelength of the Lyman series
(C) longest wavelength of the Balmer series
(D) second longest wavelength of the Balmer series
12. 1.8 g hydrogen atoms are excited to radiations. The study of spectra indicates that 27% of the
atoms are in 3rd energy level and 15% of atoms in 2nd energy level and the rest in ground state. If
I.P. of H is 21.7 10-12 erg. Calculate:
(i) No. of atoms present in III & II energy level.
(ii) Total energy evolved when all the atoms return to ground state.
13. One mole He+ ions are excited. Spectral analysis showed existence of 50% ions in 3 rd orbit, 25% in
2nd and rest in ground state. Calculate total energy evolved when all the ions return to the ground
state.

S
I

Y
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i
T in
r
a

a
S

14. The ionization of H is 13.6 eV. It is exposed to electromagnetic waves of 1028 A and given out
induced radiations. Find the wavelength of these induced radiations.

M
E

15. Find the quantum number 'n' corresponding to the excited state of He+ ion if on transition

m
u

to the ground state that ion emits two photons in succession with wavelength 108.5 nm
and 30.4 nm.
16. Hydrogen atoms in a particular excited state 'n' when all returned to ground state, 6
different photons are emitted. Then which of the following are incorrect:
(A) Out of 6 different photons only 2 photons can be of visible light
(B) If highest energy photon emitted from the above sample is incident on the metal plate
surface having work function 8 eV, average kinetic energy of liberated photoelectron may
be equal to or less than 4.75 eV.
(C) Total number of radial nodes in all the orbitals of n shell is 24

H
C
A

u
r

K
n

(D) Total number of angular nodes in all the orbitals in ( n 1)th shell is 23

Chemistry By Arun Kumar Saini

16

INORGANIC CHEMISTRYATOMIC STRUCTURE

MODERN ATOMIC MODEL

MOSELEYS EXPERIMENT

Xrays are electromagnetic radiations of very small wavelengths (0.120 angstrom) and were
discovered by Roentgen.
Moseley investigated the x ray spectra of 38 different elements, starting from aluminium and ending
in gold.
It was realized that the frequency of the particular spectral line was more precisely related with the
serial number of the element in the periodic table.
= a (Z - b)
Moseley discovered atomic number.

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COMPTON EFFECT

When monochromatic xrays are allowed to fall on some light elements i.e. intereract with the electrons,

the scattered x-rays have longer wavelength or less frequency or less energy than the incident
rays. This effect is called Compton effect.

S
I

a
S

DE BROGLIE PRINCIPLE-WAVE PARTICLE DUALITY

de-Broglie suggested that as light has the dual properties of wave and particle, the particles of matter
such as electrons, protons etc also have properties of waves.
Some
relations

E = h = mc2
=

h
h
=
mc p

M
E

m
u

If an electron is accelerated by a potential V, than

=

12.26 10 10
m=
V

H
C

150 0 12.26 0
A
A
V
V

r
a

K
n

Approval of Bohr conceptOnly that orbit is possible around the nucleus whose circumference is
equal to integral multiple of .

nh
nh
2 r = n =
or r =
2 m v
mv

u
r

or mvr (Angular momentum) =

nh
2

De-Broglie wavelength in an Bohr orbit is given by

mv

h
Ze
m

2 0 nh
2

2 0 nh 2
n
(Cons )
2
mZe
Z

or

n
Z

Davisson and Germer experimentally verifies the de-Broglie hypothesis.

Diffraction, Polarization and Interference are in favour of wave nature of light.
Photoelectric effect and Black body radiation are in favour of particle nature of light.

Chemistry By Arun Kumar Saini

17

INORGANIC CHEMISTRYATOMIC STRUCTURE

HEISENBERG UNCERTAINTY PRINCIPLE

It is impossible to specify at any given instant both the momentum and the position of a subatomic

particle like electron.

