Atomic Structure (Theory) 1

ATOMIC STRUCTURE
1. INTRODUCTION :
Structure of Atom

Rutherford's Model Bohr's Model Wave mechanical model

Dalton’s concept of the indivisibility of the atom was completely discredited by a series of experimental
evidences obtained by scientists. A number of new phenomenone were brought to light and man’s idea
about the natural world underwent a revolutionary change. The discovery of electricity and spectral
phenomena opened the door for radical changes in approaches to experimentation. It was concluded
that atoms are made of three particles : electrons, protons and neutrons. These particles are called the
fundamental particles of matter.

2. CATHODE RAYS (DISCOVERY OF ELECTRON)

In 1859 Julius Plucker started the study of conduction of electricity through gases at low pressure
(10–4atm) in a discharge tube When a high voltage of the order of 10,000 volts or more was impressed
across the electrodes, some sort of invisible rays moved from the negative electrode to the positive
electrode these rays are called as cathode rays.

2.1. Properties of Cathode Rays :

(i) Path of travelling is straight from the cathode with a very high velocity as it produces shadow of an
object placed in its path
(ii) Cathode rays produce mechanical effects. If small paddle wheel is placed between the electrodes,
it rotates. This indicates that the cathode rays consist of material part.
(iii) When electric and magnetic fields are applied to the cathode rays in the discharge tube, the rays
are deflected thus establishing that they consist of charged particles. The direction of deflection
showed that cathode rays consist of negatively charged particles called electrons.
(iv) They produce a green glow when strike the glass wall beyond the anode. Light is emitted when
they strike the zinc sulphide screen.
(v) Cathode rays penetrate through thin sheets of aluminium and metals.
(vi) They affect the photographic plates
(vii) The ratio of charge(e) to mass(m) i.e. charge/mass is same for all cathode rays irrespective of the
gas used in the tube. e/m = 1.76 × 1011 Ckg–1
Thus, it can be concluded that electrons are basic constituent of all the atoms.
Atomic Structure (Theory) 2

3. ANODE RAYS (DISCOVERY OF PROTON) :

Goldstein (1886) repeated the experiment with a discharge tube filled with a perforated cathode and
found that new type of rays came out through the hole in the cathode.

When this experiment is conducted, a faint red glow is observed on the wall behind the cathode. Since
these rays originate from the anode, they are called anode rays.
3.1. Properties of Anode Rays :
 Anode rays travel along straight paths and hence they cast shadows of object placed in their
path.
 They rotate a light paddle wheel placed in their path. This shows that anode rays are made
up of material particles.
 They are deflected towards the negative plate of an electric field. This shows that these rays
are positively charged.
 For different gases used in the discharge tube, the charge to mass ratio (e/m) of the positive
particles constituting the positive rays is different. When hydrogen gas is taken in the discharge
tube, the e/m value obtained for the positive rays is found to be maximum. Since the value of
charge (e) on the positive particle obtained from different gases is the same, the value of m must
be minimum for the positive particles obtained from hydrogen gas. Thus, the positive particle
obtained from hydrogen gas is the lightest among all the positive particles obtained from different
gases. This particle is called the proton.

4. DISCOVERY OF NEUTRON :
Later, a need was felt for the presence of electrically neutral particles as one of the constituent of atom.
These particles were discovered by James Chadwick in 1932 by bombarding a thin sheet of Beryllium
with α-particles, when electrically neutral particles having a mass slightly greater than that of the
protons were emitted. He named these particles as neutrons.
4 Be + 2 He → C+
9 4 12 1
6 0 n

5. ATOMIC MODELS :
5.1. Thomson’s Model of the Atom :
An atom is electrically neutral. It contains positive charges as well as negative charges (due to the
presence of electrons). Hence, J J Thomson assumed that an atom is a uniform sphere of positive
charges with electrons embedded in it. The magnitude of total positive charge on sphere is equal to
total negative charge of embedded electrons.
Atomic Structure (Theory) 3

5.2. Rutherford’s Experiment :

 Most of the α-particles passed straight through the gold foil without suffering any deflection from
their original path.

 A few of them were deflected through small angles, while a very few were deflected to a large
extent.

 A very small percentage (1 in 100000) was deflected through angles ranging from 90° to 180°.

Rutherford’s nuclear concept of the atom.

 The atom of an element consists of a small positively charged ‘nucleus’ which is situated at the
centre of the atom and which carries almost the entire mass of the atom.
 The electrons are distributed in the empty space of the atom around the nucleus in different
concentric circular paths, called orbits.
 The number of electrons in orbits is equal to the number of positive charges (protons) in the
nucleus. Hence, the atom is electrically neutral.
 The volume of the nucleus is negligibly small as compared to the volume of the atom.
 Most of the space in the atom is empty.

6. NUCLEUS :
Electrons, protons & neutrons are the fundamental particles present in all atoms,(Except hydrogen)

Particles Symbol Mass Charge Discoverer

Electron –1e
0 or β 9.1096 x 10-31 kg – 1.602 x l0–19 J.J. Thompson
Coulombs Stoney Lorentz 1887
0.000548 amu – 4.803 × 10–10 esu

1
1H
Proton 1.6726 x 10–27 kg + 1.602 x 10–19 Goldstein
Coulombs Rutherford1907
1.00757 amu + 4.803 x 10–10 esu
1
0n
Neutron 1.6749 x 10–27 kg Neutral James Chadwick
1.00893 amu 0 1932
1 amu ≈ 1.66 × 10–27 kg
Atomic Structure (Theory) 4

Uncommon Fundamental Particles :– Other less important fundamental particles of atom are
0
positrons, neutrinos and mesons.Positron (Positive electron, 1e ) :– It is the positive counterpart of
electron, discovered by Anderson in 1932. It is very unstable and combines with electron producing γ–
0 +
rays (energy radiations). Positron is symbolised as 1e or e

A. Neutrino :– These are particles of small ( ≅ 0) mass and zero charge. These were postulated
by Paulling in 1934.
B. Antineutrino :– These are particles of small ( ≅ 0) mass and zero charge. These were
postulated by Fermi in 1934. "Identical to neutrino but opposite spin"
C. Mesons :– (postulated by Yukawa in 1935) Mesons may be either positively or negatively
charged or neutral. Their mass is intermediate between that of electron and proton.
MESONS CHARGE MASS
µ +/– 286 me

π +/–/0 270 me

k +/–/0 970 me

D. Anti proton :– Discovered by Segre (1955) its mass equal to proton and charge equal to
electron.
E. Anti neutron :– Discovered by Cork (1956) its mass equal to neutron and charge equal to
zero."Identical to neutron but opposite spin"

7. ATOMIC NUMBER AND MASS NUMBER :

 Atomic number of an element
= Total number of protons present in the nucleus
= Total number of electrons present in the atom
• Atomic number is also known as proton number because the charge on the nucleus depends
upon the number of protons.
• Since the electrons have negligible mass, the entire mass of the atom is mainly due to protons
and neutrons only. Since these particles are present in the nucleus, therefore they are
collectively called nucleons.
• As each of these particles has one unit mass on the atomic mass scale, therefore the sum of
the number of protons and neutrons will be nearly equal to the mass of the atom.
 Mass number of an element = No. of protons + No. of neutrons.
• The mass number of an element is nearly equal to the atomic mass of that element. However,
the main difference between the two is that mass number is always a whole number whereas
atomic mass is usually not a whole number.
• The atomic number (Z) and mass number (A) of an element ‘X’ are usually represented
alongwith the symbol of the element as

23 35
e.g. 11 Na, 17 Cl and so on.
 Atomic Structure (Theory) 5

7.1. Important Definations :

7.1.1 Isotopes :
(i) First proposed by soddy.
(ii) The isotopes have same atomic number but different atomic weight.
(iii) They have same chemical properties because they have same atomic number.
(iv) They have different physical properties because they have different atomic masses.
16 17 18 12 13 14 14 15
eg. 8O , 8O , 8O ; 6C , 6C , 6C ; 7N , 7N
1 2 3
eg. 1H 1H 1H

Protium deuterium Tritium

Z=1 1 1
A=1 2 3

7.1.2 Isobar :
The different atoms which have same atomic masses but different atomic number are called as Isobar.
40 40 40
eg. 18Ar 19K 20Ca

Atomic mass 40 40 40
Atomic number 18 19 20

7.1.3 Isotone :
Elements which contain same no. of neutron are called as Isotones.
30 31 32
eg. 14Si 15P 16S

Number of neutrons 16 16 16

7.1.4 Isoelectronic :
Ion or atom or molecule or species which have the same number of electrons are called as
isoelectronic species.
– + +2
eg. 17Cl 18Ar 19K 20Ca

No. of electron 18 18 18 18

Solved example
Example 1. The triad of nuclei that is isotonic -
14 15 17 12 14 19 14 14 17 14 14 19
(1) 6C , 7N , 9F (2) 6C , 7N , 9F (3) 6C , 7N , 9F (4) 6C , 7N , 9F Ans. (1)

Example 2. Complete the following table :

Particle Mass No. Atomic No. Protons Neutrons Electrons

Nitrogen atom – – – 7 7
Calcium ion – 20 – 20 –
Oxygen atom 16 8 – – –
Bromide ion – – – 45 36
Atomic Structure (Theory) 6

Sol. For nitrogen atom.

