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PHYSICAL CHEMISTRY

TARGET JEE 2018


CRASH COURSE

ATOMIC STRUCTURE
PREREQUISITE:
Basic concept of electrostatics force,
electrostatic potential energy, circular motion.
Basic idea of wave, electromagnetic wave,
dual nature of light and spectrum

CONTENTS
" A SPECIALLY DESIGNED KIT FOR LEARNING."

THE KEY  Basic principles of subjects.An outline of the topics to be


discussed in class lectures.
THEATLAS  Basic layout of subject.Aroute map correlatingdifferent subtopics
in coherent manner.
EXERCISE I  Introductory problems to get first hand experience of problem
solving for JEE.
EXERCISE II  Collection of problems to test analytical, reasoning and
comprehensive skills as per New JEE pattern.
EXERCISE III A  A collection of previous ten years JEE Advance problems.
EXERCISE III B  A collection of previous ten years JEE Main problems.

Corporate Office : "BANSAL TOWER", A-10, Road No.-1, I.P.I.A., Kota-324 005 (Raj.) INDIA
Tel.: (0744) 2791000
Website : www.bansal.ac.in | Email : admin@bansal.ac.in
ATOMIC STRUCTURE

TENTATIVE LECTURE SCHEDULE

Lec-1: Dalton’sAtomic theory, Cathode rays-Properties & Experiments for charge and specific charge
determination.

Lec-2: Anode rays, Thomson’s model.

Lec-3: Rutherford model, Mosley experiment,Atomic terms.

Lec-4: Wave, EM Wave, Spectrum, Planck’s Quantum theory.

Lec-5: Photoelectric effect, Bohr’sAtomic Model.

Lec-6: Numericals portion of Bohr theory & hydrogen spectrum.

Lec-7: De-Broglie theory & Heisenberg uncertainity principle.

Lec-8: Wave mechanical model & Radial probability graphs.

Lec-9: Angular probabilityof orbitals & applications based on quantum number & pending discussion.

* The above schedule is tentative & can be modified as per the batch.

* Tutorial sheet discussion should be done along with completion of theory.

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ATOMIC STRUCTURE

TEACHER’S ADVICE:
GENERAL MISTAKE:
Special Highlights
BRAIN TEASERS:



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ATOMIC STRUCTURE

ATOMIC STRUCTURE
1. PRE - REQUISITES
"In order to have a clear understanding of some of the concepts of Atomic Structure, an elementary
knowledge of concepts from other topics is required. The following section gives an overview of such
concepts which would be used during the chapters. Students are advised to get acquainted to these
terms and formulae as these would be frequently used in the chapters. An in-depth knowledge in the
following areas at this level is not required and these would be covered in detail later as a part of course
curriculum in Physics."

1.1 Concepts of Electrostatics from physics [Elementary level]


K q1q2
(a) Electrostatic force, F  .
D r2

D = Dielectric constant (1 for vacuum)


q1 q2 are charge on particles & r is distance between them.
1
K  9  109 (S.I. units)
4 0
Force is along the line joining center and is attractive when q1 & q2 are of
opposite sign.

k.q1q2
(b) Potential Energy [Due to Electrostatic force] 
r
P.E. + ve for forces of repulsion & P.E. –ve for forces of attraction.

(c) Electric force on charged particle in an electric field E, FEF = q. E


E - Electric field strength, q – Charge on electron
(d) Increase in energy of a charged particle (q) accelerated from rest by a potential
difference of V volts = qV

(e) Magnitude of magnetic force on a moving charge under specific arrangement.*


FMF = q v B
q = Charge on Body, v = velocity of Body, B = Magnetic field strength.

* For the above expression to be applicable velocity should be  to the magnetic field vector..

1.2 Elementary knowledge of waves [To be discussed later in chapter]

1.3 Expertise in unit conversion from one system to another.

2. DALTON’S ATOMIC THEORY

John Dalton 1808, believed that matter is made up of extremely minute indivisible particles, called
atom which takes part in chemical reactions. These particles can neither be created nor be destroyed.
However, modern researchers have conclusively proved that atom is no longer an indivisible particle.
Modern structure of atom is based on Rutherford's scattering experiment, quantization of energy and
wave mechanical model.
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ATOMIC STRUCTURE

Can you guess how and into what an atom can be divided ?

3. COMPOSITION OF ATOM

The works of J.J. Thomson and Ernst Rutherford actually laid the foundation of the modern picture of
the atom. It is now verified that the atom consists of several sub-atomic particles like electron, proton,
neutron, positron, neutrino, meson etc. Out of these particles, the electron, proton and the neutron are
called fundamental subatomic particles.

Does all the atoms contain all the three fundamental subatomic particles

4. ELECTRON (-1e0 , e)

4.1 Electron was discovered by J.J. Thomson (1897) and it is a negatively charged particle.

4.2 Cathode rays were discovered by William Crooke & J.J. Thomson using a cylindrical hard glass tube
fitted with two metallic electrodes. This tube was known as discharge tube. They passed electricity
(10,000V) through a discharge tube at very low pressure. Blue rays emerged from the cathode. These
rays were termed as Cathode rays.

Cathode rays Gas at low


pressure To Vaccum pump
Cathode Anode

High voltage
– +

Discharge tube experiment for production of cathode rays

4.3 Properties of Cathode rays


(i) Cathode rays travel in straight line.
(ii) Cathode rays produce mechanical effect, as they can rotate the wheel placed in their path.
(iii) Cathode rays consist of negatively charged particles known as electron.
(iv) Cathode rays travel with high speed.
(v) Cathode rays can cause fluorescence.
(vi) Cathode rays heat the object on which they fall due to transfer of kinetic energy to the object.
(vii) When cathode rays fall on heavy metals, X-rays are produced.
(viii) Cathode rays possess ionizing power i.e., they ionize the gas through which they pass.

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ATOMIC STRUCTURE

(ix) The cathode rays produce scintillation on the photographic plates.


(x) They can penetrate through thin metallic sheets.
(xi) The nature of these rays does not depend upon the nature of gas or the cathode material used in
discharge tube.

The television picture tube is a cathode ray tube in which a picture is produced
due to fluorescence on the television screen coated with suitable material.
Similarly, fluorescent light tubes are also cathode rays tubes coated inside
with suitable materials which produce visible light on being hit with cathode
rays.

R.A. Millikan measured the charge on an electron by oil drop experiment. The
charge on each electron is –1.602 × 10–19 C.

The specific charge (e/m) on electron was first determined by J.J. Thomson.
e/m = 1.758 × 10–11 C/kg

Rest mass of electron is 9.109 × 1031 kg or, 0.00054 amu

4.4 Determination of e/m ratio of electrons. (By Thomson):

+
Cathode P1
Fluoroscent screen
O
P2 O1
+
anode Magnet
v

Firstly the magnetic field is applied perpendicular to the plane of the figure and directed inward. This
deflects the electrons downward striking the screen at O1. Magnetic force Fm = q × v × B.

Now the electric field is applied between the plates P1 & P2. This exerts a force on the electron in the
upward direction. The strength of electric field (E) is so adjusted that electrons strikes at point O on the
screen.
 Electric force Fe = q × E
Since there is no net deviation, Fm = Fe
 qvB = q.E.
E
v … (1)
B
Since V is the potential difference voltage between the anode and cathode,
1 2qV
q.V  m.v 2  v  … (2)
2 m

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ATOMIC STRUCTURE

E 2qV 2qV E 2 q E2
From equation (1) & (2)    2  
B m m B m 2B 2V

e E2
For electron, q = e  
m 2B 2V

Knowing the values of E, B & V (which are experimentally controlled), we can calculate e/m.

e
This value   is found to be 1.76 × 1011 coulomb per kg.
m
The e/m ratio for electron was found to be same irrespective of the nature of cathode and nature of gas
taken in discharge tube. This shows that the electrons are universal constituent of all matter.

4.5 Millikan Oil drop Experiment

R.A. Millikan (1868-1953) devised a method known as oil drop experiment (1906-14), to determine
the charge on the electrons. In this method, oil droplets in the form of mist, produced by the atomiser,
were allowed to enter through a tiny hole in the upper plate of electrical condenser. The downward
motion of these droplets was viewed through the telescope, equipped with a micrometer eye piece. By
measuring the rate of fall of these droplets, Millikan was able to measure the mass of oil droplets. The air
inside the chamber was ionized by passing a beam of X-rays through it. The electrical charge on these oil
droplets was acquired by collisions with gaseous ions. The fall of these charged oil droplets can be
retarded, accelerated or made stationary depending upon the charge on the droplets and the polarity
and strength of the voltage applied to the plate. By carefully measuring the effects of electrical field
strength on the motion of oil droplets, Millikan concluded that the magnitude of electrical charge, q, on
the droplets is always an integral multiple of the electrical charge, e,
That is, q = n e, where n = 1, 2, 3...............

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ATOMIC STRUCTURE

He found that the charge on the electron to be – 1.6 ×10–19 C. The present accepted value of electrical
charge is – 1.6022 ×10–19 C. The mass of the electron (me) was determined by combining these results
with Thomson's value of e/m ratio.

Calculation of mass of electron. With the help of the experiments discussed above, it is possible to
calculate the values of e/m ratio and also the charge (e) on the electron. The mass (m) of the electron can
be calculated as follows.
e (1.60 10 19 C )
Mass of electron (m)  
e / m (1.76  108 Cg  1 )  9.10 10 g  9.10 10 kg
28 31
=

An electron may be defined as : A fundamental particle present in an atom, which carries one unit
negative charge (1.60 × 10–19 C) and negligible mass (9.1 × 10–28 g) which is 1/1837 of the mass of an
atom of hydrogen.

If in the above experimental setup terminal velocities are calculated in the


presence and absence of electric field then can you figure out the procedure
of calculating radius of the oil drop and charge on the oil drop. You can assume
that the drag force on the oil droplet will be equal to 6rv & will act opposite
to the motion of the oil drop)

Illustration:
1. An electron gun accelerates the e- through 320 volts which enters in a uniform magnetic field of
6×10–4 tesla acting as to it and an electric field of 6.4 ×103 volt/m, then calculate the ratio for no net
deviation for cathode rays.
e E2 (6.4  103 )2
Sol.   = 1.77 ×1011 Coulomb/kg
m 2VB 2 2  320  (6  10 4 ) 2

Illustration:
2. In oil drop experiment, the terminal velocity of an oil droplet was found to be 1 mm/sec in absence of
electric field and 2mm /sec (in upward direction) in presence of electric field of strength 6.75 ×106 
V/m. If the density of oil is 1 gm/ml and viscosity of air is 2×10–5 N – S/m2, calculate (i) the radius of oil
drop (ii) the charge on oil drop. (given that the drag force on the oil droplet will be equal to 6rv & is
acting opposite to the motion of the oil drop)
Sol. v1  1103 m / sec, v2  2 103 m / sec ,
E  6.75 106  V / m,  oil = 103 kg/m3, n = 2 ×10–5 N – S/m2

4 3 9 nv1
(i) 6n.r.v1  r ,  oil .g  r 
3 2 oil g

9  2  10 5 10 3
  3 10  6 m
2  10  10
3

6 nr(v1  v 2 ) 6  2  10 5  3  10 6 (1 10 3  2 10 3 )


(ii) q 
E 6.75  106 

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ATOMIC STRUCTURE

6  18
  10 20 = 16 × 10–20 = 1.6 × 10–19 Coulomb
6.75
We know that an atom is electrically neutral, if it contains negatively charged electrons it must also
contain some positively charged particles. This was confirmed by Goldstein in his discharge tube
experiment with perforated cathode. On passing high voltage between the electrodes of a discharge tube
it was found that some rays were coming from the side of the anode which passed through the holes in
the cathode. These anode rays (canal rays) consisted of positively charged particles formed by ionization
of gas molecules by the cathode rays. The charge to mass ratio ( e/m value) of positively charge particles
was found to be maximum when the discharge tube was filled with hydrogen gas as hydrogen is the
lightest element. e/m varies with the nature of gas taken in the discharge tube. The positive particles are
positive residues of the gas left when the gas is ionized.

5. PROTON (1H1, H+, P)

5.1 Introduction
Proton was discovered by Goldstein and it is positively charged particle. It is a component particle of
anode rays. Goldstein (1886) used perforated cathode in the discharge tube and repeated cathode
rays experiment and observed the formation of anode rays. These rays were also termed as positive or
canal rays.

Cathode rays
Anode rays
To Vaccum pump

Perforated High voltage


cathode – +

Perforated tube experim ent for production of anode rays

5.2 Properties of anode rays


(i)Anode rays travel in straight line.
(ii)Anode rays are material particles.
(iii)Anode rays are positively charged.
(iv)Anode rays may get deflected by external magnetic field.
(v) Anode rays also affect the photographic plate.
(vi) The e/m ratio of these rays is smaller than that of electrons.
(vii) Unlike cathode rays, their e/m value is dependent upon the nature of the gas taken in the tube. It is
maximum when gas present in the tube is hydrogen.
(viii) These rays produce flashes of light on ZnS screen.

Charge on proton = 1.602 × 10–19 coulombs

Mass of proton = 1.673 × 10–27 kg = 1.00728 amu

Proton is ionized hydrogen atom H+

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ATOMIC STRUCTURE

Specific charge of a proton is 9.58  10 7 Coulomb/kg

Can you guess why specific charge of cathode rays is independent of the gas
taken whereas that of anode rays is dependent.

6. NEUTRON (0n1, n)

Neutron was discovered by James Chadwick (1932) according to the following nuclear reaction,
9 4 12 1 11 4 14 1
4 Be  2 He  6 C  o n or 5 B  2 He  7 N  o n
The reason for the late discovery of neutron was its neutral nature.

Mass of neutron = 1.675  10 27 kg = 1.00866 amu

Specific charge of a neutron is zero.

Neutron is fundamental particle of all the atomic nucleus, except hydrogen or


protium.

Illustration
3. The mass to charge ratio for A+ ion is 1.97 × 10–7 kg C–1. Calculate the mass of A atom.
m
Sol. Given = 1.97 × 10–7
e

(since e = 1.602 × 10–19 C)  m = 1.97 × 10–7 × 1.602 × 10–19 kg

7. THOMSON’S MODEL
After discovery of electron and proton attempts were made to find out their arrangement in an atom. The
first simple model was proposed by J.J. Thomson known as Thomson’s atomic model.
He proposed that the positive charge is spread over a sphere of the size of the atom (i.e. 10–8 cm radius)
in which electrons are embedded to make the atom as whole neutral.
This model could not explain the experimental results of Rutherfords -particle scattering, therefore it
was rejected.
Positively charged
+ – + sphere
– –
+ – +
+ Electron
+ –
– +
Po s itive c harge s pre aded thro ugho ut the s phere

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ATOMIC STRUCTURE

8. RUTHERFORD’S MODEL
Rutherford carried out -particles scattering experiment by the bombardment of high speed
-particle on thin foil of gold, emitted from radium and gave the following observations, which was
based on his experiment.
Very few Thin gold Few
Radioactive
substance foil

Most
Lead block
Lead plate
with hole Few
8.1 Observations :
(a) Most of the  - particles (nearly 99%) continued with their straight path.
(b) Some of the  - particles passed very close to the centre of the atom and deflected by small angles.
(c) Very few particles thrown back (180º).