It is applicable on both microscopic and macroscopic bodies, but have significance only for
microscopic bodies.
If
the uncertainty in the position of a moving electron is zero, then its velocity will be completely

uncertain.
Electron /Positron cannot remain inside the nucleus. Due to small size of nucleus uncertainty in the
velocity becomes greater than the light, which is impossible.

x.p

h
4

E.t

h
4

or

x.v

h
4 m

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( E is the uncertainty in energy & t is the uncertainty in time)

SCHRODINGER WAVE EQUATION: QUANTUM MECHANICS

S
I

a
S

Bohr treated electron as a particle. However, de Broglie suggested that e has a dual nature,
i.e., behaves both as a particle as well as wave.
According to wave theory, an electron is a stationary wave moving around the nucleus in a
circular path. The wave character was later on confirmed by Davison, Germer (1927) and Thomson
(1928).

M
E

r
a

According to Schrodinger, the electron does not move round the nucleus in fixed orbits, but may,

infact, be any where with different probabilities. The probability of its presence near the nucleus is
greatest and as the distance from nucleus increases the probability decreases. Schrodinger
from mathematical treatment of wave motion gave a general wave equation describing the behaviour of
a small particle.
The wave motion of the electron in an atom, moving in the three-dimensional space is given by
Schrodinger wave equation. It provides a methematical description of much of the dual particle like
and wave like behavior and interaction of energy and matter. The name quantum mechanics derives
from the observation that some physical quantities can change only in discrete amounts & not in
contineous way.

H
C

u
r

m
u

K
n

2 2 2 8 2 m
+

( E V ) 0
x2 y2 z2 h2

(Mathematical function) is the amplitude of the wave at any point whose co-ordinates are x, y

and z. It provides information about the probability amplitude of position, momentum & other physical
properties of particle. m is the mass of electron. E is the total energy of the electron and V is its
potential energy.
is also called wave function as it describes the wave motion of the electron and its value is a
function of the co-ordinates x, y, z. So it is represented in a more correct way as (x, y, z).
This equation, being a differential equation of second order, can have many solutions for the
amplitude function but only those values of are acceptable or have significance, which satisfy
certain conditions.

Chemistry By Arun Kumar Saini

18

INORGANIC CHEMISTRYATOMIC STRUCTURE

Acceptable values of are those, which correspond to some definite values of the total energy E. Such
values of the total energy, E are called Eigen values. The corresponding values of the function are
called Eigen function. These values are same as given for the energy levels of hydrogen atom according
to Bohrs modal.
The existence of quantized electronic energy levels is a direct result of the wave like properties of
electrons and are allowed solution of schrodinger wave equation.
All the information about the electron in an atom is contained in its orbital wave function ` ` and
quantum mechanics makes it possible to extract this information from ` `.

RADIAL DISTRIBUTION FUNCTION

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The electronic wavefunction, as we have seen above, describes the distribution of the electron

positions in terms of the distance of the electron from the nucleus, r, and the orientaion of the
electron relative to the nucleus. We can separate the wavefunction into an orientationally
dependent part, known as the angular wavefunction, and an orientationally independent
part, which is known as the radial wavefunction.

nlm ( r , , ) R nl ( r )
Radial

. Ylm ( , )
Angular

part

part

S
I

a
S

The Radial Wave function, Rnl(r), depends only on the distance of the electron from the nucleus,
and is characterized by the values of the principal and azimuthal quantum numbers.

r
a

The Angular Wavefunction, Ylm ( , ) , depends on the angles of the electron from the nucleus, and

M
E

is characterized by the values of the azimuthal quantum number and magnetic quantum
numbers. The s orbitals consist only of a radial part to the wavefunction.
Radial
distribution function, Pnl(r), is the probability density. It is defined as probability of

finding electron at a given distance from the nucleus.

Pnl ( r ) 4 r 2 Rnl ( r )

H
C

1s [ 1,0,0 R1,0 . Y0,0 ] :

2 s [ 2,0,0 R2,0 . Y0,0 ] :

3s [ 3,0,0 R3,0 .Y0,0 ] :

u
r

m
u

K
n
(RWF)

(RDF)

(RWF)

(RDF)

(RWF)

(RDF)

Chemistry By Arun Kumar Saini

19

INORGANIC CHEMISTRYATOMIC STRUCTURE

(RWF)

2 p [ 2,1,0 or 1or 1 R2,1 . Y1,0 or 1or 1 ] :

3p:

(RWF)

(RDF)

3d:

(RDF)

(RWF)

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(RDF)