No. of electron = 7 (given)
No. of neutrons = 7 (given)
∴ No. of protons = Z = 7 (∴ atom is electrically neutral)
tomic number = Z = 7 Mass No. (A) = No. of protons + No. of neutrons
= 7 + 7 = 14
For calcium ion.
No. of neutrons = 20 (Given)
Atomic No. (Z) = 20 (Given)
∴ No. of protons = Z = 20 ;
No. of electrons in calcium atom = Z = 20
But in the formation of calcium ion, two electrons are lost from the extranuclear part according to the
equation Ca → Ca2+ + 2e– but the composition of the nucleus remains unchanged.
∴ No. of electrons in calcium ion
= 20 – 2 = 18
Mass number (A) = No. of protons + No. of neutrons
= 20 + 20 = 40.
For oxygen atom.
Mass number (A) = No. of protons + No. of neutrons
= 16 (Given
Atomic No. (Z) = 8 (Given)
No. of protons = Z = 8,
No. of electrons = Z = 8
No. of neutrons = A – Z = 16 – 8 = 8

8. ELECTROMAGNETIC RADIATIONS :
The oscillating electrical/magnetic field are electromagnetic radiations. Experimentally, the direction of oscillations
of electrical and magnetic field are prependicular to each other.

→ →
E = Electric field, B = Magnetic field

Direction of wave propogation.

Atomic Structure (Theory) 7

8.1. Wave nature of light :

 Wavelength of a wave is defined as the distance between any two consecutive crests or troughs. It
is represented by λ (lambda) and is expressed in Å or m or cm or nm (nanometer) or pm
(picometer).
1 Å = 10– 8 cm = 10–10 m
1 nm = 10– 9 m, 1 pm = 10–12 m

 Frequency of a wave is defined as the number of waves passing through a point in one second. It
is represented by ν (nu) and is expressed in Hertz (Hz) or cycles/sec or simply sec–1 or s–1.
1 Hz = 1 cycle/sec
 Velocity of a wave is defined as the linear distance travelled by the wave in one second. It is
represented by v and is expressed in cm/sec or m/sec (ms–1).
 Amplitude of a wave is the height of the crest or the depth of the trough. It is represented by ‘a’
and is expressed in the units of length.
 Wave number is defined as the number of waves present in 1 cm length. Evidently, it will be equal
to the reciprocal of the wavelength. It is represented by ν (read as nu bar).
1
ν=
λ
If λ is expressed in cm, v will have the units cm–1.
Relationship between velocity, wavelength and frequency of a wave. As frequency is the number
of waves passing through a point per second and λ is the length of each wave, hence their product will
give the velocity of the wave. Thus
c=ν×λ

Order of wavelength in electromagnetic spectrum

Cosmic rays < γ – rays < X-rays < Ultraviolet rays < Visible < Infrared < Micro waves < Radio waves.

9. PARTICLE NATURE OF LIGHT (PLANK’S QUANTUM THEORY)

The smallest quantity of energy that can be emitted or absorbed in the form of electromagnetic radiation is called
as quantum of light.
According to Planck, the light energy coming out from any source is always an integral multiple of a smallest
energy value called quantum of light.
Let quantum of light be = E0(J), then total energy coming out is = nE0 (n = Integer)
Quantum of light = Photon ( Packet or bundle of energy)
Energy of one photon is given by
E0 = hν (ν- Frequency of light)
h = 6.625 x 10–34 J-Sec (h - Planck const.)
hc
E0 = (c - speed of light)
λ
(λ - wavelength)
10−34 × 108
Order of magnitude of Eo = = 10–16 J
10−10
Some of the experimental phenomenon such as diffraction and interference can be explained by the
wave nature of the electromagnetic radiation. However, following are some of the observations which
could not be explained
(i) the nature of emission of radiation from hot bodies (black - body radiation)
(ii) ejection of electrons from metal surface when radiation strikes it (photoelectric effect)
Atomic Structure (Theory) 8

9.1. Photoelectric Effect :

When certain metals (for example Potassium, Rubidium, Caesium etc.) were exposed to a beam of light
electrons were ejected as shown in Fig.

The phenomenon is called Photoelectric effect. The results observed in this experiment were :
(i) The electrons are ejected from the metal surface as soon as the beam of light strikes the surface,
i.e., there is no time lag between the striking of light beam and the ejection of electrons from the
metal surface. This phenomenon is called SINGLE COLLISION event. The electron at the surface
collides with only one photon once.
(ii) The number of electrons ejected is proportional to the intensity or brightness of light.
(iii) For each metal, there is a characteristic minimum frequency, ν0 (also known as threshold
frequency) below which photoelectric effect is not observed. At a frequency ν > ν0, the ejected
electrons come out with certain kinetic energy. The kinetic energies of these electrons increase with
the increase of frequency of the light used.
When a photon of sufficient energy strikes an electron in the atom of the metal, it transfers its
energy instantaneously to the electron during the collision and the electron is ejected without any
time lag or delay. Greater the energy possessed by the photon, greater will be transfer of energy to
the electron and greater the kinetic energy of the ejected electron. In other words, kinetic energy of
the ejected electron is proportional to the frequency of the electromagnetic radiation. Since the
striking photon has energy equal to hν and the minimum energy required to eject the electron is hν0
(is also called work function, W0) then the difference in energy (hν – hν0) is transferred as the kinetic
energy of the photoelectron. Following the conservation of energy principle, the kinetic energy of
the ejected electron is given by the equation
1
hν = hν0 + m ν2
2 e
where me is the mass of the electron and v is the velocity associated with the ejected electron.
Solved example
Example 1. The threshold frequency ν0 for a metal is 6 × 1014 s–1. Calculate the kinetic energy of an electron
emitted when radiation of frequency ν = 1.1 × 1015 s–1 hits the metal.
1
Sol. K.E. = meV2 = h (ν – ν0)
2
∴ K.E. = (6.626 × 10–34) (1.1 × 1015 – 6 × 1014)
∴ K.E. = (6.626 × 10–34) (5 × 1014)
= 3.313 × 10–19 J
Example 2. When electromagnetic radiation of wavelength 310 nm fall on the surface of Sodium, electrons
are emitted with K.E. = 1.5 eV. Determine the work function (W0) of Sodium.
Atomic Structure (Theory) 9

12400
Sol. hν = = 4 eV
3100
1
m V2 = 1.5 eV
2 e
1
∴ hν0 = W 0 = hν – m V2 = 4 – 1.5 = 2.5 eV
2 e

Some Important formulae :

1. A = Z + N (Number of neutrons)
2. dynamic mass of particle m = m0 / [1 – (v/c)2]1/2
3. Radius of nucleus R = R0 (A)1/3, R0 = 1.2 x 10–15 m
4. c = υλ
5. wave number υ = 1 / λ
6. E = h υ = hc / λ = hc υ
q q 1
7. F=K 1 2 2 ;K= = 9.0 × 109 Nm2/C2
r 4πε0
8. ∆E = hυ = E2 – E1

Solved example
Example 1. Calculate number of photon coming out per sec. from the bulb of 100 watt. If it is 50% efficient
and wavelength coming out is 600 nm.
Sol. Energy = 100J
hc 6.625 × 10 −34 × 3 × 108 6.625
Energy of one photon = = −9
= × 10–19
λ 600 × 10 2
100
no. of photon = × 1019 = 15.09 × 1019
6.625
Example 2. Certain sun glasses having small of AgCl incorporated in the lenses, on exposer to light of
appropriate wavelength turns to gray colour to reduce the glare following the reactions:
AgCl hv → Ag(Gray) + Cl
If the heat of reaction for the decomposition of AgCl is 248 kJ mol–1, what maximum
wavelength is needed to induce the desired process?
Sol. Energy needed to change = 248 × 103 J/mol
If photon is used for this purpose, then according to Einstein law one molecule absorbs one
hc
photon. Therefore, ∴ NA . = 248 × 103
λ
6.625 × 10 −34 × 3.0 × 108 × 6.023 × 1023
λ= = 4.83 × 10–7 m
248 × 103

Example 3. Sodium street lamp gives off a characteristic yellow light of wavelength 588 nm. Calculate the
energy mole (in kJ/mol) of these photons.
Sol. λ = 588 nm = 588 × 10–9 m
c = 3 × 108 ms–1
c
E = N0hν = N0 h
λ
6.02 × 1023 × 6.63 × 10 −34 × 3 × 108
=
588 × 10−9
= 2.04 × 10 J mol–1 = 2.04 × 102 kJ mol–1
5
Atomic Structure (Theory) 10

Example 4. Find the wavelength of 100 g particle moving with velocity 100 ms–1
h 6.626 × 10 −34 kg m2s−1
Sol. λ= =
mv 0.1 kg ×100 ms−1
= 6.626 × 10–35 m.