Atom of metal foil


Few
Beam of –particles Majority
 of –rays

Very Few
Majority
of –rays
Few
Atom of metal foil

8.2 Main features :


(a) Most of the  - particles were continued their straight path that means most of the space inside
the atom is empty.
(b) The centre of an atom has a positively charged body called nucleus which repel positively charged
 - particles and thus explained the scattering phenomenon.
(c) Almost all mass of an atom is concentrated in its nucleus.
(d) The size and volume of the nucleus is very small as compared to the total size and volume of atom.

8.3 Properties of the Nucleus


(i) Nucleus is a small, heavy, positively charged part of the atom and is located at the centre of the
atom.
(ii) All the positive charge of atom (i.e. protons) are present in nucleus.
(iii) Nucleus contains neutrons and protons, and hence these particles collectively are also referred to
as nucleons.
(iv) The size of nucleus is measured in Fermi (1 Fermi = 10-13 cm = 10-15 m). Generally, the radius
of the nucleus (rn) is given by the following relation :
rn  ro  A1/ 3
where r0 is a constant and A is the mass number.
(v) The Volume of the nucleus is about 10–42 m3 and that of atom is 10–27 m3 , i.e., volume of the
nucleus is 10–15 times that of an atom.

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ATOMIC STRUCTURE

8.4 Di st ance of cl osest appr oach : When the -particle approaches the nucleus to made a head-
on collision with the nucleus, the -particle approaches the nucleus until coulombic potential

Z1Z 2 e 2 1
energy of repulsion , k , becomes equal to its initial K.E., m.v2.
r 2

1 2
Z1Z 2 e 2
Thus mv = k
2 r

k z1z 2 e 2
Hence, the distance of closest approach, r =
1 2
 mv 
2 
The nucleus must be further smaller than the distance of closest approach.

8.5 Drawbacks of Rutherford's model


(i) It does not obey the Maxwell theory of electrodynamics. According to this theory a small charged
particle moving around an oppositely charged centre continuously loses its energy. If an electron does
so, it should also continuously lose its energy and should set up spiral motion ultimately falling into the
nucleus.
Nucleus

Electron

(ii) It could not explain the line spectra of atom.


Illustration
4. Atomic radius is of the order of 10–8 cm and nuclear radius is of the order of 10–13 cm. Calculate what
fraction of atom is occupied by nucleus ?

4 4
Sol. Volume of nucleus = r3 =  (10–13)3 cm3
3 3

4 VN 10–39
Volume of atom =  (10–8)3 cm3, VAtom = = 10–15
3 10–24
VNucleus = 10–15 × VAtom

5. With what velocity should an particle travel towards the nucleus of a Cu atom so as to arrive at a
distance 1013 m .
1 kz1z 2 k 2e  63e 
Sol. mv2 = r 2 = 2
rmin
2 min

2k 2e  63e 
v 2  2
m  rmin
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ATOMIC STRUCTURE

2k.2e.63e
v = 2 = 6.3 × 106 m/s
m  .rmin

9. MOSELEY EXPERIMENT (DISCOVERY OF ATOMIC NUMBER)


Moseley (1912–1913), investigated the X–rays spectra of 38 different elements, starting from aluminium
and ending in gold. He measured the frequency of principal lines of a particular series (the -lines in the
K series) of the spectra. It was observed that the frequency of a particular spectral line gradually
increased with the increase of atomic mass of the element. But, it was soon realised that the frequency
of the particular spectral line was more precisely related with the serial number of the element in the
periodic table which he termed as atomic number (Z). He presented the following relationship :
v  a Z  b 
where, v = frequency of X-rays, Z=atomic number, ‘a’and ‘b’are constants. When the values of square
root of the frequency were plotted against atomic number of the elements producing X–rays, a straight
line was obtained.

20

v / 108 s 1 15

10

5
10 20 30 40
Atomic number (Z)

Illustration
6. If the straight line is at an angle 45° with b= 1 calculate frequency when atomic number Z is 50.
(A) 2000 (B) 2010 (C) 2401 (D) None
Ans. (C)
Sol.   tan 45  1  a
b=1 a= tan 

   50  1  49  s 1

  2401s 1. z

10. SOME ATOMIC TERMS


10.1 Atomic number = Number of unit positive charge on nucleus = Number of protons in nucleus =
Number of electrons in neutral atom.
Two different elements can never have identical atomic number.
10.2 Mass number (A) = Number of protons or Atomic number (Z) + Number of neutrons
Hence Number of neutrons = A - Z .

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ATOMIC STRUCTURE

The atom of an element X having mass number (A) and atomic number (Z) may be represented by a
symbol,
Element Mass number
A
Atomic number X
Z
e.g. 9 F , 8 O 16 , 7 N 14 etc.
19

A part of an atom up to penultimate shell is a kernel or atomic core.


Negative ion (anion) is formed by gaining electrons and positive ion (cation) by the loss of electrons.
10.3 Isotopes :Atoms of an element with the same atomic number but different mass number.
1 2 3
eg. 1H 1H 1H
Protonium deuterium Tritium
10.4 Isodiapheres : The elements which have same value of (n – p) is called Isodiapheres.
14 16
eg. 7N 8O
Values of (n – p) 0 0
10.5 Isotone : Elements which contain same no. of neutron is called Isotone.
30 31 32
eg. 14Si 15P 16S
number of neutrons 16 16 16
10.6 Isobar : The two different atoms which have same mass number but different atomic number is called
Isobar.
40 40 40
eg. 18Ar 19 K 20Ca
10.7 Isoelectronic : Ion or atom or molecule which have the same number of electron is called Isoelectronic
species.
– + +2
eg. 17Cl 18Ar 19K 20Ca
No. of electrons 18 18 18 18
10.8 Isosters : Substance which have same number of electrons and the same number of total atoms are
called Isosters.
eg. CO 2 N 2 O
No. of electrons 22 22
No. of atoms 3 3
Illustration
7. From the following list of atoms, choose the isotopes, isobars and isotones -
16
8O , 39
19 K , 235
92 U , 40
19 K , 14
7N , 18
8O , 14
6C , 40
20 Ca , 238
92 U

Sol. Isotopes : ( 168 O , 18


8O ), ( 39
19 K , 19 K ), ( 92 U , 92 U )
40 235 238

Isobars : ( 40
19 K ,
40
20 Ca ) , ( 147 N , 14
6C )
Isotones : ( 39
19 K ,
40
20 Ca ), ( 146 C , 16
8O )
8. Total number of electrons, protons and neutrons present in the nucleus of 92U238 is
(A) e = 92, p = 92, n= 146 (B) e = 92, p = 92, n= 148
(C) e = 0, p = 92, n= 146 (D) None of these
Ans. (C)
Sol. There is no electron in the nucleus.
ne = 0, np = 92, nn = 238–92 = 146

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ATOMIC STRUCTURE

11. WAVE
A wave motion is a means of transferring energy from one point to another point without any actual
transportation of matter between these points. When we throw a piece of stone on the surface of water
in a pond, we observe circles of ever increasing radius, till they strike the wall of the pond. When we put
a piece of cork on the surface of this water, we observe that the cork moves up and down as the wave
passes, but the piece does not travel along with the waves. The water waves carries the energy but there
is no transfer of matter. Thus in a wave motion, disturbance travels through the medium, but the medium
does not travel along with the disturbance.

Some important terms related with wave motion.

Crest Wavelength

Vibrating
Energy
source
n
Trough

(i) Wave length () : The distance between two adjacent crest or trough of the wave (or the distance
between two similar neighbouring points)
OR
(ii) Time period (T) : Time for one complete oscillation of wave is called the period (T).
Time taken by the wave to travel a distance equal to one wavelength. If C is the

speed of wave, then C =
T
(iii) Frequency () : Number of oscillations per unit time is called frequency.
C


(iv) Wave number ( ) : Number of wavelength per unit length.
1


(v) Amplitude (A) : It is the height of crest or depth of a trough of a wave.

11.1 Electromagnetic Wave :


Light is also a type of wave which is known as electromagnetic wave i.e. wave consisting of oscillating
electric and magnetic field.
There are various types of electromagnetic waves (radiation) which differs from one another in wavelengths
e.g. Visible light, ultraviolet rays, X-rays, infra-red rays, radio waves etc.

11.2 Characteristics of electromagnetic radiations:


(a) All electromagnetic waves move or travel with the same speed equal to that of light.
(b) They do not require any medium to propagate.
(c) These consist of electric and magnetic field that oscillate in the direction perpendicular to each other
and to the direction in which the wave propagates (as shown in above diagram)

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ATOMIC STRUCTURE

Z Y
Direction of propagation

Ele
ctr
ic f
ield
X


11.3 Electromagnetic Spectrum
Arrangement of various types of electromagnetic radiations in order of their increasing (or decreasing)
wavelengths or frequencies is known as electromagnetic spectrum.
 increases 

Cosmic -rays X-rays Vaccum UV Visible Near Far Micro Radio


Rays UV IR IR Waves Waves

= –14 –11 –9 –7 –6 –5 –3 –1 0
10 10
–13
10 10 10 10 10 10 10 10
–10 –8 –4 –2
10 10 10 10
–12
10
12. SPECTRUM
When light coming from a source is dispersed by a prism, light of different wavelength are deviated
through different angles and get separated. This phenomenon is called dispersion and such a dispersed
light may be received on a photographic plate or it may be viewed directly by eye. A collection of
dispersed light giving its wavelength composition is called a spectrum.
12.1 Types of spectrum
1. Emission spectrum : A substance gets excited on heating at a very high temperature or by giving
energy and subsequently radiations are emitted. These radiations when analysed with the help of
spectroscope, spectral lines are obtained. A substance may be excited-
(a) By heating at a higher temperature.
(b) By passing electric current at a very low pressure in a discharge tube filled with a gas.
(c) By passing electric current into metallic filament.
Emission spectra may be classified as :

(i) Continuous spectrum : When sunlight is passed through a prism, it gets dispersed into continuous
bands of different colours. If the light of an incandescent object is resolved through prism or
spectroscope, it also gives continuous spectrum of colours.

Ultraviolet
Violet 4000 Å
Indigo
Blue
Green
Prism
Yellow
Orange
Red 6500 Å
Narrow beam
of while light Infrared

Continuous

Continuous spectrum of white light

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ATOMIC STRUCTURE

(ii) Line spectrum : If the radiations obtained by the excitation of a substance are analysed with the
help of a spectroscope, a series of thin bright lines of specific colours are obtained. There is dark
space in between two consecutive lines. This type of spectrum is called line spectrum or atomic
spectrum. For example on heating sodium chloride or any other salt of sodium in Bunsen flame
bright yellow light is emitted. The emitted light when viewed through a spectroscope two isolated
yellow lines separated by dark space are obtained. The wave lengths of these lines are 5890Å and
5896Å.

2. Absorption spectrum
When the white light of an incandescent substance is passed through any other substance, this
substance absorbs the radiations of certain wavelength from the white light. On analysing the
transmitted light we obtain a spectrum in which dark lines of specific wave lengths are observed.
These lines constitute the absorption spectrum. The wave length of the dark lines correspond to
the wavelength of light absorbed.

13. MAXWELL THEORY OF ELECTROMAGNETIC WAVE


(i) All the radiations have wave nature which explains interference (linear superposition) and diffraction.
(ii) They consist of oscillating electric and magnetic field perpendicular to each other and to the direction of
propagation.
(iii) All the radiations (radio waves, micro waves, infra red waves, visible, UV, X-rays, -rays) travel at the
speed of light in vacuum.
(iv) Energy of electromagnetic wave is proportional to amplitude and not linked with frequency of waves.
Draw backs : This theory could not explain the following
(a) Phenomenon of black body radiations (b) Photoelectric effect (c) Line spectra of atoms

14. PLANCK’S QUANTUM THEORY


According to this theory atoms or molecules could emit or absorb energy only in discrete quantities
(small packets) and not in any arbitrary amount. Planck gave the name quantum to the smallest quantity
of energy that can be emitted in the form of E.M. radiation.
The energy of a photon is proportional to its frequency and is given by
E = h where h = 6.626 × 10–34 Jsec.

A body can emit or absorb energy only in terms of the integral multiples of quantum, i.e.
E = n . h , where n = 1, 2, 3, .......
i.e. a body can emit or absorb energy as h, 2h ....... but it can not emit or absorb energy in fractional
values of h such as 1.5 h, 2.5 h.

Einstein supported the planck’s theory and explained the photoelectric effect considering that
electromagnetic radiations also propagate in the form of photon. Energy of each photon depends on
 hc 
frequency of light  E  h   .
 
Since wave character of light explains the interference and diffraction phenomenon while the particle
character explains, black body radiations and photoelectric effect, the light was considered to have
wave as well as particle character [Dual character of light.]
1. Wave nature : diffraction, interference, polarisation.
2. Particle nature : photoelectric effect.

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ATOMIC STRUCTURE

Illustration
9. (i) What is the energy and wavelength of photons of frequency 3.4 MHz ?
(ii) Also calculate the energy per mole of photons of the same wavelength.
Sol.  = 3.4 MHz = 3.4 × 106 Hz = 3.4 × 106 s–1
c 3 x 108 ms 1
   88.2m
 3.4 x 106 s 1
Energy, E  h = 6.626 × 10-34 × 3.4 × 106 J
= 2.253 × 10-27J
Energy per mole of photon = 6.02 × 1023 × 2.253 × 10 -27 J mol-1
= 1. 356 × 10-3 J mol-1

10. The vapours of Hg absorb some electrons accelerated by a potential diff. of 4.5 volt as a result of which
light is emitted. If the full energy of single incident e is supposed to be converted into light emitted by
single Hg atom, find the wave no. of the light.
hc hc
Sol. E = e.V =  = = 3.63 ×106 m–1
 e.V

15. PHOTOELECTRIC EFFECT


Emission of electrons from a metal surface when exposed to light radiations of appropriate wavelength is
called photoelectric effect. The emitted electrons are called photoelectrons.
Incident Energy
light of electron
= 1/2 mv2

Electron Metal

Work function or threshold energy may be defined as the minimum amount of energy required to eject
electrons from a metal surface.
According to Einstein,
Maximum kinetic energy of the ejected electron = absorbed energy - work function

1 1 1 
mv2max = hv – hv0 = hc   
2   0 

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

Stopping potential : The minimum potential at which the photoelectric current becomes zero is called
stopping potential.
If V0 is the stopping potential , then

h    0  K.E.max .
eV0 = h (v – v0) or V0 = 
e e

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Some facts of Photoelectric Effect


(i) There is no time lag between incidence of light and emission of photoelectrons.
(ii) For emission of photoelectrons, the frequency of incident light must be equal to or greater than the
threshold frequency.
(iii) Rate of emission of photoelectrons from a metal surface is directly proportional to the intensity of
incident light.
(iv) The maximum kinetic energy of photoelectrons depends on the frequencyof incident radiation; but, it is
independent of the intensity of light used.