S
I

ATOMIC ORBITALS

a
S

An orbital is the electron distribution described by a wave function and associated with a particular

energy.
The orbital wave function has no physical significance. It only represents the amplitude of the
wave.
The square of the absolute value of the orbital wave function 2 has physical significance (measures
the electron probability density at a point in an atom around the nucleus i.e. orbital).
All the orbitals of the same shell in absence of magnetic field posses same energy,i.e. they are
degenerate.
All the orbitals of the same subshell differ in the direction of their space orientation.
Total number of orbitals in a main energy shell is equal to n2 (but not more than 16 in any of the main
shell of the known elements).
s = Sharp (2 e), p = Principle (6 e), d = Diffused (10 e), f = Fundamental (14 e), g = Degenerate
(18 e). The next subshell is h, which is concerned with alphabatic order.

H
C

y
x

M
E

u
r

m
u

K
n

x
+

px Orbitals
+

x
y

1s Orbital
(a)

r
a

2s Orbital

(b)
The shapes of s-orbital

z
pxpypz Orbitals

py Orbitals
Shape of p orbitals

Chemistry By Arun Kumar Saini

pz Orbitals

20

INORGANIC CHEMISTRYATOMIC STRUCTURE

NODES & NODAL PLANES

Node is the place where wave function changes its sign. Angular nodal plane is the plane node with it.

S
I

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Radial nodes are concerned with distance. These are equal to ( n l 1) .

Angular nodes are concerned with direction. These are equal to l .
sorbital has no nodal plane (no node), porbital has one nodal plane (one node), dorbital has

a
S

two nodal planes (two nodes).

s-orbital
has spherical (radial) nodes only while others have planar nodel planes as well as

radial nodes.

M
E

r
a

d Z 2 has two conical nodal planes (two nodes). The angle from the z axis is 54.70 at which this plane

is present.

H
C
A

u
r

m
u

K
n

Chemistry By Arun Kumar Saini

21

INORGANIC CHEMISTRYATOMIC STRUCTURE

EXERCISE-IV
MODERN ATOMIC MODELS
REVISE SOME IMPORTANT FACTS:
If an electron is accelerated by a potential V, than
=

12.26 1010
150 0 12.26 0
m=
A
A
V
V
V

2 2 2 8 2m
Schrodinger wave equation: x2 + y2 z 2 h2 (E V ) 0

Wave function ( nlm ( r , , ) ): nlm ( r , , ) Rnl ( r ) . Ylm ( , )

Radial

Angular

part

part

Y
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Radial probability density (Probability of finding electron at a given distance):

Pnl (r ) 4 r2 Rnl (r )

Graphs of radial part of wave function

1s:

2s:

3s:

S
I

2p:

M
E

3p:

r
a

a
S
3d:

Radial node or spherical node is the place where radial wave function ( Rnl ( r ) ) changes its sign.
Number of radial nodes = n l 1.

SOLVE THESE QUESTIONS:

H
C

m
u

1. If uncertainty in position and momentum are equal , then uncertainty in velocity is:
h

(a)

K
n

h
2

(b)

1
2m

(c)

(d)

2 times

(d)

2. If the kinetic energy of a particle is doubled, de Broglie wavelength becomes:

(a) 2 times

u
r

(b) 4 times

(c)

1 h
m
1
2

3. The uncertainly in the position of an electron moving with a velocity of 3.0 10 4 cm s 1 accurate upto
0.011 % will be
(a) 1.92 cm
(b) 7.68 cm
(c) 0.175 cm
(d) 3.84 cm
4. Identify the correct statement(s) amongst the following

(A) For H atom energy ratio of 2s and 2p orbitals is equal to one.