Example 5. A bulb emits light of wavelength 4500 Å. The bulb is rated as 150 watt and 8% of the energy is
emitted as light. How many photons are emitted by the bulb per second.
Sol. A 150 watt bulb emits 150 J of energy per second.
The energy emitted by the bulb as light
8
= 150 × = 12 J
100
suppose the bulb emits n photons per second
nhν
E = nhν =
λ
E×λ 12J × 4500 × 10 −10 m
n= = = 2.715 × 1019
c × h 3 × 108 ms−1 × 6.63 × 10 −34 Js

9.2. Black Body Radiation :

When solids are heated they emit radiation over a wide range of wavelengths.
The ideal body, which emits and absorbs all frequencies, is called a black body and the radiation
emitted by such a body is called black body radiation. The exact frequency distribution of the emitted
radiation (i.e., intensity versus frequency curve of the radiation) from a black body depends only on its
temperature.

The above experimental results cannot be explained satisfactorily on the basis of the wave theory of
light. Planck suggested that atoms and molecules could emit (or absorb) energy only in discrete
quantities and not in a continuous manner.

10. BOHR’S ATOMIC MODEL :

It is based on quantum theory of light.
It is applicable only for Hydrogen like species, for example He+, Li2+, Be3+, etc.

10.1. Assumptions of Bohr’s model :

 There are certain orbits around the nucleus such that if electron will be revolving in these orbit,
then it does not emit any electromagnetic radiation. These are called stationary orbit for the e–.
The neccessary centripetal force is produced by attraction forces of nucleus.

mv 2 Ke2 Z
=
r r2
h
 Angular momentum of the electron in these stationary orbit is always an integral multiple of
2π
 Atomic Structure (Theory) 11

nh
mvr = 2π

 Electron can make jump from one stationary orbit to another stationary orbit by absorbing or
emitting a photon of energy equal to difference in the energies of the stationary orbit i.e. energy
change does not take place in continuous manner.

hc
=∆E ∆E – difference in the energy of orbit
∆

∆E
ν= This is Bohr’s frequency rule.
h

10.2. Mathematical forms of Bohr’s Postulates :

10.2.1 Calculation of the radius of the Bohr’s orbit : Suppose that an electron having mass ‘m’ and charge
‘e’ revolving around the nucleus of charge ‘Ze’ (Z is atomic number & e = charge) with a
tangential/linear velocity of ‘v’. Further consider that ‘r’ is the radius of the orbit in which electron is
revolving.
According to Coulomb’s law, the electrostatic force of attraction (F) between the moving electron and
nucleus is :
KZe2 1
F= where : K = constant = = 9 x 109 Nm2/C2
r2 4πε0
mv 2
and the centrifugal force F =
r
For the stable orbit of an electron both the forces are balanced.
mv 2 KZe2
i.e =
r r2
KZe2 V
then v2 = ......... (i)
mr
e
From the postulate of Bohr,
r
nh nh
mvr = ⇒ v=
2π 2πmr +Ze
n2h2
On squaring v2 = ........ (ii)
4π2m2r 2
From equation (i) and (ii)
KZe2 n2h2
=
mr 4π2m2r 2
On solving, we will get
n2h2
r=
4π2mKZe2
On putting the value of e , h , m, the radius of nth Bohr orbit is given by :
n2
rn = 0.529 x Å
Z

Solved example
Example 1. Calculate radius ratio for 2nd orbit of He+ ion & 3rd orbit of Be+++ ion.
Atomic Structure (Theory) 12

 22 
Sol. r1 (radius of 2nd orbit of He+ ion) = 0.529   Å
 2 
 
 32 
r2 (radius of 3rd orbit of Be+++ ion) = 0.529   Å
 4 
 
r1 0.529 × 22 / 2 8
Therefore = =
r2 0.529 × 32 / 4 9

10.2.2 Calculation of velocity of an electron in Bohr’s orbit :

Angular momentum of the revolving electron in nth orbit is given by
nh
mvr =
2π
nh
v= ......... (iii)
2πmr
put the value of ‘r’ in the equation (iii)
nh × 4π2mZe2K
then, v=
2πmn2h2
2πZe2K
v=
nh
on putting the values of π, e-, h and K
Z 1
velocity of electron in nth orbit vn = 2.18 x 106 x m/sec ; v ∝Z ; v∝
n n
2πr
T, Time period of revolution of an electron in its orbit =
v
v
f, Frequency of revolution of an electron in its orbit =
2πr

10.2.3 Calculation of energy of an electron :

The total energy of an electron revolving in a particular orbit is
T.E. = K.E. + P.E.
where : P.E. = Potential energy , K.E. = Kinetic energy , T.E. = Total energy
1
The K.E. of an electron = mv2
2
KZe2
and the P.E. of an electron = –
r
2
1 KZe
Hence, T.E. = mv2 –
2 r
2
mv KZe2 KZe2
we know that, = 2 or mv2 =
r r r
substituting the value of mv2 in the above equation :
KZe2 KZe2 KZe2
T.E. = – =–
2r r 2r
KZe2
So, T.E. = –
2r
substituting the value of ‘r’ in the equation of T.E.
KZe2 4π2 Ze2m 2 π 2 Z 2 e 4m K 2
Then T.E. = – x = –
2 n2h2 n2h2
th
Thus, the total energy of an electron in n orbit is given by
Atomic Structure (Theory) 13

2π2 me4 k 2  z2 
T.E. = En = –  2  ... (iv)
h2 n 
Putting the value of m,e,h and π we get the expression of total energy
Z2
En = – 13.6 2 eV / atom n ↑ T.E. ↑ ; Z ↑ T.E. ↓
n
Z2
En = – 2.18 × 10–18 J/atom
n2
1
T.E. = P.E.
2
T.E. = – K.E.
Note : - The P.E. at the infinite = 0
The K.E. at the infinite = 0

10.2.4 Conclusion from equation of energy :

a. The negative sign of energy indicates that there is attraction between the negatively charged
electron and positively charged nucleus.
b. All the quantities on R.H.S. in the energy equation [Eq. iv] are constant for an element having
atomic number Z except ‘n’ which is an integer such as 1,2,3, etc . i.e. the energy of an electron
is constant as long as the value of ‘n’ is kept constant.
c. The energy of an electron is inversely proportional to the square of ‘n’ with negative sign.
d. Negative charge of the energy of e– in the atom indictes that the energy of e– in the atom is at
lower energy than the energy of a free e– at rest (which is taken to be zero).

Solved example
Example 1. What are the frequency and wavelength of a photon emitted during a transition from n = 5 state
to the n = 2 state in the hydrogen atom ?
Sol. Since ni = 5 and nf = 2, this transition gives rise to a spectral line in the visible region of the
Balmer series.
 1 1
∆E = 2.18 × 10–18 J  2 – 2  = – 4.58 × 10–19 J
5 2 
It is an emission energy
The frequency of the photon (taking energy in terms of magnitude) is given by
∆E 4.58 × 10 –19 J
ν= = = 6.91 × 1014 Hz
h 6.626 × 10 –34 Js
c 3.0 × 108 ms –1
λ= = = 434 nm
ν 6.91× 1014 Hz
Example 2. If the energy of an electron in 3rd Bohr orbit is –E, what is the energy of the electron of the
electron in (i) 1st Bohr orbit (ii) 2nd Bohr orbit ?
Sol. According to Bohr’s model,
E
En = 21
n
E
E3 = 12 = –E (given)
(3)
∴ E1 = – 9E
E1 9E
E2 = 2
=– = 2.25 E
(2) 4

Example 3. The ratio of (E2 – E1) to (E4 – E3) for He+ ion is approximately equal to (where En is the energy of
nth orbit)
(1) 10 (2) 15 (3) 17 (4) 12
Atomic Structure (Theory) 14

 1 1 
13.6 (2)2  2 − 
 (1) (2)2 
Sol. = 15 Ans. (2)
 1 1 
13.6 (2)  2 −
2

 (3) (4)2 

10.2.5 Failures / limitations of Bohr’s theory:

a. He could not explain the line spectra of atoms containing more than one electron.
b. He also could not explain the presence of doublet i.e. 2 closely spaced lines.
c. He was unable to explain the splitting of spectral lines in magnetic field (Zeeman effect) and in
electric field (Stark effect)
d. No conclusion was given for the principle of quantisation of angular momentum.
e. He was unable to explain the de-Broglie’s concept of dual nature of matter.
f. He could not explain Heisenberg’s uncertainty principle.
g. Could’t explain the ability of atoms to form molecules by chemical bonds.