KE of K.E. of
photo electrons
photoelectrons

v0 v
Frequency of absorbed photons Intensity of
incident radiation

Illustration
11. The minimum energy required to overcome the attractive forces electron and surface ofAg metal is 7.52
× 10– 19 J. Calculate the maximum K.E. of electron ejected out fromAg which is being exposed to U.V.
light of  = 360 Å
hc
Sol. Energy absorbed =

6.62  10 27  3.0  10 10
=
360  10  8
= 5.52 × 10–11 erg
= 5.52 × 10–18 Joule
Maximum kinetic energy of electron= ( 7.52 × 10–19) – (0. 552 × 10–19)
= 6.968 × 10–19 Joule
12. A metal was irradiated by light of frequency 3.2 × 1015 s1. The photoelectron produced had its KE,
2 times the KE of the photoelectron which was produced when the same metal was irradiated with a
light of frequency 2.0 ×1015 S1. What is work function.
Sol. E1 = hv1–0, E2 = hv2 – 0
E1 hv1  0 h  3.2  1015  0

E 2 hv 2  0 , 2 = h  2  1015  0
0 = 319.2 KJ/Mol

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ATOMIC STRUCTURE

16. BOHR'S ATOMIC MODEL


This model was based on the quantum theory of radiation and the classical law of physics. It gave new
idea of atomic structure in order to explain the stability of the atom and emission of sharp spectral lines.
16.1 Postulates
(i) The atom has a central massive core nucleus where all the protons and neutrons are present. The size of
the nucleus is very small.
(ii) The electron in an atom revolve around the nucleus in certain discrete orbits. Such orbits are known as
stable orbits or non - radiating or stationary orbits.
(iii) An electron can move only in those permissive orbits in which the angular momentum (mvr) of the
electron is an integral multiple of h/2 Thus,
h
mvr  n
2
where, m = mass of the electron, r = radius of the electronic orbit, v = velocity of the electron in its orbit.
h 2h 3h nh
(iv) The angular momentum can be , , ,...... . This principal is known as quantization of angular
2  2 2 2
momentum. In the above equation 'n' is positive integer which has been called as principal quantum
number. It can have the values n=1,2,3, ------- (from the nucleus). Various energy levels are designed as
K(n=1), L(n=2), M(n=3) ------- etc. Since the electron present in these orbits is associated with some
energy, these orbits are called energy levels.
(v) The emission or absorption of radiation by the atom takes place when an electron jumps from one
stationary orbit to another.

Electrons excited
by absorbing
energy
(Energy absorbed)

Nucleus
Energy radiated
n=1 when electrons
(K) n = 2 fall back
(L) n = 3 (Energy emitted)
(M) n = 4
(N) n = 5 n = 6
(O)
(P)

(vi) The radiation is emitted or absorbed as a single quantum (photon) whose energy is equal to the difference
in energy of the electron in the two orbits involved. Thus, E  h , where h =Planck's constant and v,
frequency of the radiant energy. Hence the spectrum of the atom will have certain fixed frequency.
(vii) The lowest energy state (n=1) is called the ground state. When an electron absorbs energy, it gets
excited and jumps to an outer orbit. It has to fall back to a lower orbit with the release of energy.

16.2 Advantage of Bohr's theory


(i) Bohr's theory satisfactorily explains the spectra of species having one electron, viz. hydrogen atom,
He  , Li 2 etc.
(ii) 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 is charge) with a tangential / linear velocity of ‘v’. Further consider
that ‘r’ is the radius of the orbit in which electron is revolving.
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According to Coulomb’s law, the electrostatic force of attraction (F) between the moving electron
and nucleus is -
KZe 2
F =
r2
1
Where : K = constant = = 9 × 109 Nm2/C2
4  0

mv 2
and the centripetal force F=
r

mv 2 KZe 2
Hence =
r r2

KZe 2
or, v2 = …(1)
mr
From the postulate of Bohr,
nh
mvr=
2

n 2h 2
or, v2 = …(2)
4 2m 2r 2
From equation (1) and (2) :
n 2h 2
 r =
4 2mKZe 2

On putting the value or e, h, m,


n2
r  0.529  Å
Z

(iii) Calculation of velocity of an electron in Bohr’s orbit :


Velocity of the revolving electron in nth orbit is given by –
nh nh
mvr = v=
2 2mr

Putting the value of r in above equation


nh  4  2mZe 2
then v=
2mn 2h 2

2Ze 2
v
nh
on putting the values of e and h,
Z
v  2.188  10 6  m / sec
n

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ATOMIC STRUCTURE
(iv) Calculation of energy of an electron :
The total energy of an electron revolving in a particular orbit is -
T. E. = K. E. + P. E.
1
The K.E. of an electron = mv2
2

KZe2
and the P.E. of an electron = –
r

1 KZe 2
Hence, T.E. = mv2 – .........(3)
2 r

mv 2 KZe 2 KZe 2
But = or mv2 =
r r2 r
Substituting the value of mv2 in the equation (3)
KZe 2 KZe 2 KZe 2
T.E. = – =–
2r r 2r
KZe 2
So, T.E. = –
2r
Substituting the value of ‘r’ in the equation of T.E. .

kZe2 4 2 Ze 2 mk 2 2 Z 2 e 4 mk 2
E =  × =–
2 n 2h 2 n 2h 2
Thus, the total energy of an electron in nth orbit is given by

2 2 Z 2 e 4 mk 2
En =
n 2h 2

Z2
= – 13.6 × eV / atom
n2

Z2
= – 21.8 × 10–19 × J / atom
n2

Z2
= – 313.6 × Kcal / mole
n2

(v) Relation between P. E., K. E. & T. E. :

All the above relationships between Total Energy, Kinetic Energy and
Potential Energy are applicable when P.E. at infinity is assigned as zero.
Can you guess what will be the changes if this reference value is changed
to something else?
kZe 2 1 kZe 2 1 kZe 2
P. E. = – , K. E. = , T. E. = –
r 2 r 2 r
P.E.
T.E.   –K.E.
2

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(vi) Calculation of the number of revolutions of the electron in an orbit per second
velocity of the electron
Number of revolutions per sec. = Circumference of the orbit

v nh 1 nh
= = × [On substituting the value of v from mvr = ]
2r 2mr 2r 2

nh
=
42 mr 2
2
nh nh  4 2 mze 2 k 
× 
4  2 m  n h
No. of revolutions per second = = 2 2
42 mr 2 
4 2 mz 2 e 4 k 2
=
n 3h 3
3 3
42 mr 2 nh
Time taken for one revolution (Time period) = =
nh 4 2 mz 2 e 4 k 2
Illustration
13. The radius of an orbit of hydrogen atom is 0.85 nm. Calculate the velocity of electron in this orbit.
Sol. r = r0 n2 n2 = 16,
n=4
Z 1
V = V0. = 2.186 × 106 × = 5.44 × 105 m/s
n 4
14. The energy of an excited H-atom is –3.4 eV. Calculate angular momentum of e– in the given orbit.
Z2 13.6
Sol. E = – 13.6 2  n2 = 4
n 3 .4
n=2
nh h
Angular momentum = mvr = =
2 
15. Ionisation energy of hydrogen atom is 13.6 eV. Calculate the ionisation energy for Be3+ in the first
excited state.
Sol. Ionization energy of hydrogen = - E1 ( Energy of first Bohr orbit )
 Z2  12
I.E.   E1    13.6 2   13.6  2  13.6 eV
 n  1
Ionization energy of Be3+
Z =4
n =2 ( for 1st excited state )
 42 
I.E.  13.6 2   54.4 eV
 2 

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16.3 Hydrogen Spectrum
Hydrogen spectrum is an example of line or atomic emission spectrum. When an electric discharge is
passed through hydrogen gas at low pressure, a bluish light is emitted. This light shows discontinuous line
spectrum of several isolated sharp lines through prism.All these lines of H-spectrum have Lyman, Balmer,
Paschen, Brackett, Pfund and Humphrey series. These spectral series were named by the name of
scientist discovered them. To evaluate wavelength of various H-lines Rydberg introduced the following
expression,

1  1 1
   R 2  2 
 c  n1 n 2 
Where R is a constant known as Rydberg's constant its value is 109, 67800 m–1 .
Although H- atom consists only one electron yet it's spectra consist of many spectral lines because
electrons in different hydrogen atoms absorb different amount of energies and are excited to
different energy levels. Since life time of electrons in these excited states is very small, they return
to some lower energy level or even to the ground state in one or more jumps
P

N
Paschen
series
M

K
Balmer
series
Brackett
series

Pfund
series

Lyman
series

n n  1
Maximum number of lines produced when an electron jumps from nth level to ground level = .
2
(A) Lyman Series
(a) It is a first series of spectral series of H.
(b) It was found out in ultraviolet region in 1898 by Lyman.
(c) It’s 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.
(d) If the electron goes to n1 = 1 from n2 = 2 — first Lyman series
If the electron goes to n1 = 1 from n2 = 3 — Second Lyman series
If the electron goes to n1 = 1 from n2 = 4 — third Lyman series ----- so on.
1 1LM 1 OP
(e)   R H 12  2 where n2 > 1 always.
N n2 Q

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n12
(f) For marginal line or limiting line n2 =  . Hence the wavelength of marginal line = for all series.
RH
1
So, for lyman series it is
RH
(B) Balmer series :
(a) It is the second series of H-spectral series.
(b) It was found out in 1892 in visible region by Balmer.
(c) Balmer series was found out before all series because it was found in visible region.
(d) It’s value of n1 = 2 and n2 = 3, 4, 5 ...........
(e) If the electron goes to n1 = 2 from n2 = 3 — First Balmer series
If the electron goes to n1 = 2 from n2 = 4 — Second Balmer series
If the electron goes to n1 = 2 from n2 = 5 — third Balmer series .... so on
2
n1 22 4
(f) The wavelength of marginal line of Balmer series =  
RH RH RH
1 F
1 1 I
(g)
 GH
 RH 2  2
2 n2
JK where n2 > 2 always

(C) Paschen series :


(a) It is the third series of H - spectrum.
(b) It was found out in infra red region by Paschen.
(c) It’s value of n1 = 3 and n2 = 4, 5, 6 ............
(d) If the electron goes to n1 = 3 from n2 = 4 — First paschen series
If the electron goes to n1 = 3 from n2 = 5 — second paschen series
If the electron goes to n1 = 3 from n2 = 6 — third paschen series ------ so on.
2
n1 32 9
(e) The wavelength of marginal line of paschen series =   .
RH RH RH

1 1LM 1
 RH 2  2
OP
(f)
 N
3 n2 Q where n2 > 3 always.

(D) Brackett series :


(a) It is fourth series of H - spectrum.
(b) It was found out in infra red region by Brackett.
(c) It’s value of n1 = 4 and n2 = 5, 6, 7 ................
(d) If the electron goes to n1 = 4 from n2 = 5 — first brackett series
If the electron goes to n1 = 4 from n2 = 6 — second brackett series
If the electron goes to n1 = 4 from n2 = 7 — third brackett series ------ so on.
n12 42 16
(e) The wavelength of marginal line of brackett series =  
RH RH RH

1 1 LM 1 OP
(f)   R H 4 2  2
N n2 Q Where n 2 > 4 always.

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(E) Pfund series :


(a) It is fifth series of H - spectrum.
(b) It was found out in infra red region by Pfund.
(c) It’s value of n1 = 5 and n2 = 6, 7, 8 ...............
(d) If the electron goes to n1 = 5 from n2 = 6 — first Pfund series
If the electron goes to n1 = 5 from n2 = 7 — second Pfund series
If the electron goes to n1 = 5 from n2 = 8 — third Pfund series -----so on.
n12 52 25
(e) The wavelength of marginal line of Pfund series =  
RH RH RH
1 1 LM
1 OP
(f)   R H 52  2
N
n2 Q where n2 > 5 always.

(F) Humphrey series :


(a) It is the sixth series of H - spectrum.
(b) It was found out in infra-red region by Humphrey.
(c) It’s value of n1 = 6 and n2 = 7, 8, 9 ---------
(d) If the electron goes to n1 = 6 from n2 = 7 — first Humphrey series
If the electron goes to n1 = 6 from n2 = 8 — second Humphrey series
If the electron goes to n1 = 6 from n2 = 9 — third Humphrey series ... so on.

1 n2 62 36
(e) The wavelength of marginal line of Humphrey series = R  R  R
H H H

1 LM 1 1 OP
(f)   RH 6 2  n2 where n2 > 6.
MN 2 PQ
Note :  - line = first line of series.
Similarly -line = second line of series
For example : First line (-line) of Paschen series will be from n2 = 4 to n1 = 3

16.4 Calculation of Rydberg Constant from bohr’s atomic model


Suppose that an electron transist from first energy level to second energy level. Then, the change
of energy is given by
E = E n 2 – E n1

  2 2 mZ2e 4 k 2    2 2 mZ2e 4 k 2  hc  2 2 mZ2 e 4 k 2 LM 1 1 OP


or, =   –  or, = × n2 – n2
 n 22 h 2   n12 h 2   h 2
MN1 2 PQ
1 2 2 mz 2e 4 k 2 1 1  1 1 
or,   2  2  = RH.Z2  2  2 
 ch 3  n1 n 2   n1 n 2 

2 2 me 4 k 2
or, RH = = Rydberg constant
ch 3

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Illustration
16. Calculate the wavelength of radiation emitted, producing a line in Lyman series, when an electron falls
from fourth stationarystate in hydrogen atom.