(B)

d orbital of H-atom is 9a0

(C) The average distance of the 3s-electron from the nucleus of H-atom is 4a0

(D) de-Broglie wavelength in a Bohr orbit for H-like species is directly proportional to

Chemistry By Arun Kumar Saini

n
Z

22

INORGANIC CHEMISTRYATOMIC STRUCTURE

5. If 0 is the threshold wavelength for photoelectric emission, wavelength of light falling on the
surface of metal, and m, mass of electron, then de Broglie wavelength of emitted electron is
1

h ( 0 ) 2
(A)

2 mc ( 0 )

(B)

h ( 0 ) 2

2mc 0

(C)

h ( 0 ) 2

2 mc 0

h 0 2
(D)

2 mc

6. Total number of electrons occupied in an energy level is given by

(A)

l n1

2(2l 1)

(B)

l 0

l n 1

(C)

2(2 l 1)

l 1

l n

[2 l 1]

(D)

l 0

7. The scrodinger wave eq for hydrogen atom is

3

1 1 2 ro r0 ao
2s
2 e
4 2 ao ao

l n 1

[2l 1]

l 0

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Where ao is Bohr radius of the radial node in 2s be at r o then find r in term of ao

(a) ro 2ao

(b) 2ro ao

S
I
(c)

8. Which of the following statements is /are correct?

(a) 2 represents atomic orbital

3
ro a o
2

r
a

(d) ro ao

a
S

(b) Number of radial nodes in an orbital is equal to n l 1

(c) A node is a point in space where wave function ( ) has zero amplitude & its sign changes
(d) None

M
E

m
u

9. Which of the following sets of quantum number is correct for an orbital 432 ?
(A) n = 4, l = 2, m = 3

H
C

(C) n = 3, l = 2, m = 3

K
n

(B) n = 4, l = 3, m = 2

(D) n = 4, l = 3, m = 3

10. If , be the angular function of angle and respectively involved in the polar co-ordinates,
which of the following is the incorrect statement regarding to probability density ( 2 ) of 2s
atomic orbital?

u
r

2
(A) 2s
is independent on only

(B)

2
2s

is independent on both and

2
(C) 2s
is independent on only
2
(D) 2s
is independent on both and & dependent only radius

11. Which of the following statements is correct about angular nodes?

(A) These nodes are directional in nature
(B) These nodes are dependent on angle and
(C) These nodes are independent from the radial wave function (R)
(D) These nodes are dependent on the radial wave function

Chemistry By Arun Kumar Saini

23

INORGANIC CHEMISTRYATOMIC STRUCTURE

12. An electron practically at rest, is initially accelerated through a potential difference of 100 volts. It
then has a De-Broglie wavelength 1 A0 . It then gets retarded through 19 volts and then has a
wavelength 2 A0 . A further retardation through 32 volts changes the wavelength to 3 A0 . What is
the value of

2
1

13. From the following observations predict the type of orbital:

Observation 1: xy plane acts as a nodal plane
Observation 2: The angular function of the orbital intersect the three axis at origin only.
Observation 3: R2(r) / v/s r curve is obtained for the orbital is

(A) 5pz

(B) 6dxy

H
C
A

M
E

u
r

Y
R
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(C) 6 dx2y2

S
I

r
a

m
u

K
n

Chemistry By Arun Kumar Saini

(D) 6 dyz

a
S

24

INORGANIC CHEMISTRYATOMIC STRUCTURE

ELECTRONIC CONFIGURATION & QUANTUM NUMBERS

Aufbau Principle
Hund's Principle
Pauli's Exclusion Principle
Quantum Numbers

Topics:

AUFBAU PRINCIPLE OR (n + l ) RULE

It gives the electronic distribution in different subshells.

Aufbau is not a name of scientist.
In the ground state of the atom, the orbitals are filled in order of their increasing energies, starting

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with the orbital of lowest energy.

1s < 2s < 2p < 3s < 3p < 4s < 3d < 4p < 5s < 4d < 5p < 6s < 4f < 5d
Moeller diagram nicely explains Aufbau Principle.

1s

H
C

2p

3s

3p

3d

4s

4p

4d

5s

5p

6s

6p

M
E

r
a

4f

a
S

m
u
5d

K
n
7s

For Hatom

S
I

2s

Is < 2s = 2p < 3s = 3p = 3d <4s = 4p = 4d = 4f

u
r

For 30Zn, the energy of 3d subshell is lower than 4s subshell.

The last electron in Zn, Cd and Hg enters the 4s, 5s and 6s orbitals respectively.
Orbitals are filled in order of increasing (n + l) values.
If two orbitals have the same (n + l) value, the orbital with lower value of n is filled first.

HUNDS RULE

It gives the electronic distribution in degenerate orbitals.