11. ENERGY LEVEL DIAGRAM :

(i) Orbit of lowest energy is placed at the bottom, and all other orbits are placed above this.
(ii) The gap between two orbits is proportional to the energy difference of the orbits.

0 eV n= ∞
-0.85 eV n=4
-1.51eV n=3
-3.4eV n=2

12.1eV
10.2eV
-13.6eV n=1
Energy level diagram of H-atom

12. DEFINITION VALID FOR SINGLE ELECTRON SYSTEM :

12.1. Ground state :
Lowest energy state of any atom or ion is called ground state of the atom. For it n = 1.
Ground state energy of H–atom = – 13.6 ev
Ground state energy of He+ Ιon = – 54.4 ev

12.2. Excited State :

States of atom other than the ground state are called excited states :
n=2 first excited state
n=3 second excited state
n=4 third excited state
n=n+1 nth excited state

12.3. Ionisation energy (ΙE) :

Minimum energy required to move an electron from ground state to
n = ∞ is called ionisation energy of the atom or ion.
Ιonisation energy of H–atom = 13.6 ev
Ιonisation energy of He+ ion = 54.4 ev
Ιonisation energy of Li+2 ion = 122.4 ev

12.4. Ionisation Potential (Ι.P.) :

Potential difference through which a free electron must be accelerated from rest, such that its kinetic
energy becomes equal to ionisation energy of the atom is called ionisation potential of the atom.
Atomic Structure (Theory) 15

Ι.P. of H atom = 13.6 V, Ι.P. of He+ Ιon= 54.4 V

12.5. Excitation Energy :

Energy required to move an electron from ground state of the atom to any other state of the atom is
called excitation energy of that state.
Excitation energy of 2nd state = excitation energy of 1st excited state = 1st excitation energy = 10.2 ev.

12.6. Excitation Potential :

Potential difference through which an electron must be accelerated from rest to so that its kinetic
energy become equal to excitation energy of any state is called excitation potential of that state.
Excitation potential of third state = excitation potential of second exicited state = second excitation
potential = 12.09 V.

12.7. Binding Energy ‘or’ Seperation Energy :

Energy required to move an electron from any state to n = ∞ is called binding energy of that state.
Binding energy of ground state = Ι.E. of atom or Ιon.

Solved example
Example 1. A single electron system has ionization energy 11180 kJ mol–1 . Find the number of protons in
the nucleus of the system.
Z2
Sol. Ι.E. = 2 × 21.69 × 10–19 J
n
11180 × 103 Z2
= × 21.69 × 10–19 Ans. Z = 3
6.023 × 1023 12
Example 2. The ionization energy of He+ is 19.6 × 10–18 J/atom. Calculate the energy of the first stationary
state of Li2+.
Sol. For H–like species
I.E. = I.E.(H) × Z2
∴ I.E.(He+ ) = Z2 × I.E.(H)
19.6 × 10–18 J = (2)2 × I.E.(H)
19.6 × 10−18
I.E.(H) = J
4
I.E.(Li+2 ) = Z2 × I.E.(H)

(3)2 × 19.6 × 19−18

=
4
= 4.41 × 10–17 J/atom
I.E.(Li+2 ) = E ∞ – E1
4.41 × 10–17 = 0 – E1
E1 = – 4.41 × 10–17 J/atom.
Example 3. If the binding energy of 2nd excited state of a hydrogen like sample is 24 eV approximately, then
the ionisation energy of the sample is approximately
(1) 54.4 eV (2) 24 eV (3) 122.4 eV (4) 216 eV
13.6(Z)2
Sol. = 24
(3)2
I.E. = 13.6(Z)2 = (24 × 9) = 216 ev Ans. (4)
Example 4. The ionisation energy of H atom is 21.79 × 10–19 J . Then the value of binding energy of second
excited state of Li2+ ion
(1) 32 × 21.7 × 10–19 J (2) 21.79 × 10–19 J
Atomic Structure (Theory) 16

1 1
(3) × 21.79 × 10–19 J (4) × 21.79 × 10–19 J
3 32
21.79 × 10 −19 (3)2
Sol. B.E. = = 21.79 × 10–19 J Ans. (2)
(3)2

13. HYDROGEN SPECTRUM :

13.1. Study of Emission and Absorption Spectra :

An instrument used to separate the radiation of different wavelengths (or frequencies) is called
spectroscope or a spectrograph. Photograph (or the pattern) of the emergent radiation recorded on the
film is called a spectrogram or simply a spectrum of the given radiation.
The branch or science dealing with the study of spectra is called spectroscopy.
Spectrum

Based on Based on
Nature origin

Continuous Discrete Absorption Emission

spectrum spectrum
Band Line
Spectrum Spectrum

13.1.1 Emission spectra :

When the radiation emitted from some source e.g. from the sun or by passing electric discharge
through a gas at low pressure or by heating some substance to high temperature etc, is passed directly
through the prism and then received on the photographic plate, the spectrum obtained is called
‘Emission spectrum’.
Depending upon the source of radiation, the emission spectra are mainly of two type :

a. Continuous spectra :
When white light from any source such as sun, a bulb or any hot glowing body is analysed by passing
through a prism it is observed that it splits up into seven different wide band of colours from violet to
red. These colours are so continuous that each of them merges into the next. Hence the spectrum is
called continuous spectrum.

b. Discrete spectra : It is of two type

(i) Band spectrum
Band spectrum contains colourful continuous bands sepearted by some dark space.
Generally, molecular spectrum are band spectrum.
(ii) Line Spectrum :
This is the ordered arrangement of lines of particular wavelength seperated by dark space eg.
hydrogen spectrum.
Line spectrum can be obtained from atoms.
Atomic Structure (Theory) 17

13.1.2 Absorption spectra :

When white light from any source is first passed through the solution or vapours of a chemical
substance and then analysed by the spectroscope, it is observed that some dark lines are obtained in
the continuous spectrum. These dark lines are supposed to result from the fact that when white light
(containing radiations of many wavelengths) is passed through the chemical substance, radiations of
certain wavelengths are absorbed, depending upon the nature of the element.

13.2. Emission spectrum of Hydrogen :

When hydrogen gas at low pressure is taken in the discharge tube and the light emitted on passing
electric discharge is examined with a spectroscope, the spectrum obtained is called the emission
spectrum of hydrogen.
Line Spectrum of Hydrogen :
Line spectrum of hydrogen is observed due to excitation or de-excitation of electron from one stationary
orbit to another stationary orbit
Let electron make transition from n2 to n1 (n2 > n1) in a H-like sample
2
– 13.6 Z
eV n2
n22
– 13.6 Z2 n1
2 eV
n1

photon

−13.6Z2  −13.6Z2   1 1 
Energy of emitted photon = (∆E)n2 → n1 = –   = 13.6Z2  2 − 2 
n22 n12 n 
   1 n2 
Wavelength of emitted photon
hc
λ=
( ∆E)n2 →n1

hc
λ=
 1 1 
13.6Z2  2 − 2 
n 
 1 n2 

1 (13.6)z2  1 1 
=  − 
λ hc  n12 n22 

Atomic Structure (Theory) 18

1  1 1 
Wave number, = ν = RZ2  2 − 2 
λ n 
 1 n2 
13.6eV
R = Rydberg constant = 1.09678 × 107m–1 ; R  1.1 × 107 m–1 ; R = ; R ch = 13.6 eV
hc

Solved example
Example 1. Calculate the wavelength of a photon emitted when an electron in H- atom maker a transition
from n = 2 to n = 1
1  1 1 
Sol. = RZ2  2 − 2
λ  n1 n2 