1 1 1
Sol. = RZ2  2
 2
  n1 n 2 

1 1 1 
=R  2  2 (For H-atom, Z = 1, Lyman series; n1 = 1)
 1 4 
 = 9.7 × 10–8 m

17. Calculate the wave no. for the shortest wavelength transition in the Balmer series of atomic hydrogen.
Sol. For shortest wavelength n2  
1 1  R
V  R 2  2  = = 27419.25 cm–1
2   4

18. Calculate the energy emitted when electrons of 1.0 gm atom of Hydrogen undergo transition
giving the spectral lines of lowest energy in visible region of its atomic spectra. Given that , RH = 1.
1 × 107 m-1, c = 3 × 108 m / sec, h = 6. 625 × 10-34 J sec.
Sol. Visible region of H- spectrum correspond to Balmer series n1 = 2, n2 = 3 (for minimum energy
transition )
1 1 1 1 1
1 /   R H  2  2    R H  2  2    1.110 7   
1 1 1
 n1 n 2   2 3   4 9
[RH = 109677 cm–1 = 109677 × 100 m–1  1.1 107 m–1]

  6.55x107 m
hc 6.625x10 34 x3x108
E  = 3. 03 × 10-19 Joule
 6.55x10 7
 Energy released by 1 gm atom of H ( 1 mol )
= 3. 03 × 10-19 × 6. 023 × 1023 = 18 . 25 × 104 J = 182. 5 k J
16.5 Failure of Bohr Model
(i) Bohr theorywas very successful in predicting and accounting the energies of line spectra of hydrogen
i.e. one electron system. It could not explain the line spectra of atoms containing more than one electron.
(ii) This theory could not explain the presence of multiple spectral lines.
(iii) This theory could not explain the splitting of spectral lines in magnetic field (Zeeman effect) and in
electric field (Stark effect). The intensity of these spectral lines was also not explained by the Bohr
atomic model.
(iv) This theory could not explain uncertainty principle.

17. PARTICLE AND WAVE NATURE OF ELECTRON


In 1924, de Broglie proposed that an electron, like light, behaves both as material particle and as a
wave. This proposal gave a new theory, known as wave mechanical theory of matter.According to this
theory, the electrons, protons and even atoms, when in motion, posses wave properties.
de Broglie derived an expression for calculating the wavelength of the wave associated with the electron.

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According to Planck’s equation


c
E = hv = h. ..........(1)

The energy of a photon on the basis of Einstein’s mass-energy relationship is
E = mc2 ..........(2)
where, c is the velocity of the electron.
From (1) and (2) equation
c
h× = mc2

h h
=  ...........(3)
mc p
Momentum of the moving electron is inversely proportional to its wavelength.
Let kinetic energy of the particle of mass ‘m’ is E.
1
E= mv2
2
2Em = m2v2
2Em = mv = p (momentum)
h h
=  ...........(4)
p 2Em
Let a charged particle, with charge q be accelerated with a potential of V; then the kinetic energy may be
given as : E = qV
1
mv2 = qV
2
m2v2 = 2qVm
mv = 2qVm
h
and, = 2qVm ................(5)

(A) de Broglie wavelength associated with charged particles


12.27
For electron :  Å
V
0.286
For proton : = Å
V
0.101
For  - particles :  Å
V
where, V = accelerating potential of these particles

(B) de Broglie wavelength associated with neutron


h 6.62  10 34 0.286
For neutron : =  =
2Em 2  1.67  10  27  E EeV  Å

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The wavelength decreases if the value of mass (m) increases i.e. de Broglie equation is applicable in the
case of smaller particles like electron and has no significance for larger particles.

Derivation of Angular Momentum from de Broglie Equation:


According to Bohr's model, the electron revolves around the nucleus in circular orbits.According to de
Broglie concept, the electron is not onlya particle but also has a wave character . If the wave is completely
in phase, the circumference of the orbit must be equal to an integral multiple of wave length ().
2r = n
where 'n' is an integer and 'r' is the radius of the orbit
But  = h/mv
 2r = nh /mv
or mvr = nh / 2
which is Bohr's postulate of angular momentum, where 'n' is the principal quantum number.
"Thus, the number of waves an electron makes in a particular Bohr orbit in one complete revolution is
equal to the principal quantum number of the orbit".

Illustration
19. What is de Broglie wavelength for a hydrogen atom moving with a velocity of 2000 ms-1 ? (Atomic
mass of hydrogen = 1. 00797 a.m. u )
1.0097
Sol. Mass of a hydrogen atom = g = 1.68 × 10–24 g = 1.68 × 10–27 kg
6.02 1023

h 6.62 10 34


  = 1.97 × 10–10 m
mv 1.68  1027  2000

18. HEISENBERG’S UNCERTAINTY PRINCIPLE


(a) While treating e– as a wave it is not possible to ascertain simultaneously the exact position and
velocity of the e– more precisely at a given instant since the wave is extending throughout a region
of space
(b) As the photons of longer wavelengths are less energetic, hence they have less momentum and
cannot be located exactly
(c) In 1927, Warmer Heisenberg presented a principle known as Heisenberg’s uncertainty principle
(d) According to this principle it is impossible to measure simultaneously the exact position and exact
momentum of a body as small as an electron.
(e) If uncertainty of measurement of position is x and uncertainty of measurement of momentum is
p or mv, then according to Heisenberg
h h
x . p  or x . mv 
4 4
where h is planck’s constant
(f) For other conjugates of motion the equation for Heisenberg’s uncertainty principle may be given
as
h
E. t  (for energy and time)
4
(g) Like de Broglie equation, this principle has significance only for microscopic particles.

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Illustration
6.62
20. An electron having velocity 2 × 106 m/s has uncertainty in kinetic energy is × 10– 21 J, then

calculate the uncertainty in position (inAngstrom, Å) of the electron. [Given : h = 6.62 × 10–34 J-sec]
1
Sol. KE= mv2 v = 2 × 106 m/s
2
d(KE) = mvdv
d( KE ) h
dv = ....(1) But x = 4 m v ....(2)
mv

h 6.62  10 34  2  10 6
x = ; x = = 500 Å
d (KE ) 6.62
4 m 4   10  21
mv 

19. WAVE MECHANICAL MODEL OF ATOM


The atomic model which is based on the particle and wave nature of the electron is known as wave
mechanical model of the atom. This was developed byErwin Schrodinger in 1926. This model describes
the electron as a three-dimensional wave in the electronic field of positivelycharged nucleus. Schrodinger
derived an equation which described wave motion of an electron. The differential equation is :

d 2 d 2 d 2 82 m
+ + + (E – V)  = 0
dx 2 dy 2 dz 2 h2

Where x, y and z are cartesian coordinates of the electron; m = mass of the electron; E = total energy of
the electron; V= potential energy of the electron; h = Planck’s constant and (psi) = wave function of
the electron.

Significance of  : The wave function may be regarded as the amplitude function expressed in terms of
coordinates x, y and z. The wave function may have positive or negative values depending upon the
values of coordinates.

The main aim of Schrodinger equation is to give a solution for the probability approach. When the
equation is solved, it is observed that for some regions of space, the value of  is positive and for other
regions the value of  is negative. But the probabilitymust be always positive and cannot be negative. It
is, thus, proper to use 2 in favour of .

Significance of 2 : 2 is a probability factor. It describes the probability of finding an electron within


a small space. The space in which there is maximum probability of finding an electron is termed as
orbital.
The important point of the solution of this equation is that it provides a set of number, called quantum
numbers, which describe energies of the electrons in atoms, information about the shapes and orientations
of the most probable distribution of electron around the nucleus .
Wave function  can be plotted against distance ‘r’from nucleus as,

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1s
 
3s
2p

Node Node
2s 3p

For hydrogen wave function, number of nodes can be calculated as,


(i) Number of radial nodes = (n – l – 1)
(ii) Number of angular nodes = l
(iii) Total number of nodes = (n –1)

Examples : (i) For 1s – orbital n = 1, l = 0, it will have no radial or angular node


(ii) For 2s–orbital, n = 2, l = 0, it will have only one radial node
(iii) For 3s-orbital, n = 3, l = 0, it will have two radial nodes
(iv) For 2p-orbital, n = 2, l = 1, it will have no radial node but it has only one angular node
(v) For 3p-orbital, n = 3, l = 1, it will have one radial and one angular node

Solution of Schrodinger wave equation :


In spherical co-ordinates (x, y, z) is represented by  (r, , ) such that complete wave function can
be given as
R r  
 (r, , ) =    
Radial part Angular part

Dependance of the wave function on quantum number can be given as,


nlm (r, , ) = Rnl (r) lm ()  m ()
Radial wave function angular wave function
The function R depend only on r, therefore they describe the distribution of the electron as a function of
r from the nucleus. These functions depend upon two quantum numbers, n and l. The two functions 
and  taken together give the angular distribution of the electron.
The radial part the wave function for some orbitals may be given as,

n l Rnl
3/ 2
Z
1s 1 0 2   e  zr / a 0
 a0 
3/ 2
 Z   Zr 
2s 2 0    2  e zr / 2a 0
2a
 0  a0 

3/ 2
1  Zr   Zr  Zr / 2a 0
2p 2 1    e
3 2a
 0  a0 
where, Z = atomic number, a0 = radius of first Bohr orbit of hydrogen.

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19.1 Probability Distribution Curve


It is found that wave functions () can be expressed as the product of two functions, one of which the
radial part R(r) depends only on the distance from the nucleus, the other being the angular part depends
only on the angles  & .
 (r, , ) = R (r) ×f ( , )
Radial wave function angular wave function
Hence, Probability distribution curves which give the variation of probability of finding the electron can
also be classified into two types (i) one which give the variation of probabilityof finding the electron with
radial distance (r), termed as radial probability distribution curves, and (ii) and one which give the
variation of probability of finding the electron with angle keeping the radial distance same ( &  ).
Let us understand each of them separately.

19.2 Radial Probability distribution curves


We had earlier studied that  2r gives the radial probability density of finding an electron at a point. It
refers to the radial probability of finding an electron in a unit volume in an atom at a radial distance of r
from the nucleus. Hence, total radial probability in a spherical shell of thickness dr at a radial distance of
r from the nucleus (which will have a volume of 4r2dr) is given by 4r2  2r dr. Sometimes,  2r is often
represented as R2.

Calculation of Radial probability distribution function


As stated above, the radial probability density at a radial distance r is R2(r). Therefore radial probability
of finding the election in a volume dv will be R2(r) dv.
The radial probability is the probability of finding the election in a radial shell between spheres of radii r
and r + dr, where dr is small radial distance.
4 4
Volume of spherical shell of thickness dr  (r  dr)3   r3
3 3

dr

4 4 3 2 2
  r 3  (dr)3  3rdr(r  dr)  r 3  =  [(dr )  3r dr  3r (dr ) ]
3 3
Since dr is very small, so the terms can be neglected.
4
 dv    3r 2dr  4r 2dr
3
Radial probability of finding an e– in a shell of thickness dr at a distance 'r'
= R2 (r)  4r 2dr ; = 4r 2R2 (r)dr Radial distribution function.

Radial Probability Density curves are between  2r vs r whereas Radial Probability Distribution curves
which would be more useful are between 4r2  2r vs r..

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Can you determine what would be the area under the curve for Radial Probability
Distribution Curves?

RADIAL PART OF HYDROGEN ATOM WAVE FUNCTIONS.


2 / 2
1. For 1s, R(r) = a 3 / 2 e
0

h2 2r
Where a0 = constant =  Bohr radius  0.529 Å & 
4 2mke 2 na 0 , For 1 s, n = 1.
1
2. For 2 s, R(r) = 3/ 2
(2  )e  / 2 [n  2]
2 2a 0

1
3. For 3 s, R(r) = 3/ 2
(6  6  2 )e  / 2 [n = 3]
9 3a 0

1
4. For 2 p, R(r) = 3/ 2
 e  / 2 [n  2]
2 6a 0

1  / 2
5. For 3 p, R(r) = 9 6 a3 / 2 (4  ) e [n  3]
0

1 2  / 2
6. For 3 d, R(r) = 9 30 a 3 / 2  e [n  3]
0

The above wave-functions are not to be remembered. However, after having a


look at the wave-functions above can you devise a general formula for the
expression of the radial component of the wave-functions?

Plot of Radial wave function R(r) for 1 s


2r
2  / 2 2  a 0 2
For 1 s, R(r) = e  e
a 30 / 2 a 30 / 2

2 r / a0
R(r) = a 3 / 2 e . Since this is an exponential function. As r increases, R(r) decreases.
0

R(r) 1s

r (distance from nucleus)

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Can you plot the probability density curves R2(r) and probability distribution
curves 4r2R2(r)

Can you find the radial distance where radial probability will be maximum

Plot of Radial wave function R(r) for 2 s:


2r
1  / 2 1  2r   2a0  2
(2  ) e 2 e
For 2 s, R(r) = = 3/ 2 
2 2 a 30 / 2 2 2 a0  2  a0 
r
1  r  2a0
=  2  e
2 2 a 03 / 2  a0 

node
R(r)

node (Radial)

r
Note that 2a appears in the exponential and shows that as r increases, the
0

r
R(r) function in 2 s decreases more slowly than, does for 1 s, which has
in the
a
exponential that why 2s electron tends to stay farther from the nucleus, and
has higher energy than does the 1 s - electron. The pre-exponential factor
 r 
 2   in the function R(r) for 2 s controls the sign of the function. For small
 a0 

r r
values of r, a is smaller than 2, and R(r) is +ve, but for larger values of r, a is
0 0

greater than 2 and the function is negative.

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 r 
At r = 2a0, the factor  2   zero and the radial function R(r) becomes zero, this is called as radial
 a0 
node.
Similarlyfor 3 s:

nodes (radial)

3s

R(r)
Two radial nodes

In general, for an ns-orbital, there are (n - 1) radial nodes. The point (at a
finite distance from nucleus) at which the probability of finding the electron
is zero is called a nodal point.