Pairing of electrons in the orbitals belonging to the same sub-shell (degenerate orbitals) does not
take place till each orbital of that subshell has got one electron each i.e. singly occupied.

PAULIS EXCLUSION PRINCIPLE

No two electrons in an atom can have the same set of four quantum numbers.
In an orbital only two electrons may exit and their spins are opposite.
No two electrons can have the same quantised states.
Chemistry By Arun Kumar Saini

25

INORGANIC CHEMISTRYATOMIC STRUCTURE

ELECTRONIC CONFIGURATION

Elements with atomic numbers 24Cr, 42Mo and 74W have ns1 (n - 1) d5 configuration and not ns2 (n 1)
d4 configuration leading to extra stability.
Elements with atomic numbers 29Cu, 47Ag and 79Au have ns1 (n-1) d10 configuration and not ns2 (n 1)
d9 configuration leading to extra stability.
Cr = 1s2, 2s2, 2p6, 3s2, 3p6, 3d5, 4s1
24
Cu = 1s2, 2s2, 2p6, 3s2, 3p6, 3d10, 4s1
29
Mo = 1s2, 2s2, 2p6, 3s2, 3p6, 3d10, 4p6, 4d5, 5s1
42
Pd = 1s2, 2s2, 2p6, 3s2, 3p6, 4s2, 3d10, 4p6, 4d10, 5s
46
Higher the exchange energy, higher is the stability and exchanges are maximum when degenerate
orbitals are exactly half filled or completely filled.
All
fblock elements are exception of Aufbau rule.

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QUANTUM NUMBERS

Quantum numbers are the addressee of electron.

Principle quantum no. (n) represents main energy level or size of shell.
Azimuthal quantum no.(l) represents shape of orbitals or identifies subshell
Magnetic quantum no. (m) represents orientation of orbitals
For different p- orbitals
Px
py
pz
1
1
0
For different d-orbitals
d xy
dyz
d zx
dx2 -y2
dz2
2
1
1
2
0
Spin quantum no.(s) represents orientation of spin.

M
E

S
I

r
a

a
S

m
u

DISCOVERER OF QUANTUM NUMBERS

H
C

Principal quantum no. by Bohr.

Azimuthal quantum no. by Sommerfeld.
Magnetic quantum no. by Lande
Spin quantum no. by Unlenback and Goldschmidt.
n, l and m are the solution of Schrodinger wave equation but s is not.

u
r

K
n

TOTAL SPIN & SPIN MAGNETIC MOMENT

The total spin in ground state is given by

x
S (x is the number of unpaired electrons)
2
The
"spin
only" magnetic moment of electron (excluding orbital magnetic moment) is given by

spin only 4 S ( S 1) x ( x 2)

ORBITAL ANGULAR MOMENTUM

The magnitude of angular momentum is given by

| L |

l ( l 1)

l ( l 1)
h

Chemistry By Arun Kumar Saini

26

INORGANIC CHEMISTRYATOMIC STRUCTURE

EXERCISE-IV
ELECTRONIC CONFIGURATION & QUANTUM NUMBERS
REVISE SOME IMPORTANT FACTS:
The magnitude of orbital angular momentum is given by

h
| L | l (l 1)
l (l 1)
h
2

x
The total spin in ground state is given by: S 2 (x is the number of unpaired electrons)
The "spin only" magnetic moment of electron (excluding orbital magnetic moment) is given by
spin only 4 S ( S 1) x ( x 2) BM (Bohr Magnetron)

SOLVE THESE QUESTIONS:

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1. What are the values of the orbital angular momentum of an electron in the orbitals 1s, 3s,
3d and 2p?
(a) 0, 0, 6 h ,