1 1 1
∴ = R(1)2  2 − 2 
λ 1 2 
1 3R 4
∴ = or λ =
λ 4 3R

13.3. Spectra lines of Hydrogen Atom :

13.3.1 lyman series

 It is first spectral series of H.
 It was found to be in ultraviolet region by Lyman in 1898.
 For it value of n1 = 1 and n2 = 2,3,4 where ‘n1’ is ground state and ‘n2’ is called excited state of
electron present in a H - atom.
1 1 1
 = RH  2 − 2  where n2 > 1 always.
λ  1 n2 
n12 1
 The wavelength of marginal line (i.e. n2 = ∞) = for all series. So for lyman series λ = .
RH RH
 Ιst line of lyman series ⇒ 2 → 1
ΙΙnd line of lyman series = 3 → 1
Last line of lyman series = ∞ → 1
Atomic Structure (Theory) 19

[10.2 eV ≤ (∆E) lyman ≤ 13.6 eV]

12400 12400
≤ λ lyman ≤ Aº
13.6 10.2
12400
 Longest line : longest wavelength line λ longest or λ max. =
( ∆E)min
12400
 Shortest line : shortest wavelength line λ shortest or λ min =
( ∆E)max
 First line of any spectral series is the longest (λ max) line.
 Last line of any spectral series is the shortest (λ min) line.
Series limit :
Ιt is the last line of any spectral series.
1 1 1 
Wave no of Ιst line of Lyman series = = ν = R × 12  2 − 2 
λ 1 2 
 4 − 1
ν = R × 12  
 4 
R×3 3 R
ν = =
4 4
 4 
∴ λ = 3R 
 
Wave no of last line of Lyman series
1 1 
ν = R × 12  2 − 2 
1 ∞ 
ν =R
For Lyman series,
12400 12400
λ longest = , λshortest =
( ∆E)2−1 ( ∆E )∞ → 1

13.3.2 balmer series :

 It is the second series of H-spectrum.
 It was found to be in visible region by Balmer in 1892.
 For it value of n1 = 2 and n2 = 3,4,5,.............
n12 22 4
 The wavelength of marginal line of Balmer series = = =
RH RH RH
1  1 1 
 = RH  2 − 2
2  where n2 > 2 always.
λ  n2 
1.9 ≤ (∆E)balmer ≤ 3.4 eV.
All the lines of balmer series in H spectrum are not in the visible range. Ιnfact only Ιst 4
lines belongs to visible range.
12400 12400
Aº ≤ λ balmer ≤ Å
3.4 1.9
3648 Å ≤ λ balmer ≤ 6536 Å
Lines of balmer series (for H atom) lies in the visible range.
Ist line of balmer series = 3 → 2
last line of balmer series = ∞ → 2
 1 1  5R
( ν ) 1st line = R ×1  2 − 2  =
2 3  36
 Atomic Structure (Theory) 20

 1 1  R
( ν ) last line = R  2 − 2  =
2 ∞  4

13.3.3 Paschen series :

a. It is the third series of H - spectrum.
b. It was found to be in infrared region by Paschen.
c. For it value of n1 = 3 and n2 = 4,5,6 ........
n12 32 9
d. The wavelength of marginal line of Paschen series = = = .
RH RH RH
1  1 1
e. = RH  2 − 2  where n2 > 3 always.
λ  3 n2 

13.3.4 Brackett series :

a. It is fourth series of H - spectrum.
b. It was found to be in infrared region by Brackett.
c. For it value of n1 = 4 and n2 = 5,6,7 ..............
n12 42 16
d. The wavelength of marginal line of brackett series = = =
RH RH RH
1  1 1
e. = RH  2 − 2  where n2 > 4 always.
λ  4 n2 

13.3.5 Pfund series :

a. It is fifth series of H- spectrum.
b. It was found to be in infrared region by Pfund.
c. For it value of n1 = 5 and n2 = 6,7,8 ............... where n1 is ground state and n2 is excited state.
n12 52 25
d. The wavelength of marginal line of Pfund series = = =
RH RH RH
1  1 1
e. =  2 − 2  RH where n2 > 5 always.
λ  5 n2 

13.3.6 Humphry series :

a. It is the sixth series of H-spectrum.
b. It was found to be in infrared region by Humphry.
c. For it value of n1 = 6 and n2 = 7 , 8 , 9 ...................
n12 62 36
d. The wavelength of marginal line of Humphry series = = =
RH RH RH
1  1 1
e. = RH  2 − 2  where n2 > 6.
λ  6 n2 

Solved example
Example 1. Electron in hydrogen atom is in fourth stationary state. What is the maximum number of
spectral lines that can be observed as it de-excites.
n ( n − 1)
Sol. Maximum number of spectral lines from nth state =
2
n=4
n ( n − 1) 4 ( 4 − 1)
= =6 Ans. 6
2 2
Example 2. Calculate wavelength for 2nd line of Balmer series of He+ ion
Atomic Structure (Theory) 21

1 1 1
Sol. = R(2)2  2 − 2 
λ  n1 n2 
n1 = 2 n2 = 4
1  1 1
= R(22 )  2 − 2 
λ 2 4 
1 3 R 4
= λ= Ans.
λ 4 3 R
Example 3. Calculate the wavelength and energy of radiation emitted for the electronic transition from
infinity to stationary state one of the hydrogen atom.
1 1 1
Sol. = 109678  2 − 2 
λ  n1 n2 
 1 1
= 109678  2 −  = 109678 cm–1
 (1) ∞
1
λ= cm = 9.1 × 10–6 cm
109678
= 9.1 × 10–8 m = 91 nm.
hc 6.63 × 10−34 J.s ×3 × 108 ms−1
E= =
λ 9.1× 10−8 m
= 2.186 × 10–18 J
Example 4. Calculate the wavelength of the radiation emitted, producing a line in the Lyman series when an
electron falls from fourth stationary state in hydrogen atom (RH = 1.1 × 107 m–1)
Sol. For Lyman series n1 = 1
1 1 1  1 1 
= RH  2 − 2  = 1.1 × 107 m–1  2 − 
λ  n1 n2   (1) (4)2 
15
= 1.1 × 107 ×
16
λ = 9.7 × 10–8 m = 97 nm
Example 5. Calculate the wave number for the shortest wavelength transition in the Balmer series of atomic
hydrogen.
Sol. The shortest wavelength transition corresponds to n2 = to n1 = 2 transition
1 1
v = 109678  2 − 2  cm–1
 n1 n2 
 1 1
= 109678  2 − 
 (2) ∞
109678
= = 27419.5 cm–1
4

Example 6. The energy of the electron in the second and third Bohr orbits of hydrogen atom is – 5.42 × 10–12 ergs
and – 2.41 × 10–12 ergs respectively. Calculate the wavelength of the emitted ratiation when
electron drops from third to second orbits.
Sol. ∆E = E3 – E2
= –2.41 × 10–12 – (–5.42 × 10–12) ergs
= – 2.41 × 10–12 + 5.42 × 10–12 ergs
= 3.01 × 10–12 ergs
Now h = 6.63 × 10–27 ergs s,
c = 3 × 1010 cm/s
Atomic Structure (Theory) 22

hc
∆E =
λ
hc 6.63 × 10−27 ergs.s ×3 × 1010 cms−1
λ= = = 6.6 × 10–5 cm = 6.6 × 103 Å
∆E 3.01× 10−12 ergs

Example 7. Calculate the energy emitted when electrons of 1.0 g atom of hydrogen undergo transition
giving the spectral line of lowest energy in the visible region of its atomic spectrum. (RH =
1.1 × 107 m–1)
1 1 1
Sol. = RH  2 − 2
λ  n1 n2 
 1 1 
= 1.1 × 107 m–1  2 − 2 
 (2) (3) 
5
= 1.1 × 107 × m–1
36
λ = 6.545 × 10–7 m.
hc
Energy emitted per atom, E =
λ
6.62 × 10−34 J.s ×3 × 108 × ms−1
=
6.545 × 10−7 m
= 3.03 × 10–19 J
1.0 g atom hydrogen contains 1 mole hydrogen atoms
Energy emitted by 1.0 g atom of hydrogen
NA × 3.03 × 10–19 J
= 6.02 × 1023 × 3.03 × 10–19 J
= 1.82 × 105 J

Example 8. The wave number of the first line in the Balmer series of hydrogen is 15200cm−1. What would
be the wavenumber of the first line in the Lyman series of the Be3+ ion?
(1) 2.4 x 105cm−1 (2) 24.3 x 105cm−1 (3) 6.08 x 105cm−1 (4) 1.313 x 106 cm−1
 1 1 
Sol. Given 15200 = R(1)2  2 − 2  ..... (1)
 (2) (3) 
 1 1 
Then ν = R(4)2  2 −  ..... (2)
 (1) (2)2 
from (1) and (2) equation
ν = 1.313 × 106 cm–1 Ans. (4)

Example 9. What would be the maximum number of emission lines for atomic hydrogen that you would
expect to see with the naked eye if the only electronic energy levels involved are those as
shown in the Figure?
Atomic Structure (Theory) 23

Hint : Balmer series lines lies in visible region.