Plot of radial wave function R(r) for 2 p :


1 1 2r 2r
For 2 p, R(r) =  e  / 2 =  e
2 6a 0 3 /2
2 6a0 3/ 2
2  a0 2a 0  2

1 r  r 1
= e = r e r / 2a 0
2 6a0 3 /2
a0 2a0 2 6a0 5/ 2

R(r)

2p There is no radial node

For 3 p :

R(r)

node

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Plot of radial wave function R(r) for 3 d:


2 1 2r
1  2r   2 3a0 4 r
For 3 d, R(r) =    e ; = r 2e
81 30 a 0 7/2
3a0
9 30a0 3 / 2  3a 0 

R(r)

3d (There is no node)

Comparison between 3 s, 3 p and 3d orbitals:

3s

rmax

3p
4r2 R2

rmax

3d
3d (There is no node)

rmax r

1. For the same value of n, the distance of max probability, rmax of various orbitals is inversely dependent
upon the value of .
 , rmax 
(rmax )3 s  (rmax )3p  (rmax )3d

2. Penetration power of an orbital is a measure of its closeness to the nucleus. Due to the additional
maximas in 3 s curve, electron in 3 s spends some of its time near the nucleus making it to be more
penetrating than 3 p which in turn more penetrating than 3 d.
3s 3p 3d

Decreasin g order of penetration power 

Important points to note about the 4 r2R2 vs. r plots:


(i) Radial probability is ALWAYS SMALLnear the nucleus (4r2 small near the nucleus).
(ii) The maximum in the 4r2R21s vs. r plot occurs at 0.53Å - just the radius of the n=1 orbit of the Bohr
model.
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(iii) On the average a 2s electron spends its time a greater distance from the nucleus than the 1s electron -
consistent with the observation that (r1s)max < ( r2s)max
(iv) The position of the principal (i.e. largest) maximum depends on n and l. For fixed l, as n increases the
position of the principal maximum moves to larger r values. (For fixed n, the position of the principal
maximum moves to shorter r values as l increased.)

i.e., (r2p)max < (r2s)max ; (r3d)max < (r3p)max < (r3s)max ; r2p max < ( r3p) max

Summary of Radial Probability Density and Radial Probability Distribution Curves

1s 2s 2p

R(r) R R

node

r r
r

R2 R2 R2

node

r r r

(3 s) (3 s) (3 s)

2
R(r) R (r)
nodes 4 2 r 2R 2

r r r

(3 p) (3 p) (3 p)

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2
R(r) R (r)
4 2r 2R2 (r)

r r
r

(3 d) (3 d) (3 d)

R(r) R(r) R(r)

r r r

4 2r 2R 2 (r) 4 r 2R 2 4 2r 2R 2
node

0.529 A r
r r
Bohr rdius
= 0.529 A

19.3 Plots of Angular wave functions


Angular probability density f2 (, ) determines the shape of orbitals and its orientation in space f (, )
for s-orbitals does not depend upon angles & , for all other orbitals f (, ) will be a function in terms
of & . The angular probability density curves are same as the shape and orientation of the orbital in
space.

 Elengated
 Spherical
two lobes
 two lobes

f 2 (, ) f 2 (, )

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Angular nodes (Nodal Planes) :


Total no. of angular nodes for any orbital = 
For s orbital there will be no angular node.

 px
For px orbital,  = 1  no. of angular nodal = 1 (yz plane)
For py orbital, nodal plane (xz plane)
For pz orbital, nodal plane (xy plane)
For dxy orbital,  = 2 therefore 2 nodal planes
z

d xy
Nodal planes: xz & yz planes
For dyz orbital : xy & xz planes are nodal planes.

d x22 - yy22
for dx Y

For dzx orbital : xy & yz planes are nodal planes.


y

nodal planes
x

Can you guess where will be the two angular nodes for d z 2 located ?

no. of radial nodes = n –  – 1


no. of angular nodes = 
total no. of nodes = n –  – 1 + 
= (n – 1)
No. of peaks in  2r vs r curve is (n – )

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20. QUANTUM NUMBERS


(a) The measurement scale by which the orbitals are distinguished, can be represented by sets of
numbers called as quantum number.
(b) Quantum numbers are to specify and display to complete information about size, shape and
orientation of the orbital. These are principle, azimuthal and magnetic quantum number, which
follows directly from solution of schrodinger wave equation.
(c) Except to these quantum numbers, one additional quantum number designated as spin quantum
number, which specify the spin of electron in an orbital.
(d) Each orbital in an atom is specified by a set of three quantum numbers and each electron is
designated by a set of four quantum numbers.
20.1 Principal quantum number (n) :
(a) It was proposed by Bohr and denoted by ‘n’.
(b) It determines the average distance between electron and nucleus, means it denotes the size of atom.
(c) It determine the energy of the electron in an orbit where electron is present.
(d) The maximum number of an electron in an orbit represented by this quantum number as 2n2.
(e) It gives the information of orbit K, L, M, N, ...
(f) The value of energy increases with the increasing value of n.
(g) It represents the major energy shell from which the electron belongs.

20.2 Azimuthal quantum number or angular quantum number (l) -


(a) It was proposed by Sommerfield and denoted by ‘l’.
(b) It determines the number of subshells or sublevels to which the electron belongs.
(c) It tells about the shape of subshells.
(d) It also expresses the energies of subshells s < p < d < f (Increasing energy).
(e) The value of l is integral values upto (n – 1), starting from zero where ‘n’ is the number of principle
shell.
(f)
Value of l 0 1 2 3
Name of s p d f
subshell

Shape of spherical Dumbbell Clover leaf Complex


orbital (Except d z 2
doughtnut)
h
(g) It represent the orbital angular momentum, which is equal to (   1) .
2
(h) The number of electrons in subshell = 2(2l + 1).
(i) For a given value of ‘n’ the total value of ‘’ is always equal to the value of ‘n’ .

20.3 Magnetic quantum number (m) :


(a) It was proposed by Linde and denoted by ‘m’.
(b) It gives the number of permitted orientation of subshells.
(c) The value of m varies from – l to + l through zero.
(d) It tells about the splitting of spectral lines in the magnetic field i.e. this quantum number proved the

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Zeeman effect.
(e) For a given value of ‘n’ the total value of ‘m’ is equal to n2.
(f) For a given value of ‘l’ the total value of ‘m’ is equal to (2l + 1).
(g) Degenerate orbitals - Orbitals having the same energy are known as degenerate orbitals.
e.g. for p subshell Px, Py and Pz are degenerate orbital
(h) The number of degenerate orbitals of s subshell = 0.

20.4 Spin quantum number (s) :


(a) It was proposed by Goldshmidt & Uhlenbeck and denoted by the symbol of ‘s’.
Magnetic field

N S

+ 1/2 –1/2

S N

(b) The value of ‘s’is + ½ or – ½, which is signified as the spin or rotation or direction of electron on it’s axis
during the movement.
(c) The spin may be clockwise or anticlockwise.
h
(d) It represents the value of spin angular momentum which is equal to s( s  1) .

(e) Maximum spin of an atom = ½ × number of unpaired electron.

Illustration
21. The correct order of atomic orbitals in terms of energy between 8s and 8p orbital are
(A) 7d, 6f (B*) 5g, 6f, 7d (C) 6d, 7f (D) 4h, 5g, 6f, 7d
Sol. (n+l): 8s  8 + 0 = 8
8p  8 + 1 = 9
5g  5 + 4 = 9
6f  6 + 3 = 9
7d  7 + 2 = 9
correct order  8s 5g 6f 7d 8p
22. Which of the following set of quantum number is valid/invalid. In case of valid set write the symbol of the
orbital it represents [may have more than one answers] & in case it is invalid mention the reason.
n l m
(i) 3 not known 0
(but less than 3)
(ii) –2 –1 +1
(iii) 4 2 –1
Sol. (i) Valid, 3s/3px/3py/3pz/ 3d 2 2 / 3d 2 /3dxy/3dxz/3dyz
x y z
(ii) Invalid 'n' cannot be negative
(iii)Valid 4d 2 2 / 4d z2 /4dxy/4dxz/4dyz
x y

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ATOMIC STRUCTURE

21. SHAPE AND SIZE OF ORBITALS


An orbital is the region of space around the nucleus within which the probability of finding an electron of
given energy is maximum (90-95%). The shape of this region (electron cloud) gives the shape of the
orbital. It is basically determined by the azimuthal quantum number l, while the orientation of orbital
depends on the magnetic quantum number (m).

21.1 s-orbital (l = 0) : These orbitals are spherical and symmetrical about the nucleus. The probability of
finding the electron is maximum near the nucleus and keeps on decreasing as the distance from the
nucleus increases. There is vacant space between two successive s-orbitals known as radial node. But
there is no radial node for 1s orbital since it is starting from the nucleus.
The size of the orbital depends upon the value of principal quantum number (n). Greater the value of n,
larger is the size of the orbital. Therefore,
2s-orbital is larger than 1s orbital but both of them are non-directional and spherically symmetrical
in shape.
21.2 p-orbital (l = 1): The probability of finding the p-electron is maximum in two lobes on the opposite
sides of the nucleus. This gives rise to a dumb-bell shape for the p-orbital. For p-orbital l = 1.
Hence, m = -1, 0, +1. Thus, p-orbital have three different orientations. These are designated as
px, py & pz depending upon whether the density of electron is maximum along the x y and z axis
respectively. As they are not spherically symmetrical, they have directional character. The two lobes
of p-orbitals are separated by a nodal plane, where the probability of finding electron is zero.
The three p-orbitals belonging to a particular energy shell have equal energies and are called
degenerate orbitals.
21.3 d-orbital (l = 2):
For d-orbitals, l = 2. Hence m = -2,-1, 0, +1, +2. Thus there are 5 d-orbitals. They have relatively
complex geometry. Out of the five orbitals, the three (dxy, dyz, dzx) project in between the axis and the
other two d z 2 and d x 2  y 2 lie along the axis.
21.4 Spherical nodes : The spherical surface where probability of finding the electron is zero, is called
spherical nodes.
No. of spherical nodes in any orbital = n – l – 1
21.5 Nodal Plane : This is a plane passing through the nucleus where the probability of finding the electron
is zero.
Number of nodal plane in a orbital = l

Orbital Nodal plane


px yz
py xz
pz xy
d xy yz, zx
dyz xy, xz
dzx xy, yz

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ATOMIC STRUCTURE

22. ELECTRONIC CONFIGURATION


The distribution of electrons in different orbitals of atom is known as electronic configuration of the
atoms.
Filling up of orbitals in the ground state of atom is governed by the following rules:

22.1 Aufbau principle


(i) Auf bau is a German word, meaning 'building up'.
(ii) According to this principle, "In the ground state, the atomic orbitals are filled in order of increasing
energies i.e. in the ground state the electrons first occupy the lowest energy orbitals available".
(iii) In fact the energy of an orbital is determined by the quantum number n and l with the help of (n+l)
rule or Bohr Bury rule. According to this rule
(a) Lower the value of n + l, lower is the energy of the orbital and such an orbital will be filled
up first.
(b) When two orbitals have same value of (n + l) the orbital having lower value of "n" has lower
energy and such an orbital will be filled up first .
Thus, order of filling up of orbitals is as follows:
1s  2s  2p  3s  3p  4s  3d  4p  5s  4d  5p  6s  4f  5d
However, in one electron system, orbital of same principal quantum number have same energy,
which is independent of (l). In this system l only determines the shape of the orbital. Energy of
orbitals are
1s < 2s = 2p < 3s = 3p = 3d < 4s = 4p = 4d = 4f

22.2 Pauli's exclusion principle


(i) According to this principle, "No two electrons in an atom can have same set of all the four quantum
numbers n, l, m and s .
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ATOMIC STRUCTURE

(ii) In an atom any two electrons may have three quantum numbers identical but fourth quantum
number must be different.
(iii) Since this principle excludes certain possible combinations of quantum numbers for any two electrons
in an atom, it was given the name exclusion principle. Its results are as follows :
(a) One orbital cannot have more than two electrons.
(b) The maximum capacity of a main energy shell is equal to 2n2 electrons.
(c) The maximum capacity of a subshell is equal to 2(2l + 1) electrons.
(d) Number of sub-shells in a main energy shell is equal to the value of n.
(e) Number of orbitals in a main energy shell is equal to n2
(iv) According to this principle an orbital can accommodate at the most two electrons with spins
opposite to each other. It means that an orbital can have 0, 1, or 2 electron.
(v) If an orbital has two electrons they must be of opposite spin.

Correct Incorrect

22.3 Hund's Rule of maximum multiplicity


(i) This rule provides the basis for filling up of degenerate orbitals of the same sub-shell.
(ii) According to this rule "Electron filling will not take place in orbitals of same energy until all the
available orbitals of a given subshell contain one electron each with parallel spin".
(iii) This implies that electron pairing begins with fourth, sixth and eighth electron in p, d and f orbitals
of the same subshell respectively.
(iv) The reason behind this rule is related to repulsion between identical charged electron present in the
same orbital.
(v) They can minimise the repulsive force between themselves by occupying different orbitals.
(vi) Moreover, according to this principle, the electron entering the different orbitals of subshell have
parallel spins. This keep them farther apart and lowers the energy through electron exchange.
(vii) The term maximum multiplicity means that the total spin of unpaired is maximum in case of correct
filling of orbitals as per this rule.
Spin multiplicity = (no. of unpaired electron + 1)

Electronic configuration of some elements


S.No. Elements Symbol Atomic No. Electronic configuration

(1) Hydrogen H 1 1s1


(2) Nitrogen N 7 1s2 2s2 2p3 or [He] 2s2 2p3
(3) Sulphur S 16 1s2 2s2 2p6 3s2 3p4 or [Ne] 3s2 3p4
(4) Manganese Mn 25 1s2 2s2 2p6 3s2 3p6 3d5 4s2 or [Ar] 3d5 4s2

Exceptional electronic configuration

S.No. Elements Symbol Atomic No. Electronic configuration

(1) Chromium Cr 24 1s2 2s2 2p6 3s2 3p6 3d5 4s1 or [Ar] 3d5 4s1
(2) Copper Cu 29 1s2 2s2 2p6 3s2 3p6 3d10 4s1 or [Ar] 3d10 4s1

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ATOMIC STRUCTURE

Element At.No. 1s 2s 2p 3s 3p 3d 4s 4p 4d 4f 5s 5p 6d 5f
H 1 1
He 2 2
Li 3 2 1
Be 4 2 2
B 5 2 2 1
C 6 2 2 2
N 7 2 2 3
O 8 2 2 4
F 9 2 2 5
Ne 10 2 2 6
Na 11 2 2 6 1
Mg 12 2 2 6 2
Al 13 2 2 6 2 1
Si 14 2 2 6 2 2
P 15 2 2 6 2 3
S 16 2 2 6 2 4
Cl 17 2 2 6 2 5
Ar 18 2 2 6 2 6
K 19 2 2 6 2 6 1
Ca 20 2 2 6 2 6 2
Sc 21 2 2 6 2 6 1 2
Ti 22 2 2 6 2 6 2 2
V 23 2 2 6 2 6 3 2
*Cr 24 2 2 6 2 6 5 1
Mn 25 2 2 6 2 6 5 2
Fe 26 2 2 6 2 6 6 2
Co 27 2 2 6 2 6 7 2
Ni 28 2 2 6 2 6 8 2
*Cu 29 2 2 6 2 6 10 1
Zn 30 2 2 6 2 6 10 2
Ga 31 2 2 6 2 6 10 2 1
Ge 32 2 2 6 2 6 10 2 2
As 33 2 2 6 2 6 10 2 3
Se 34 2 2 6 2 6 10 2 4
Br 35 2 2 6 2 6 10 2 5
Kr 36 2 2 6 2 6 10 2 6
Rb 37 2 2 6 2 6 10 2 6 1
Sr 38 2 2 6 2 6 10 2 6 2
Y 39 2 2 6 2 6 10 2 6 1 2
Zr 40 2 2 6 2 6 10 2 6 2 2
*Nb 41 2 2 6 2 6 10 2 6 4 1
*Mo 42 2 2 6 2 6 10 2 6 5 1
Tc 43 2 2 6 2 6 10 2 6 5 2
*Ru 44 2 2 6 2 6 10 2 6 7 1
*Rh 45 2 2 6 2 6 10 2 6 8 1
*Pd 46 2 2 6 2 6 10 2 6 10
*Ag 47 2 2 6 2 6 10 2 6 10 1
Cd 48 2 2 6 2 6 10 2 6 10 2
In 49 2 2 6 2 6 10 2 6 10 2 1
Sn 50 2 2 6 2 6 10 2 6 10 2 2
* Exceptional electronic configuration
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ATOMIC STRUCTURE

22.4 Extra stability of half filled and completely filled orbitals


Half-filled and completelyfilled sub-shell have extra stability due to the following reasons :
(i) Symmetry of orbitals
(a) It is a well known fact that symmetry leads to stability.
(b) Thus, if the shift of an electron from one orbital to another orbital differing slightlyin energyresults in the
symmetrical electronic configuration. It becomes more stable.
(c) For example p 3 , d 5 , f 7 configurations are more stable than their near ones.