2
h

(b) 1,1, 4 h ,

2
h

S
I

(c) 0,1, 6 h ,

3
h

a
S

(d) 0, 0, 20 h ,

6
h

2. Total number of electrons in all the p-orbitals of bromine are:

(a) 17
(b) 24
(c) 27
(d) 33
3. Which one of the following forms a colourless solution in aqueous medium:
(a) V3+
(b) Cr 3+
(c) Ti3+
(d) Sc3+
4. The atomic number of an element is 17. The number of orbitals containing electron pairs in its
valence shell is:
(a) 3
(b) 4
(c) 6
(d) 8
5. Which one is paramagnetic among the following:
(a) Cl
(b) Be
(c) Ne
(d) As+
6. A compound of vanadium has amagnetic moment of 1.73 BM. The electronic configuration of vanadium ion in the compound is:
(a) [Ar]3d2
(b) [Ar]3d1
(c) [Ar]3d3
(d) [Ar]3d04s2
2+
7. Which have the same number of s-electrons as the d-electron is Fe ?
(a) Li
(b) Na
(c) N
(d) P

H
C

M
E

u
r

r
a

m
u

K
n

8. The magnetic moment of Cr+x is 15 BM. The value of ratio of number of paired e and unpaired
e in Cr+x is--------.
9. If m = magnetic quantum number, l = azimuthal quantum number, then:
(a) m l 1

(b) m 2 l 2 1

(c) l

m 1
2

Chemistry By Arun Kumar Saini

(d) l 2 m 1

27

INORGANIC CHEMISTRYATOMIC STRUCTURE

10. Match List-I with List-II and select the correct answer using the codes given below the lists:
( l and m are respectively the azimuthal and magnetic quantum numbers)
ListI
ListII
(A) Number of values of l for an energy level
1. 0, 1, 2, ......(n 1)
(B) Actual values of l for a particular type of orbital
2. + l to l through zero
(C) Number of values of m for l = 2
3. 5
(D) Actual values of m for a particular type of orbital
4. n
(a) A-4, B-1, C-2, D-3
(b) A-4, B-1, C-3, D-2
(c) A-1, B-4, C-2, D-3
(d) A-1, B-4, C-3, D-2
11. The correct set of quantum numbers is:
(a) n = 2, l = 1, m = 0, s = +
(b) n = 2, l = 2, m = 1, s = +

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(c) n = 2, l = 2, m = 1, s = -
(d) n = 2, l = 1, m = 0, s = 0
12. Consider the following two statements (Atomic number of Ag = 47):
(I) In silver atom, 23 electrons have a spin of one type and 24 of the opposite type.
(II) Ground state electronic configuration of nitrogen atom can be represented by:

S
I

(a) Both (I) and (II) are correct

(b) Both (I) and (II) are incorrect
(c) (I) is correct & (II) is incorrect
(d) (I) is incorrect & (II) is correct
13. For a shell of principle quantum number n = 4, there are
(a) 16 orbitals
(b) 4 subshells
(c) 32 electrons (maximum)
(d) 4 electrons with l = 3
14. Given set of quantum numbers for a multielectronic atom is:

M
E
s

H
C

m
u

r
a

a
S

K
n

Which is the next higher allowed set of 'n' and ' l ' quantum numbers for this atom in the ground
state?
(a) n = 2, l = 0
(b) n = 2, l = 1
(c) n = 3, l = 0
(d) n = 3, l = 1
15. Select the correct statement(s) among the following:
(i) Total number of orbitals in a shell with principle quantum numer 'n' is n 2
(ii) Total number of subshells in the nth energy level is n
(iii) The maximum number of electrons in a subshell is given by the expression (4l 2)

u
r

(iv) m l 2 , where l and m are azimuthal and magnetic quantum numbers

(a) (i), (iii) & (iv) are correct
(b) (i), (ii) & (iii) are correct
(c) (ii), (iii) & (iv) are correct
(d) (i), (ii) & (iv) are correct
16. If magnetic quantum number of a given atom represented by 3, then what will be its principal
quantum number
(a) 2
(b) 3
(c) 4
(d) 5

Chemistry By Arun Kumar Saini

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INORGANIC CHEMISTRYATOMIC STRUCTURE

17. Five valence electron of

A B

X Y Z

3s

3p

P are labelled as

15

If the spin quantum number of B & Z is + 2 , the group of electrons with three of the quantum
1

numbers same are

(a) AB, XYZ, B & Any one from X, Y, Z
(b) AB
(c) XYZ, AZ
(d) AB, XYZ
18. If n l = 6, than total possible number of subshell would be:
(a) 3
(b) 4
(c) 2

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(d) 5

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Chemistry By Arun Kumar Saini

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