(1) 4 (2) 6 (3) 5 (4) 15
Sol. Only four lines are present in visible region, 6 → 2, 5 → 2, 4 → 2 & 3 → 2.

13.4. No. of photons emitted by a sample of H atom :

If an electron is in any higher state n = n and makes a transition to ground state, then total no. of
n × (n − 1)
different photons emitted is equal to .
2
If an electron is in any higher state n = n2 and makes a transition to another excited state n = n1, then

∆n ( ∆n + 1)
total no. of different photons emitted is equal to , where ∆n = n2 – n1
2
Note : In case of single isolated atom if electron make transition from nth state to the ground state then
max. number of spectral lines observed = (n-1)

Solved example
Example 1. If electron make transition from 7th excited state to 2nd state in H atom sample find the max.
number of spectral lines observed.
Sol. ∆n = 8 – 2 = 6

 6 + 1 7
spectral lines = 6   = 6× 2 = 21
 2 

14. DUAL NATURE OF ELECTRON (DE-BROGLIE HYPOTHESIS):

a. Einstein had suggested that light can behave as a wave as well as like a particle i.e. it has dual
character.
b. In 1924, de-Broglie proposed that an electron behaves both as a material particle and as a
wave.
c. This proposed a new theory, the wave mechanical theory of matter. According to this theory,
the electrons protons and even atom when in motion possess wave properties.
d. According to de-Broglie, the wavelength associated with a particle of mass m, moving with
velocity v is given by the relation,
Atomic Structure (Theory) 24

h
λ=
mv
where h is Planck’s constant
e. This can be derived as follows according to Planck’s equation.
h.c
E = hν =
λ
Energy of photon on the basis of Einstein’s mass energy relationship
h
E = mc2 or λ=
mc
Equating both we get
h.c
= mc2
λ
h
or λ=
mc
Which is same as de - Broglie relation.
h
λ=
p

h h h
λ= λ= λ=
mv 2mKE 2mqV

• If an electron is accelerated through a potential difference of ‘V’ volt from rest then :
h
⇒ λ=
2me (eV)

 150 
⇒ λ=  V Å (on putting values of h, me and e)
 
12.3
λ= Å (V in volt)
V
h
• mvr = n ×
2π
h
λ=
mv
h nh
mv = putting this in mvr =
λ 2π
h nh  2πr 
∴ r ⇒ λ = = de Broglie wavelength
λ 2π  n 

Solved example
Example 1. What will be the wavelength of a ball of mass 0.1 kg moving with a velocity of 10 m s–1 ?
Sol. According to de Broglie equation
h (6.626 × 10 –34 Js)
λ= = = 6.626 × 10–34 m (J = kg m2 s–2).
mv (0.1 kg) (10 m s –1)

Example 2. A moving electron has 5 × 10–25 J of kinetic energy. What is the de-broglie wavelength ?
Sol. Mass of the electron m = 9.1 × 10–31 kg
Atomic Structure (Theory) 25

1
K.E. = mv2 = 5 × 10–25 J
2
h
λ=
2m × K.E.
6.626 × 10 −34
=
2 × 9.1× 10−31 × 5 × 10 −25
= 6.95 × 10–7 m.

Example 3. The de Brogile wavelength of an electron moving in a circular orbit is λ. The minimum radius of
orbit is
λ λ λ λ
(1) (2) (3) (4)
π 2π 4π 3π
Sol. We know 2πr = nλ
For minimum radius n = 1
λ
2πrmin = λ ; rmin = Ans. (2)
2π

Example 4. An electron, practically at rest, is initially accelerated through a potential difference of 100 volts.
It then has a de Broglie wavelength = λ1 Å. It then get retarded through 19 volts and then has a
wavelength λ2 Å. A further retardation through 32 volts changes the wavelength to λ3, What is
λ3 − λ 2
?
λ1
20 10 20 10
(1) (2) (3) (4)
41 63 63 41
150 150
Sol. λ1 = Å .... (1) λ2 = Å .... (2)
100 81
150
λ3 = Å .... (3)
49
From (1), (2) and (3)
λ3 − λ 2 20
= Ans. (3)
λ1 63

15. HEISENBERG’S UNCERTAINITY PRINCIPLE :

It is impossible to measure simultaneously both the position and velocity (or momentum) of a
microscopic particle with absolute accuracy or certainity.
h h h
∆x.∆p ≥ or m ∆x.∆v ≥ or ∆x.∆v ≥
4π 4π 4πm
where, ∆x = uncertainity in position
∆p = uncertainity in momentum
h = Plank’s constant
m = mass of the particle
∆v = uncertainity in velocity
• In terms of uncertainity in energy ∆E, and uncertainity in time ∆t, this principle is written as,
Atomic Structure (Theory) 26

h
∆E.∆t ≥ .
4π
• Heisenberg replaced the concept of definite orbits by the concept of probability.

Solved example
Example 1. Alveoli are the tiny sacs of air in the lungs whose average diameter is 50 pm. Consider an
oxygen molecule trapped within a sac. Calculate uncertainty in the velocity of oxygen
molecule?
(1) 1.98 × 10–2 ms–1 (2*) 19.8 ms–1 (3) 198 × 10–4 ms–1 (4) 19.8 × 10–6ms–1
Sol. ∆x = 50 pm
h 6 . 625 × 10−34 × 6.022 × 1023
So ∆v = = m/sec
4π . m∆x 4 × 3.14 × 32 × 10 −3 × 50 × 10 −12
= 0.0019853 × 104 m/sec
= 19.853 m/sec
Example 2. Determine the de-Broglie wavelength associated with an electron in the 3rd Bohr's orbit of He+
ion?
(1) 10 Å (2) 2 A (3*) 5 Å (4) 1 Å
Sol. nλ = 2πr
2πr 2π 9
so λ= = × (53 pm) ×  5Å
3 3 2
Example 3. If the light of wavelength 5.77 × 10–10 cm is used to detect an electron then the uncertainly in
velocity (approximately) will be (h = 6.6 × 10–34 Js, me = 9.1 × 10–31 kg).
(1) 106 m/s (2) 106 m/s (3*) 107 m/s (4) None of these
−34
h 6.6 × 10
Sol. ∆V = = = 107 m/s
4π m ∆x 4 × 3.14 × 9.1× 10 −31 × 5.77 × 10 −12

Example 4. The uncertainty in position and velocity of the particle are 0.1 nm and 5.27×10–24 ms–1
respectively then the mass of the particle is : (h = 6.625 × 10–34Js)
(1) 200 g (2) 300 g (3*) 100 g (4) 1000 g
h 6.6 × 10−34
Sol. m= =
4π∆x 4 × 3.14 × 10−10 × 5.27 × 10 −24
 100 gm.
Example 5. Uncertainty in position of a hypothetical subatomic particle is 1Å and uncertainty in velocity is
3.3
× 105 m/s then the mass of the particle is approximately [h = 6.6 × 10–34 Js]
4π
(1) 2 × 10–28 kg (2) 2 × 10–27 kg (3) 2 × 10–29 kg (4) 4 × 10–29 kg
Sol. ∆x × m × ∆v ≥ h/4π
3.3 6.6 × 10−34
1 × 10-10 × m × × 105 ≥ m = 2 × 10– 29 kg Ans. (3)
4π 4×π

16. THE SCHRODINGER EQUATION :

This equation determines the probability of position and energy of electron which is moving around the
nucleus.
Atomic Structure (Theory) 27