(ii) Exchange energy


(a) The electron in various subshells can exchange their positions, since electron in the same subshell have
equal energies.
(b) The energy is released during the exchange process with in the same subshell.
(c) In case of half filled and completely filled orbitals, the exchange energy is maximum and is greater than
the loss of energy due to the transfer of electron from a higher to a lower sublevel e.g. from 4s to 3d
orbitals in case of Cu and Cr .
(d) The greater the number of possible exchanges between the electrons of parallel spins present in the
degenerate orbitals, the higher would be the amount of energy released and more will be the stability.
(e) Let us count the number of exchange that are possible in and configuration among electrons with
parallel spins.

d4 (1)
3 exchanges by 1st e – 2 exchanges by 2nd e – Only 1 exchange by 3rd e –

To number of possible exchanges = 3 + 2 + 1 =6

d5 (2) (3)
d5 (1) –
4 exchanges by 1st e – 3 exchanges by 2nd e
2 exchange by 3rd e –

(4)
1 exchange by 4th e –

To number of possible exchanges = 4 + 3 + 2 +1 = 10

22.5 Writing electronic configuration of ions


In ionization electron(s) are removed from outer-shell first (i.e. 4s) while, electrons are filled according
to energy level.
For example : -
(i) Fe : 1s2 2s2 2p6 3s2 3p6 4s2 3d6 (ii) Fe2+ : 1s2 2s2 2p6 3s2 3p6 3d6
(iii) Fe3+ : 1s2 2s2 2p6 3s2 3p6 3d5 (iv) Cr : 1s2 2s2 2p6 3s2 3p6 4s1 3d5
(v) Cr2+ : 1s2 2s2 2p6 3s2 3p6 3d5 (vi) Cl¯ : 1s2 2s2 2p6 3s2 3p6

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ATOMIC STRUCTURE

THE ATLAS

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EXERCISE - I
BOHR’S MODEL
Q.1 Calculate the wavelength of radiation emitted, producing a line in Lyman series, when an electron falls
 1 
from fourth stationary state in hydrogen atom. [Given :  R  = 912 Å]

 h 

Q.2 Calculate energyof electron which is moving in the orbit that has its radius. sixteen times the radius of first
Bohr orbit for H–atom. [Given : E1,H = 2.176 × 10–18 J/atom]

Q.3 The wavelength of a certain line in the Paschen series in 1094.4 nm of H-atom. What is the value of nhigh
for this line.

Q.4 Wavelength of the Balmer H line is 6565 Å. Calculate the wavelength of H , line of same hydrogen
like atom.

Q.5 Calculate the Rydberg constant R if He+ ions are known to have the wavelength difference between the
first (of the longest wavelength) lines of Balmer and Lyman series equal to 133.7nm.

Q.6 What transition in the hydrogen spectrum would have the same wavelength as the Balmer transition, n=4
to n=2 of He+ spectrum.

Q.7 Calculate the total energyemitted 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.[Given:E1(H) = 2.176 × 10–18 ]

Q.8 A photon having = 800 Å causes theionization of anitrogen atom. Give theI.E. per mole ofnitrogen in KJ.
[Given : E = 1240 eV-nm, 1eV = 96.43 kJ/mol]

Q.9 H- atom is exposed to electromagnetic radiation of 1028 Å and gives out induced radiations (radiations
emitted when e– returns to ground state).Calculate  of induced radiations.

 21.7 10 12


Q.10 The electron energyin hydrogen atom is given by E n  ergs. Calculate theenergyrequired
n2
to remove an e completely from n = 2 orbit . What is the largest wavelength in cm of light that can be
used to cause this transition.

Q.11 Calculate the wavelength in angstrom of photon that is emitted when an e in Bohr orbit n=2 returns to
the orbit n=1. The ionization potential of the ground state of hydrogen atom is 2.17×1011 erg/atom.

Q.12 The radius of the an orbit of hydrogen atom is 0.85 nm. Calculate the velocity of electron in this orbit.

Q.13 The velocity of e in a certain Bohr orbit of the hydrogen atom bears the ratio 1:275 to the velocity of
light. What is the quantum no. "n" of the orbit and the wave no. of the radiation emitted for the transition
from the quatum state (n+1) to the ground state.

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Q.14 A doubly ionised lithium atom is hydrogen like with atomic number z = 3. Find the wavelength of the
radiation required to excite the electron in Li2+ from the first to the third Bohr orbit.
1
[Given : R = 912 Å]
H

Q.15 Estimate the difference in energy between I and II Bohr Orbit for a hydrogen atom.At what minimum
atomic number a transition from n=2 to n=1 energy level would result in the emission of Xrays with
= 3.0 × 108 m? Which hydrogen like species does this atomic number correspond to.

Q.16 Calculate the wave number for the shortest wavelength transition in the Balmer series of atomic hydrogen.
[Given : RH = 1.097 × 107 m–]

Q.17 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.

Q.18 The energy of an excited H-atom is –3.4 eV. Calculate angular momentum of e– in the given orbit.

Q.19 The vapours of Hg absorb some electrons accelerated by a potential diff. of 4.5 volt as a result of which
light is emitted. If the full energy of single incident e is supposed to be converted into light emitted by
single Hg atom, find the wave no. of the light.

Q.20 If the average life time of an excited state of H atom is of order 10–8 sec, estimate how many orbits an e–
makes when it is in the state n = 2 and before it suffers a transition to n =1 state.

Q.21 Calculate the frequency of e– in the first Bohr orbit in a H-atom.

Q.22 A single electron orbits around a stationary nucleus of charge +Ze where Z is atomic number and ‘e’ is
the magnitude of the electric charge. The hydrogen like species required 47.2 eV to excite the electron
from the second Bohr orbit to the third Bohr orbit. Find
(i) the value of Z and give the hydrogen like species formed.
(ii) the kinetic energy and potential energy of the electron in the first Bohr orbit.

Q.23 A stationary He+ ion emitted a photon corresponding to a first line of the Lyman series. The photon
liberated a photoelectron from a stationaryH atom in ground state. What is the velocity of photoelectron.

Q.24 In a hydrogen atom, in transition of electron a photon of energy 2.55 eV is emitted, then calculate
change in wavelength of the electron.

Q.25 In a hypothetical H-atom the mass of electron & it charge is double of what we consider then calculate
the total energy of electron in the Ist orbit of such a hypothetical H-atom ?
[Assuming all others concepts and parameter to be same as we considered in Bohr's model.]

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PHOTOELECTRIC EFFECT
Q.26 Calculate the threshold frequency of metal if the binding energy is 198.9 KJ mol1 of electron.
[Given : NA = 6 × 1023]

Q.27 Calculate the binding energy per mole when threshold wavelength of photon is 240 nm.
[Given : hc = 20 × 10–26 , NA = 6 × 1023]

Q.28 A metal was irriadated by light of frequency 3.25 × 1015 S1. The photoelectron produced had its KE,
2 times the KE of the photoelectron which was produced when the same metal was irriadated with a
light of frequency 2.0 ×1015 S1. What is work function.[Given :NA = 6 × 1023]

Q.29 U.V. light of wavelength 800 Å & 700 Å falls on hydrogen atoms in their ground state & liberates
electrons with kinetic energy 1.8 eV and 4 eV respectively. Calculate planck’s constant.

Q.30 A potential difference of 20 KV is applied across an X-raytube. Find the minimum wavelength of X-ray
generated.

Q.31 The K.E. of an electron emitted from tungstan surface is 3.06 eV. What voltage would be required to
bring the electron to rest.

Q.32 The eyes of certain member of the reptile familypass a single visual signal to the brain when the visual
receptors are struck by photons of wavelength 132.6 nm . If a total energy of 3 10 14 J is required to
trip the signal, what is the minimum number of photons that must strike the receptor.

Q.33 Find the number of photons of radiation of frequency 5 × 1013 s–1 that must be absorbed in order to melt
one gm ice when the latent heat of fusion of ice is 331.5 J/g.

Q.34 Suppose 1017 J of light energy is needed by the interior of the human eye to see an object. How many
photons of green light ( = 550 nm) are needed to generate this minimum amount of energy.

GENERAL
Q.35 What is de-Broglie wavelength of a He-atom in a container at 300 K.(Use Uavg)

Q.36 Through what potential difference must an electron pass to have a wavelength of 500 Å.

Q.37 A proton is accelerated to one- tenth of the velocity of light. If its velocity can be measured with a
precision + 1%. What must be its uncertainity in position.

Q.38 To what effective potential a proton beam be subjected to give its protons a wavelength of 1 ×1010 m.

Q.39 Calculate magnitude of orbital angular momentum of an e– that occupies 1s, 2s , 2p , 3d , 3p.

Q.40 He atom can be excited to 1s1 2p1 by  = 58.44 nm. If lowest excited state for He lies 4857cm–1 below
the above. Calculate the energy for the lower excitation state.

Q.41 A certain dye absorbs 4700 Å and fluoresces at 5080 Å these being wavelengths of maximum absorption
that under given conditions 47% of the absorbed energy is emitted. Calculate the ratio of the no. of
quanta emitted to the number absorbed.

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Q.42 The reaction between H2 and Br2 to form HBr in presence of light is initiated bythe photo decomposition
of Br2 into free Br atoms (free radicals) by absorption of light. The bond dissociation energy of Br2 is
192.86 KJ/mole. What is the longest wavelength of the photon that would initiate the reaction.
[Given : E = 1240 eVnm]

Q.43 The quantum yield for decomposition of HI is 0.2. In an experiment 0.01 moles of HI are decomposed.
Find the number of photons absorbed.

Q.44 Calculate the wavelength of the radiation that would cause photo dissociation of chlorine molecule if the
Cl- Cl bond energy is 241 KJ/mol.

Q.45 The dissociation energy of H2 is 430.53 KJ/mol. If H2 is exposed to radiant energy of wavelength
253.7 nm, what % of radiant energy will be converted into K.E.

Q.46 X-rays emitted from a copper target and a molybdenum target are found to contain a line of wavelength
22.85 nm attributedto the K line of animpurityelement. The K lines of copper (Z = 29) and molybdenum
( Z = 42) have wavelength 15.42 nm and 7.12 nm respectively. Using Moseley’s law, v1/2 = a (Z – b)
calculate the atomic number of the impurity element.

Q.47 What is de Broglie wavelength associated with an e– accelerated through potential difference = 100 KV.

Q.48 Calculate the de-broglie wavelength associated with motion of earth (mass 6 × 1024 Kg) orbiting around
the sun at a speed of 3 × 106 m/s.

Q.49 A base ball of mass 200 g is moving with velocity 30 × 102 cm/s. If we can locate the base ball with an
error equal in magnitude to the  of the light used (5000 Å), how will the uncertainty in momentum be
compared with the total momentum of base ball.

Q.50 An electron has a speed of 40 m/s, accurate up to 99.99%. What is the uncertainity in locating its
position.

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EXERCISE - II
Fill in the blanks :

Q.1 Radiation of  = 155 nm was irradiated on Li (work function = 5 eV) plate. The stopping potential
(in eV) is __________.

Q.2 Increasing order of magnetic moment among the following species is ________.
Na+, Fe+3, Co2+, Cr+2

Q.3 If in the hydrogen atom P.E. at is chosen to be 13.6 eV then the ratio of T.E. to K.E. for 1st orbit of
H-atom is ________.

Q.4 The light radiations with discrete quantities of energy are called ______.