∂2 ψ ∂2 ψ ∂2 ψ 8π 2 m 8π2m
+ + + or ∇ y +
2
(E – V) y = 0
∂x 2
∂y 2
∂z 2
h 2
h2
Where = Laplacian operator.
E = Total energy of the electron.
V = Potential energy of the electron
y = Wave function or wave amplitude
2
y = Probability density (probability of finding an electron in an atom)
Important features of the quantum mechanical model of atom
Quantum mechanical model of atom is the picture of the structure of the atom, which emerges from the
application of the Schrodinger equation to atoms. The following are the important features of the
quantum mechanical model of atom :
1. The energy of electrons in atoms is quantized (i.e. can only have certain specific values), for
example when electron are bound to the nucleus in atoms.
2. The existence of quantized electronic energy levels is a direct result of the wave like properties
of electrons and are allowed solutions of schrdinger wave equation.
3. Both the exact position and exact velocity of an electron in an atom cannot be determined
simultaneously (Heisenberg uncertainty principle). The path of an electron in an atom therefore,
can never be determined or known accurately. That is why, as you shall see later on, one talks
of only probability of finding the electron at different points in an atom .
4. An atomic orbital is the wave function ψ for an electron in an atom. Whenever an electron is
described by a wave function, we say that the electron occupies that orbial
5. The probability of finding an electron at a point within an atom is porportional to the square of
2 2
the orbital wave function i.e. |ψ| at that point. |ψ| is known as probability density and is always
positive.
Hydrogen atom and the schrodinger Equation :
When Schrodinger equation is solved for hydrogen atom. The solution gives the possible energy levels
the electron can occupy and the corresponding wave function(s) (ψ) of the electron associated with
each energy level. These quantized energy states and corresponding wave functions which are
characterized by a set of three quantum numbers (principal quantum number n, azimuthal quantum
number  and magnetic quantum number m ) arise as a natural consequence in the solution of the
Schrodinger equation.
Application of Schrodinger equation to multi-electron atoms presents a difficulty : the Schrodinger
equation cannot be solved exactly for a multi electron system. This difficulty can be overcome by using
approximate methodes such calculation with the aid of modern computers show that orbitals in atoms
other than hydrogen do not differ in any radical way from the hydrogen orbitals discussed above. The
principle difference lies in the consequence of increased nuclear charge. Because of this all the orbitals
are somewhat contracted. Unlike orbitals of hydrogen or hydrogen like species, whose energies
depends only on the quantum number n, the energies of the orbitals in multi-electron atoms depends on
quantum numbers n and .

17. QUANTUM NUMBERS :

The set of four numbers required to define an electron completely in an atom are called quantum
numbers. The first three have been derived from Schrodinger wave equation.
Atomic Structure (Theory) 28

17.1. Principal quantum number (n) : (Proposed by Bohr)

It describes the size of the electron wave and the total energy of the electron. It has integral values 1, 2,
3, 4 ...., etc., and is denoted by K, L, M, N. ..., etc.

• Number of subshell present in nth shell = n

n subshell
1 s
2 s, p
3 s, p, d
4 s, p, d, f
• Number of orbitals present in nth shell = n2 .
• The maximum number of electrons which can be present in a principal energy shell is equal to 2n2.
No energy shell in the atoms of known elements possesses more than 32 electrons.
nh
• Angular momentum of any orbit =
2π

17.2. Azimuthal quantum number (l) : (Proposed by Sommerfield)

It describes the shape of electron cloud and the number of subshells in a shell.

• It can have values from 0 to (n – 1)

• value of  subshell
0 s
1 p
2 d
3 f
• Number of orbitals in a subshell = 2 + 1
• Maximum number of electrons in particular subshell = 2 × (2 + 1)
h  h 
• Orbital angular momentum L =  ( + 1) =   ( + 1)   = 2π 
2π  
h
i.e. Orbital angular momentum of s orbital = 0, Orbital angular momentum of p orbital = 2 ,
2π
h
Orbital angular momentum of d orbital = 3
2π

17.3. Magnetic quantum number (m) : (Proposed by Linde)

It describes the orientations of the subshells. It can have values from – to +  including zero, i.e., total
(2 + 1) values. Each value corresponds to an orbital. s-subshell has one orbital, p-subshell three
orbitals (px, py and pz), d-subshell five orbitals (dxy ,dyz , dzx , dx2 − y2 , dz2 ) and f-subshell has seven
orbitals. The total number of orbitals present in a main energy level is ‘n2’.

17.4. Spin quantum number (s) : (Proposed by Goldschmidt & Uhlenbeck)

It describes the spin of the electron. It has values +1/2 and –1/2. (+) signifies clockwise spinning and (–)
signifies anticlockwise spinning.
Atomic Structure (Theory) 29

eh
• Spin magnetic moment µs = s(s + 1) or µ = n(n + 2) B.M. (n = no. of unpaired
2π mc
electrons)
h
• It represents the value of spin angular momentum which is equal to s(s + 1)
2π
1
• Maximum spin of atom = × No. of unpaired electron.
2
 Total no. of e– in main energy shell = 2n2
Total no. of e– in a subshell = 2 (2 + 1)
Maximum no. of e– in an orbital = 2
Total no. of orbitals in a subshell = (2 + 1)
No. of subshells in main energy shell = n
No. of orbitals in a main energy shell = n2
h
 Orbital angular momentum L =  ( + 1)
2π
h 1
 Spin angular momentum S = S (S + 1) ; S =
2π 2
µ= n (n + 2) B.M. (n = no. of unpaired electrons)
eh
 Orbital magnetic moment µs = ×  ( + 1)
4 π me

18. ELECTRONIC CONFIGURATION

18.1. Pauli’s exclusion principle :

No two electrons in an atom can have the same set of all the four quantum numbers, i.e., an orbital
cannot have more than 2 electrons because three quantum numbers (principal, azimuthal and
magnetic) at the most may be same but the fourth must be different, i.e., spins must be in opposite
directions.

18.2. Aufbau principle :

Aufbau is a German word meaning builiding up. The electrons are filled in various orbitals in order of
their increasing energies. An orbital of lowest energy is filled first. The sequence of orbitals in order of
their increasing energy is : 1s, 2s, 2p, 3s, 3p, 4s, 3d, 4p, 5s, 4d, 5p, 6s, 4f, 5d, 6p, 7s, 5f, 6d, ....
The energy of the orbitals is governed by (n + ) rule.

18.3. (n + l) Rule :
This rule states that electrons are filled in orbitals according to their (n + ) values.Electrons are filled in
increasing order of their (n + ) values. When (n + ) is same for sub energy levels, the electrons first
occupy the sublevels with lowest "n" value.

18.3.1 Energy level diagram :

The representation of relative energy levels of various atomic orbital is made in terms of energy level
diagrams.
Atomic Structure (Theory) 30

7s
6p 5d
6s 4f

n=1 1s 5p
4d
2s 5s
n=2 2p
4p

Increasing energy
3s 3p 3d
n=3 3d 4s

n=4 4s 4p
4d 3p
4f
5s 5p
n=5 5d 3s
5f
n=6 6s 6p
6d 2p
7s 7p
n=7 2s

1s

Fig. Sequence of filling of electrons in orbitals belonging to different energy levels

18.4. Hund’s rule :

No electron pairing takes place in the orbitals in a subshell until each orbital is occupied by one electron
with parallel spin. Exactly half filled and fully filled orbitals make the atoms more stable, i.e., p3, p6, d5,
d10, f 7 and f14 configuration are most stable.

Solved example

Example 1. Calculate total spin, magnetic moment for the atoms having at. no. 7, 24 and 36.
Sol. The electronic configuration are
7N : 1s2, 2s2 2p3 unpaired electron = 3

24Cr : 1s2, 2s2 2p6, 3s2 3p6 3d5, 4s1 unpaired electron = 6

36Kr : 1s2, 2s2 2p6, 3s2 3p6 3d10, 4s2 4p6 unpaired electron = 0
∴ Total spin for an atom = ± 1/2 × no. of unpaired electron
For 7N, it is = ± 3/2 ; For 24Cr, it is = ± 3 ; For 36Kr, it is = 0
Also magnetic moment = n (n + 2)

For 7N, it is = 15 ; For 24Cr, it is = 48 ; For 36Kr, it is = 0

Example 2. Write down the four quantum numbers for fifth and sixth electrons of carbon atom.
Sol. 2 2 2
6C : 1s , 2s 2p

1 1
fifth electron : n=2 =1 m = – 1 or +1 s = + or –
2 2
1 1
sixth electron : n=2 =1 m=0 s=+ or –
2 2
Example 3. Given below are the sets of quantum numbers for given orbitals. Name these orbitals.
(a) n = 3 (b) n = 5 (c) n = 4 (d) n = 2 (e) n = 4
=1 =2 =1 =0 =2
Ans. 3p, 5d, 4p, 2s, 4d
Sol. (a) n = 3 ,  = 1 ⇒ 3p (b) n = 5 ,  = 2 ⇒ 5d (c) n = 4 ,  = 1 ⇒ 4p
Atomic Structure (Theory) 31

(d) n = 2 ,  = 0 ⇒ 2s (e) n = 4 ,  = 2 ⇒ 4d

Example 4. Which of the following set of quantum numbers is not valid.

1 1
(1) n = 3, l = 2, m = 2, s = + (2) n = 2, l = 0, m = 0, s = –
2 2
1 1
(3) n = 4, l = 2, m = –1, s = + (4) n = 4, l = 3, m = 4, s = –
2 2
Sol. Not valid Ans. (4)
Example 5. What is the total spin value in case of 26Fe3+ ion
(1) +1 or –1 (2) +2 or –2 (3) + 2.5 or – 2.5 (4) +3 or –3
 1
Sol. Total spin = no. of unpaired e– ×  ± 
 2
 1 5
= 5 × ±  =± Ans. (3)
 2 2

19. SHAPE OF THE ORBITALS :

Shape of the orbitals are related to the solutions of Schrodinger wave equation and gives the space in
which the probability of finding an electron is maximum.

19.1. s- orbital :
Shape → spherical

s- orbital is non directional and it is closest to the nucleus, having lowest energy.
s-orbital can accomodate maximum no. of two electrons.

19.2. p-orbital :
Shape → dumb bell

Dumb bell shape consists of two loops which are separated by a region of zero probability called node.

p - orbital can accomodate maximum no. of six electrons.

Atomic Structure (Theory) 32

19.3. d - Orbital :
Shape double → dumb bell

d - orbital can accomodate maximum no. of 10 electrons.

19.4. f - orbital :
Shape leaf like

f - orbital can accomodate maximum no. of 14 electrons.

Nodes in orbitals
(i). total nodes = n – 1,
(ii). angular nodes = l,
(iii). radial nodes = n – l – 1.

NUCLEAR CHEMISTRY
Spontaneous disintegration of nuclei due to emission of radiations like α, β, γ is called radioactivity.
Radioactivity is a nuclei phenomenon.
Radioactivity is not dependent on external conditions like temperature, pressure etc.
Radioactivity of a substance is independent to its physical state.
x(s), x(l), x(g), (x)+(g), (x)–(g) in all form, x is radioactive.
14
CO2, 146C(s), 146C(g) is radioactive.
Radiations :
α : 2He4 ( 24He2+) (nucleus of He-atom)
β or β– : –1e0 (fast moving electron emitted from nucleus)
γ : 0γ 0
(electromagnetic radiation (waves) of high frequency)
speed : γ>β>α
penetrating power : γ>β>α
ionisation power : α>β>γ
 Atomic Structure (Theory) 33

Emission of rays Usual condition Effect Process representation / example

n
1. α Z > 83 ratio increases Z
XA → Z– 2X’A – 4 + 2He4
p
92
U238 → 90Th234 + 2He4
n n
2. β If ratio is high. ratio decreases Z
YA → Z+ 1Y’A – 4 + –1e0
p p
n 6
eg. 6
C12 (stable) = 6
C14 → 7N14 + –1e0
p 6
n 8 n 8 n 7
6
C14 (radioactive) = (high) = =
p 6 p 6 p 7
n 13
eg. 11
Na24 (radioactive) = (high) 0
n1 → 1p1 + –1e0 (from nucleus)
p 11
n 12
11
Na23 (stable) =
p 11
n 11 n
11
Na22 = ( ratio low)
p 11 p
3. γ If nucleus energy nucleus energy 43
Tc99 → 43Tc99 + γ
level is high level decreases high low
nucleus nucleus
energy energy
(metastable)
n n
4. (a) Positron emission If ratio is low ratio increases Z
YA → Z – 1Y´A + +1e0
p p
(+1e0) 11
Na22 → 10Ne22 + +1e0
1
p1 → 0n1 + +1e0 (from nucleus)
n n
−1e →
0
(b) Electron capture If ratio is low ratio increases Z
X´A + Z–1
X´´A
p p K − shell

(EC) or K-shell 80
Hg197 + –1e0 → 79Au197

Electron capture

1p
1
+ −1 e0 → 0 x1
(K − shell)

Nuclear stability belt :

Atomic Structure (Theory) 34

200
(1.5:1 ratio) 80 Hg
B
Belt of
stability
Number of neutrons
(1.40:1 ratio) 168
70 Yb

(1.25:1 ratio) C
90
40 Zr

1 :1 neutron to
proton ratio

A
Number of protons
β-emission
0
n1 → 1p1 + –1e0
 Z upto 20 : nuclei stable with n/p ratio nearly 1 : 1
 Z > 20 : n/p ratio increases with Z in stable nuclie region.
 More number of neutrons are required to reduce repulsion between protons.
 83
Bi209 : Stable with largest n/p ratio
n 1.52
=
p 1

Even - odd rule :

no. of n no. of p no. of stable nuclie
even even 155 (max)
even odd 55
odd even 50
odd odd 5 (min)

 Expected pairing of nucleus

Magic Numbers :
Nuclei in which nucleons have magic no. (2, 8, 20, 28, 50 ....) are more stable.
e.g. 2
He4 , 8O16

Group displacement law : (Given by Soddy and Fajan)

 When 1α emission takes place from a nuclie, new formed nuclie occupy two position left in periodic
table.

 When 1β emission takes place from a nuclie, new formed nuclie occupy one position right in periodic
table.

Due to emission of 1β particle; isobars are formed.

Due to emission of 1α particle; isodiaphers are formed.

Atomic Structure (Theory) 35

Due to emission of 1α and 2β ; isotopes are formed.

Isotopes : same number of proton eg. 6C14 and 6C12

Isobars : same mass number eg. 6C14 and 7N14
Isotones : same number of neutron eg. 2He4 and 1H3

Isodiaphers : Same (n – p) difference

e.g. 9F19 and 19K39 ; (n – p) = 10

Isosters : Same number of atoms and electrons

e.g. N2 and CO
N2O and CO2

Artifical nuclear reaction :

 specific nuclei + stricking particle —→ New nuclei + emitted particle

eg.
1. (α, p type) 7
N14 + 2
He4 —→ 8
O17 + 1
p1 (or 1H1)
(s.p.) (e.p.)
2. (n, γ type) 11
N23
+ 1
n0 —→ 11
Na 24
+ γ
3. (D, p type) 13
Al27 + 1
H2 —→ 13
Al28 + 1
H1
4. (p, α type) 3
Li7 + 1
H1 —→ 2
He4 + 2
He4

Nuclear fission and nuclear fusion :

In both processes, large amount of heat evolved due to conversion of some mass into energy.
Nuclear fission : Is a process where heavy nuclei splits into large nuclei.

92
U235 + 0n1 —→ 92
U*236

eg. atom bomb is based on fission.

Nuclear fusion :
Is a process where light nuclei fused together to form heavy nuclei.
1
H2 + 1H3 —→ 2He4 + 0n1

1
H2 + 1H2 —→ 2
He4
Hydrogen bomb is based on fusion. Very high temperature is required in this process.

Solved example
24
Example 1. 23
Na is the most stable isotope of Na. Find out the process by which 11 Na can undergo
radioactive decay.
Sol. n/p ratio of 24Na is 13/11 and thus greater than one. It will therefore decay following β-emission.
0
24
11 Na → 24
12 Mg + −1e
Atomic Structure (Theory) 36

Example 2. The number of β-particle emitted during the change ca X → bd Y is :

a−b a−b c −b a−b
(A) (B) d +   +c (C) d +   –a (D) d +  –c
4  2   2   2 
0
Sol. c
aX → bd Y + m 24 He + n −1e
∴ c = b + 4m ......(i)
and a = d + 2m – n ......(ii)
by (i) & (ii)
c −b
n = d +  – a. Ans. (C)
 2 

13
Example 3. The decay product of 7 N is :
13 0 13 0
(A) 8 O + −1e (B) 6 C + +1e
13
(C) 6 C + K electron capture (D) 95 Be + 24 He
13 n
Sol. 7 N is positron emitter ; ratio is low. Ans. (B)
p

Example 4. A radioactive element X has an atomic numbers of 100. It decays directly into an element Y
which decays directly into an element Z. In both processes a charged particle is emitted. Which
of the following statement would be true?
(A) Y has an atomic number of 102. (B) Z has an atomic number of 101.
(C) Z has an atomic number of 97. (D) Z has an atomic number of 99.
Sol. X and Y can decay one α each or one β each or X-decays, 1 α, Y-decays 1 β or X-decays 1
β or Y-decays 1 α. In either case (A), (B) and (C) cannot be true. Ans. (D)