Single correct :
Q.5 The ratio of the energy of a photon of 2000 Å wavelength radiation to that of 4000 Å radiation is
(A) 1 / 4 (B) 4 (C) 1 / 2 (D) 2

Q.6 The energy of electron is maximum at


(A) Nucleus (B) Ground state
(C) First excited state (D) Infinite distance from the nucleus

Q.7 Which electronic level would allow the hydrogen atom to absorb a photon but not to emit a photon
(A) 3s (B) 2p (C) 2s (D) 1s

Q.8 The third line in Balmer series corresponds to an electronic transition between which Bohr’s orbits in
hydrogen
(A) 5  3 (B) 5  2 (C) 4  3 (D) 4  2

Q.9 The orbital angular momentum of an electron in 2s orbital is:


1   
(A)  . (B) Zero (C) (D) 2.
2 2 2 2

Q.10 Which quantum number is not related with Schrodinger equation


(A) Principal (B)Azimuthal (C) Magnetic (D) Spin

Q.11 The shortest wavelength of He atom in Balmer series is x, then longest wavelength in the Paschene series
of Li+2 is
36 x 16 x 9x 5x
(A) (B) (C) (D)
5 7 5 9

Q.12 An electron in a hydrogen atom in its ground state absorbs energy equal to the ionisation energy of Li+2.
The wavelength of the emitted electron is:
(A) 3.32 Å (B) 1.17 Å (C) 2.32 nm (D) 3.33 pm

Q.13 An electron, a proton and an alpha particle have kinetic energies of 16E, 4E and E respectively. What is
the qualitative order of their de Broglie wavelengths?
(A) e > p =  (B) p =  > e (C) p > e >  (D)  < e » p

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Q.14 Given H for the process Li(g)  Li+3(g) + 3e– is 19800 kJ/mole & IE1 for Li is 520 then IE2 & IE3
of Li+ are respectively (approx, value)
(A) 7505, 11775 (B) 520, 19280 (C) 11775, 19280 (D) Data insufficient

Q.15 The ratio of difference in wavelengths of 1st and 2nd lines of Lyman series in H–like atom to difference in
wavelength for 2nd and 3rd lines of same series is:
(A) 2.5 : 1 (B) 3.5 : 1 (C) 4.5 : 1 (D) 5.5 : 1

Q.16 If radius of second stationary orbit (in Bohr's atom) is R. Then radius of third orbit will be
(A) R/3 (B) 9R (C) R/9 (D) 2.25R

Q.17 The ratio of wave length of photon corresponding to the -line of Lyman series in H-atom and -line of
Balmer series in He+ is
(A) 1 : 1 (B) 1 : 2 (C) 1 : 4 (D) 3 : 16

Q.18 Three energy levels P, Q, R of a certain atom are such that EP < EQ < ER. If 1, 2 and 3 are the wave
length of radiation corresponding to transition R  Q ; Q  P and R P respectively. The correct
relationship between 1, 2 and 3 is
1 1 1 2 1 1
(A) 1 + 2 = 3 (B)      (C) 3 = 1 2 (D)     
3 1 2 3 1 2

Q.19  
The value of (n2 + n1) and n 22  n12 for He+ ion in atomic spectrum are 4 and 8 respectively. The
wavelength of emitted photon when electron jump from n2 to n1 is
32 9 9 32
(A) R (B) R (C) 32 R (D) 9 R
9 H 32 H H H

Q.20 Number of possible spectral lines which maybe emitted in bracket series in H atom, if electrons present
in 9th excited level returns to ground level, are
(A) 21 (B) 6 (C) 45 (D) 5

Q.21 The first use of quantum theory to explain the structure of atom was made by :
(A) Heisenburg (B) Bohr (C) Planck (D) Einstein

Q.22 The wavelength associated with a golf weighing 200g and moving at a speed of 5m/h is of the order
(A) 10–10m (B) 10–20m (C) 10–30m (D) 10–40m

Q.23 The longest wavelength of He+ in Paschen series is "m", then shortest wavelength of Be+3 in Paschen
series is (in terms of m):
5 64 53 7
(A) m (B) m (C) m (D) m
36 7 8 64

Q.24 What is uncertainityin location of a photon of wavelength 5000Å if wavelength is known to an accuracy
of 1 pm?
(A) 7.96 × 10–14 m (B) 0.02 m (C) 3.9 ×10–8 m (D) none

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Q.25 Consider the following nuclear reactions involving X & Y.
X  Y + 42 He
Y  8O18 + 1H1
If both neutrons as well as protons in both the sides are conserved in nuclear reaction then moles
of neutrons in 4.6 gm of X
(A) 2.4 NA (B) 2.4 (C) 4.6 (D) 0.2 NA

Q.26 Electromagnetic radiations having  = 310 Å are subjected to a metal sheet having work
function = 12.8 eV. What will be the velocity of photoelectrons with maximum Kinetic Energy..
(A) 0, no emission will occur (B) 2.18 × 106 m/s
(C) 2.18 2 × 106 m/s (D) 8.72 × 106 m/s

Q.27 AssumingHeisenbergUncertainityPrincipleto betruewhat could be theminimumuncertaintyin de-broglie


wavelength of a moving electron accelerated byPotential Difference of 6 V whose uncertaintyin position
7
is n.m.
22
(A) 6.25 Å (B) 6 Å (C) 0.625 Å (D) 0.3125 Å

More than one may be correct :


Q.28 Choose the correct statement among the following
(A) Radial distribution function (  2 ·4r 2dr ) give probability at a particular distance along
one chosen direction
(B)  2 ( r ) give probability density at a particular distance over a spherical surface
(C) For 's' orbitals  ( r ) () ()   ( x , y, z ) is independent of  and 
(D) '2p' orbital with quantum numbers. n = 2,  = 1, m = 0, also shows angular dependence

Q.29 Correct statement(s) regarding 3Py orbital is/are


(A)Angular part of wave function is independent of angles ( and )
(B) No. of maxima when a curve is plotted between 4r2R2(r) vs r are '2'
(C) 'xz' plane acts as nodal plane
(D) Magnetic quantum number must be '–1'

Q.30 Select the correct statement(s):


(A)All electromagnetic radiation travel with speed of light in vaccum.
(B) Energy of photon of UV light is lower than that of yellow light.
(C) He+ and H both have line spectrum.
(D) The total energy of an electron in unielectronic specie is greater than zero

Q.31 Choose the incorrect statement(s):


(A) Increasing order of wavelength is
Micro waves > Radio waves > IR waves > visible waves > UV waves
(B) The order of Bohr radius is (rn : where n is orbit number for a given atom)
r1 < r2 < r3 < r4
(C) The order of total energy is (En : where n is orbit number for a given atom)
E1 > E2 > E3 > E4
(D) The order of velocity of electron in H, He+, Li+, Be3+ species in second Bohr orbit is
Be3+ > Li+2 > He+ > H
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Q.32 Select the correct curve(s):
If v = velocity of electron in Bohr's orbit
r = Radius of electron in Bohr's orbit
P.E. = Potential energy of electron in Bohr's orbit
K.E. = Kinetic energy of electron in Bohr's orbit.

(A) (B) (C) (D)

Q.33 Which is / are correct statement.


(A) The difference in angular momentum associated with the electron present in consecutive orbits of
h
H-atom is (n–1)
2
(B) Energydifference between energy levels will be changed if, P.E. at infinity assigned value other than
zero.
(C) Frequency of spectral line in a H-atom is in the order of (2  1) < (3  1) < (4  1)
(D) On moving away from the nucleus, kinetic energy of electron decreases.

Assertion and Reason :


Q.34 It is a data sufficiency problem in which it is to be decided on the basis of given statements
whether the given question can be answered or not. No matter whether the answer is yes or no.
Question : Is the orbital of hydrogen atom 3px?
1  / 2 r
Statement-1: The radial function of the orbital is R(r) = ( 4   )  e , =
9 6 a 30 / 2 2
Statement-2: The orbital has 1 radial node & 0 angular node.
(A) Statement (1) alone is sufficient. (B) Statement (2) alone is sufficient
(C) Both together is sufficient. (D) Neither is sufficient

Q.35 Statement-1: Energy emitted when an electron jump from 5  2 (energy level) is less than
when an electron jump from 2  1 in all 'H' like atom.

Statement-2: The |total energy difference| between 1st & 2nd energy level is greater than that of
any two energy level provided level '1' is not part of those two energy levels.
(A) Statement-1 is true, statement-2 is true and statement-2 is correct explanation for statement-1.
(B) Statement-1 is true, statement-2 is true and statement-2 is NOT the correct explanation for statement-1.
(C) Statement-1 is true, statement-2 is false.
(D) Statement-1 is false, statement-2 is true.

Q.36 Statement-1 : Emitted radiations will fall in visible range when an electron jump from
higher level to n = 2 in Li+2 ion.
Statement-2 : Balmer series radiations belong to visible range in H-atoms.
(A) Statement-1 is true, statement-2 is true and statement-2 is correct explanation for statement-1.
(B) Statement-1 is true, statement-2 is true and statement-2 is NOT the correct explanation for statement-1.
(C) Statement-1 is true, statement-2 is false.
(D) Statement-1 is false, statement-2 is true.
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Match the column :
Q.37 Column I & column II contain data on Schrondinger Wave–Mechanical model, where symbols have
their usual meanings.Match the columns.
Column I Column II (Type of orbital)

(A) (P) 4s

(B) (Q) 5px

(C) (,) = K (independent of &) (R) 3s

(D) atleast one angular node is present (S) 6d xy

Q.38 Column-I Column-I

(A) Electron moving in 2nd orbit in He+ ion (P) Radius of orbit in which
electron is moving is 0.529 Å

(B) Electron moving in 3rd orbit in H-atom (Q) Total energy of electron is
(–)13.6 × 9eV

(C) Electron moving in 1st orbit in Li+2 ion (R) Velocityofelectronis


2.188  106
m/sec
3

(D) Electron moving in 2nd orbit is Be+3 ion (S) De-broglie wavelength of
150
electron is Å
13.6

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Comprehension
Question No. 39 to 41 (3 questions)
The French physicist Louis de Broglie in 1924 postulated that matter, like radiation, should exhibit a dual
behaviour. He proposed the following relationship between the wavelength  of a material particle, its
linear momentum p and planck constant h.
h h
= =
p mv
The de Broglie relation implies that the wavelength of a particle should decreases as its velocityincreases.
It also implies that for a given velocity heavier particles should have shorter wavelength than lighter
particles. The waves associated with particles in motion are called matter waves or de Broglie waves.
These waves differ from the electromagnetic waves as they
(i) have lower velocities
(ii) have no electrical and magnetic fields and
(iii) are not emitted by the particle under consideration.
The experimental confirmation of the de Broglie relation was obtained when Davisson and Germer, in
1927, observed that a beam of electrons is diffracted by a nickel crystal.As diffraction is a characteristic
property of waves, hence the beam of electron behaves as a wave, as proposed by de Broglie.
Werner Heisenberg considered the limits of how precisely we can measure properties of an electron or
other microscopic particle like electron. He determined that there is a fundamental limit of how closely
we can measure both position and momentum. The more accurately we measure the momentum of a
particle, the less accurately we can determine its position. The converse is also true. This is summed up
in what we now call the "Heisenberg uncertainty principle: It is impossible to determine simultaneously
and precisely both the momentum and position of a particle. The product of uncertainty in the position,
h
x and the uncertainty in the momentum (mv) must be greater than or equal to . i.e.
4
h
x (mv) 
4

Q.39 The correct order of wavelength of Hydrogen (1H1), Deuterium (1H2) and Tritium (1H3) moving with
same kinetic energy is
(A) H > D > T (B) H = D = T (C) H < D < T (D) H < D > T

Q.40 The transition, so that the de-Broglie wavelength of electron becomes 3 times of its initial value in He+ ion
will be
(A) 2  5 (B) 3  2 (C) 2  6 (D) 1  2

Q.41 If the uncertainty in velocity & position is same, then the uncertainty in momentum will be
hm h h 1 h
(A) (B) m (C) (D)
4 4 4m m 4

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Question No. 42 to 45 (4 questions)
The only electron in the hydrogen atom resides under ordinaryconditions on the first orbit. When energy
is supplied, the electron moves to higher energy orbit depending on the amount of energy absorbed.
When this electron returns to any of the lower orbits, it emits energy. Lyman series is formed when the
electron returns to the lowest orbit while Balmer series is formed when the electron returns to second
orbit. Similarly, Paschen, Brackett and Pfund series are formed when electron returns to the third, fourth
and fifth orbits from higher energy orbits respectively.
Maximum number of lines produced when an electron jumps from nth level to ground level is equal
n (n  1)
to . For example, in the case of n = 4 , number of lines produced is 6. (4  3, 4  2, 4  1,
2
3  2 , 3  1, 2  1). When an electron returns from n2 to n1 state, the number of lines in the spectrum
will be equal to
(n 2  n1 )(n 2  n1  1)
2
If the electron comes back from energy level having energy E2 to energylevel having energy E1, then the
difference may be expressed in terms of energy of photon as:
hc
E2 – E1 = E ,  =
E
Since h and c are constants, E corresponds to definite energy; thus each transition from one energy
level to another will produce a light of definite wavelength. This is actually observed as a line in the
spectrum of hydrogen atom.
 1 1 
Wave number of line is given by the formula   R  2  2  .
n 
 1 n2 
where R is a Rydberg's constant ( R = 1.1 × 107 m–1)

Q.42 The energy photon emitted corresponding to transition n = 3 to n = 1 is [h = 6 ×10–34 J-sec.]


(A) 1.76 ×10–18 J (B) 1.98 ×10–18 J (C) 1.76 ×10–17 J (D) None of these

Q.43 In a collection of H-atom, electrons make transition from 5th excited state to 2nd excited state then
maximum number of different types of photons observed are
(A) 3 (B) 4 (C) 6 (D) 15

Q.44 The difference in the wavelength of the 1st line of Lyman series and 2nd line of Balmer series in a hydrogen
atom is
9 4 88
(A) (B) (C) (D) None
2R R 15R

Q.45 The wave number of electromagnetic radiation emitted during the transition of electron in between two
levels of Li2+ ion whose principal quantum numbers sum is 4 and difference is 2 is
8
(A) 3.5 R (B) 4 R (C) 8 R (D) R
9

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EXERCISE - III (A)
(JEE ADVANCED Previous Year's Questions)
Q.1 With what velocity should an particle travel towards the nucleus of a Cu atom so as to arrive at a
distance 1013 m . [JEE 1997]
Q.2 A compound of Vanadium has magnetic moment of 1.73 BM work out electronic configuration of
Vanadium Ion in the compound. [JEE 1997]
Q.3 The energy of an electron in the first Bohr orbit of H atom is  13.6 eV . The possible energy value(s) 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 [JEE 1998]
Q.4 The number of nodal planes in a px orbital is:
(A) one (B) two (C) three (D) zero [JEE 2000]
Q.5 Calculate the energy required to excite one litre of hydrogen gas at 1 atmp and 298K to the first excited
state of atomic hydrogen. The energy for the dissociation of H – H is 436 KJ mol–1.
Q.6 The quantum numbers +1/2 and –1/2 for the electron spin represent:
(A) rotation of the electron in clockwise and anticlockwise direction respectively.
(B) rotation of the electron in anticlockwise and clockwise direction respectively.
(C) magnetic moment of the electron pointing up and down respectively.
(D) two quantum mechanical spin states which have no classical analogue. [JEE 2001]
Q.7 Rutherfords experiment , which established the nuclear model of atom, used a beam of :–
(A)  - particles, which impinged on a metal foil and get absorbed.
(B)  - rays, which impinged on a metal foil and ejected electron.
(C) Helium atoms, which impinged on a metal foil and got scattered.
(D) Helium nuclie, which impinged on a metal foil and got scattered. [JEE 2002]
Q.8 The magnetic moment of cobalt of the compund Hg[Co(SCN)4] is [Given : Co+2]
(A) 3 (B) 8 (C) 15 (D) 24 [JEE 2004]

Q.9 The radius of which of the following orbit is same as that of the first Bohr’s orbit of hydrogen atom?
(A) He+ (n = 2) (B) Li2+ (n = 2) (C) Li2+ (n = 3) (D) Be3+ (n = 2)
[JEE 2004]
Q.10 Given in hydrogenic atom rn, Vn, E, Kn stand for radius, potential energy, total energy and kinetic energy
in nth orbit. Find the value of U,v,x,y. [JEE 2006]
Vn
(A) U= K (P) 1
n

1
(B) x
rn µ E (Q) –2

(C) rn µ Zy (R) –1
(Z =Atomic number)
(D) v = (Orbital angular momentum of electron (S) 0
in its lowest energy )

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Q.11 Match the entries in Column I with the correctly related quantum number(s) in Column II. Indicate
your answer by darkening the appropriate bubbles of the 4 × 4 matrix given in the ORS.[JEE 2008]
Column I Column II
(A) Orbital angular momentum of the (P) Principal quantum number
electron in a hydrogen-like atomic orbital
(B) A hydrogen-like one-electron wave (Q) Azimuthal quantum number
function obeyingPauli principle
(C) Shape, size and orientation of hydrogen (R) Magnetic quantum number
like atomic orbitals
(D) Probability density of electron at the nucleus (S) Electron spin quantum number
in hydrogen-like atom
Paragraph for Questions 12 to 14
The hydrogen-like species Li2+ is in a sphericallysymmetric state S1 with one radial node. Upon absorbing
light the ion undergoes transition to a state S2. The state S2 has one radial node and its energy is equal to
the ground state energy of the hydrogen atom. [JEE 2010]
Q.12 The state S1 is
(A) 1s (B) 2s (C) 2p (D) 3s
Q.13 Energy of the state S1 in units of the hydrogen atom ground state energy is
(A) 0.75 (B) 1.50 (C) 2.25 (D) 4.50
Q.14 The orbital angular momentum quantum number of the state S2 is
(A) 0 (B) 1 (C) 2 (D) 3
Q.15 The work function () of some metals is listed below. The number of metals which will show
photoelectric effect when light of 300 nm wavelength falls on the metal is [JEE 2011]
Metal Li Na K Mg Cu Ag Fe Pt W
(eV ) 2.4 2.3 2.2 3.7 4.8 4.3 4.7 6.3 4.75

Q.16 The maximum number of electrons that can have principal quantum number, n = 3, and spin quantum
1
number, ms =  , is [JEE 2011]
2
Q.17 The atomic masses of He and Ne are 4 and 20 a.m.u., respectively. The value of the de Broglie wavelength
of He gas at –73°C is “M” times that of the de Broglie wavelength of Ne at 727°C. M is
[JEEAdvance 2013]
Q.18 In an atom, the total number of electrons having quantum numbers n = 4, | ml | = 1 and
1
ms = – is [JEEAdvance 2014]
2

Q.19 P is the probabilityof finding the 1s electron of hydrogen atom in a spherical shell of infinitesimal thickness,
dr, at a distance r from the nucleus. The volume of this shell is 4r2dr . The qualitative sketch of the
dependence of P on r is [JEEAdvance 2016]

P P P P

(A) (B) (C) (D)


0 r 0 r 0 r 0 r

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Answer Q.20, Q.21 and Q.22 by appropriately matching the information given in the three
columns of the following table.
The wave function, n, l ,m is a mathematical function whose value depends upon spherical
l
polar coordinates (r, , ) of the electron and characterized by the quantum numbers n, l and
ml . Here r is distance from nucleus,  is colatitude and  is azimuth. In the mathematical
functions given in the Table, Z is atomic number and a 0 is Bohr radius.
Column 1 Column 2 Column 3

(I) 1s orbital 3  Zr  (P)


 Z  2  a 

 n,l,m l(r)
(i)  n ,l ,m    e  0 
 a0 
l

0
r/a0
(II) 2s orbital (ii) One radial node (Q) Probability density at nucleus
1
 3
a0

(III) 2pz orbital 5  Zr  (R) Probability density is maximum


 Z  2   2 a 0 
( iii )  n ,l , m l    re cos  at nucleus
 a0 

2
(IV) 3dz orbital (iv) xy-plane is a nodal plane (S) Energy needed to excite
electron from n =2 state to
n = 4 state is 27 times the
32
energy needed to excite
electron from n = 2 state to
n = 6 state

Q.20 For He+ ion, the only INCORRECT combination is [JEEAdvance 2017]
(A) (I) (i) (R) (B) (II) (ii) (Q) (C) (I) (i) (S) (D) (I) (iii) (R)

Q.21 For the given orbital in column 1, the only CORRECT combination for any hydrogen-like species is
[JEEAdvance 2017]
(A) (I) (ii) (S) (B) (IV) (iv) (R) (C) (III) (iii) (P) (D) (II) (ii) (P)

Q.22 For hydrogen atom, the only CORRECT combination is [JEEAdvance 2017]
(A) (II) (i) (Q) (B) (I) (iv) (R) (C) (I) (i) (P) (D) (I) (i) (S)

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EXERCISE - III (B)
(JEE Main Previous Year's Questions)

Q.1 An atom has a mass of 0.02 kg & uncertainity in its velocity is 9.218 × 10–6 m/s then uncertainity in
position is (h = 6.626 × 10–34 J - s) [AIEEE- 2002]
(A) 2.86 × 10–28 m (B) 2.86 × 10–32 cm
(C) 1.5 × 10–27 m (D) 3.9 ×10–10 m

Q.2 Energy of H–atom in the ground state is –13.6 eV , Hence energy in the second excited state is –
(A) –6.8 eV (B) –3.4 eV [AIEEE- 2002]
(C) –1.51 eV (D) –4.3 eV

Q.3 Uncertainity in position of a particle of 25 g in space is 10–5 m. Hence uncertainty in velocity (ms–1) is
(Planck’s constant h = 6.6 × 10–34 Js) [AIEEE- 2002]
(A) 2.1 × 10 –28 (B) 2.1 × 10 –34

(C) 0.5 × 10–34 (D) 5.0 × 20–24

Q.4 The orbital angular momentum for an electron revolving in an orbit is given by l l  1. h . This

momentum for an s-electron will be given by - [AIEEE- 2003]
h h 1 h
(A) (B) 2. (C) + . (D) zero
2 2 2 2

Q.5 In Bohr series of lines of hydrogen spectrum, third line from the red end corresponds to where one of the
following inter-orbit jumps of electron for Bohr orbits in an atom of hydrogen. [AIEEE- 2003]
(A) 4  1 (B) 2  5 (C) 3  2 (D) 5  2

Q.6 The de Broglie wavelength of a tennis ball mass 60 g moving with a velocity of 10 m per second is
approximately - [AIEEE- 2003]
(A) 10–16 metres (B) 10–25 metres
(C) 10–33 metres (D) 10–31metres

Q.7 Which of thefollowing setsof quantum numbersiscorrect for an electron in 4f orbital?[AIEEE- 2004]

1
(A) n = 4, l = 3 , m = + 4, s = +
2

1
(B) n = 4, l = 4 , m = – 4, s = –
2

1
(C) n = 4, l = 3 , m = + 1, s = +
2

1
(D) n = 4, l = 3 , m = – 2, s = +
2
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Q.8 Consider the ground state of Cr atom (Z = 24). The numbers of electrons with the azimuthal quantum
numbers, l =1 and 2 are, respectively [AIEEE- 2004]
(A) 12 and 4 (B) 12 and 5 (C) 16 and 4 (D) 16 and 5

Q.9 The wavelength of the radiation emitted, when in a hydrogen atom electron falls from infinityto stationary
state 1, would be [AIEEE- 2004]
7 –1
(Rydberg constant = 1.097×10 m )
(A) 91 nm (B) 192 nm (C) 406 nm (D) 9.1×10–8 nm

Q.10 Which one of the following sets of ions represents the collection of isoelectronic species ?
(A) K+, Ca2+, Sc3+, Cl– (B) Na+, Ca2+, Sc3+, F– [AIEEE- 2004]
+ – 2+ 3+ + 2+ 3+ –
(C) K , Cl , Mg , Sc (D) Na , Mg , Al , Cl
(Atomic nos.: F = 9, Cl = 17, Na = 11, Mg = 12, Al = 13, K = 19, Ca = 20 , Sc = 21)

Q.11 In a multi-electron atom, which of the following orbitals described by the three quantum numbers will
have the same energy in the absence of magnetic and electric fields ? [AIEEE- 2005]
(a) n = 1, l = 0, m = 0 (b) n = 2, l = 0, m = 0 (c) n = 2, l = 1, m = 1
(d) n = 3, l = 2, m = 1 (e) n = 3, l = 2, m = 0
(A) (b) and (c) (B) (a) and (b)
(C) (d) and (e) (D) (c) and (d)

Q.12 Of the following sets which one does NOT contain isoelectronic species ? [AIEEE- 2005]
(A) CN–, N2, C22– (B) PO43–, SO42–, ClO4–
(C) BO33–, CO32–, NO3– (D) SO32–, CO32–, NO3–

Q.13 According to Bohr's theory, the angular momentum of an electron in 5th orbit is - [AIEEE 2006]
(A) 1.0 h/ (B) 10 h/
(C) 2.5 h/ (D) 25 h/

Q.14 Uncertainty in the position of an electron (mass = 9.1 × 10–31 kg) moving with a velocity 300 m/s,
accurate upto 0.001 %, will be (h = 6.63 × 10–34 Js) [AIEEE 2006]
(A) 5.76 × 10–2 m (B) 1.92 × 10–2 m
(C) 3.84 × 10–2 m (D) 19.2 × 10–2 m

Q.15 Which of the following sets of quantum numbers represents the highest energy of an atom ?
(A) n = 3,  = 1, m = 1, s = +½
(B) n = 3,  = 2, m = 1, s = +½ [AIEEE 2007]
(C) n = 4,  = 0, m = 0, s = +½
(D) n = 3,  = 0, m = 0, s = +½

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Q.16 The ionization enthalpy of hydrogen atom is 1.312 × 106 J mol–1. The energy required to excite the
electron in the atom from n = 1 to n = 2 is [AIEEE 2008]
(A) 6.56 × 105 J mol–1 (B) 7.56 × 105 J mol–1
(C) 9.84 × 105 J mol–1 (D) 8.51 × 105 J mol–1

Q.17 In an atom, an electron is moving with a speed 600m/s with an accuracy of 0.005%. Certainity with
which the position of the electron can be located is (h = 6.6 × 10–34 kg m2 s–1, mass of electron,
em = 9.1×10–31 kg) [AIEEE 2009]
–4
(A) 1.52 × 10 m –3
(B) 5.10 × 10 m
(C) 1.92 × 10–3 m (D) 3.84 × 10–3 m

Q.18 The energy required to break one mole of Cl–Cl bonds in Cl is 242 kJ mol–1. The longest wavelength
2
of light capable of breaking a single Cl–Cl [AIEEE 2010]
(A) 594 nm (B) 640 nm
(C) 700 nm (D) 494 nm

Q.19 Ionisation energy of He+ is 19.6 × 10–18 J atom–1.f The energy of the first stationary state (n = 1) of Li+2
is – [AIEEE 2010]
–16
(A) 4.41 × 10 J atom –1 –17
(B) –4.41 × 10 J atom –1

(C) –2.2 × 10–15 J atom–1 (D) 8.82 × 10–17 J atom–1

Q.20 The outer electron configuration of Gd (atomic N : 64) is - [AIEEE 2011]


(A) 4f3 5d5 6s2 (B) 4f8 5d0 6s2 (C) 4f4 5d4 6s2 (D) 4f7 5d1 6s2

Q.21 The electrons identified by quantum numbers n and l: [AIEEE 2012]


(a) n = 4, l = 1 (b) n = 4, l = 0 (c) n = 3, l = 2 (d) n = 3 = l = 1
can be placed in order of increasing energy as
(A) (b) < (d) < (a) < (c) (B) (a) < (c) < (b) < (d)
(C) (c) < (d) < (b) < (a) (D) (d) < (b) < (c) < (a)

 Z2 
  . Wavelength of light required to excite an
Q.22 Energy of an electron is given by E = –2.178 × 10–18 J  n2 
 

electron in an hydrogen atom from level n = 1 to n = 2 will be:


(h = 6.62 × 10–34 Js and c = 3.0 × 108 ms–1) [JEE Main 2013]
(A) 2.816 × 10–7 m (B) 6.500 × 10–7 m
(C) 8.500 × 10–7 m (D) 1.214 × 10–7 m

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Q.23 The correct set of four quantum numbers for the valence electrons of rubidium atom (Z = 37) is :
[JEE Main 2014]

1 1
(A) 5, 1, 0, + (B) 5, 1, 1, +
2 2

1 1
(C) 5, 0, 1, + (D) 5, 0, 0, +
2 2

Q.24 Which of the following is the energy of a possible excited state of hydrogen ? [JEE Main 2015]
(A) – 3.4 eV (B) + 6.8 eV
(C) + 13.6 eV (D) – 6.8 eV

Q.25 A stream of electrons from a heated filament was passed between two charged plates kept at a potential
difference V esu. If e and m are charge and mass of an electron, respectively, then the value of h/
(where  is wavelength associated with electron wave) is given by : [JEE Main 2016]
(A) 2meV (B) meV

(C) 2meV (D) meV

Q.26 The radius of the second Bohr orbit for hydrogen atoms is : [JEE Main 2017]
(Planck's Const. h = 6.6262 × 10–34 Js;
mass of electron = 9.1091 × 10–31 kg;
charge of electron e = 1.60210 ×10–19 C;
permittivity of vacuum 0 = 8.854185 × 10–12 kg–1 m–3 A2)
(A) 4.76Å (B) 0.529 Å (C) 2.12 Å (D) 1.65 Å

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ANSWER KEY
EXERCISE - I

Q.1 972.8 Å Q.2 – 1.36 × 10–19 Joules Q.3 6


Q.4 4863 Å Q.5 1.096 × 107 m–1 Q.6 n1 =1, n2=2
Q.7 1.82 × 105 J/mol Q.8 1494.66 KJ/mol Q.9 6563 Å ; 1216 Å ; 1028 Å
Q.10 5.425×10–12 ergs, 3.7×10–5 cm Q.11 1220 Å
Q.12 5.44 × 105 m/s Q.13 2 ; 9.75 × 104 cm–1 Q.14 114 Å
Q.15 10.2 eV , z = 2 Q.16 27425 cm–1
Q.17 292.68×1021 atoms, 162.60×1021 atoms, 832.50 KJ Q.18 h/
Q.19 3.63 ×106 m–1 Q.20 8×106 Q.21 6530×1012Hz
Q.22 340 ev , – 680 eV Q.23 3.09 × 108 cm/sec Q.24 6.64 Å
Q.25 – 13.6 × 32 eV Q.26 5 ×1014 s–1 Q.27 500 KJ/mol
Q.28 298.35 KJ/mol Q.29 6.57 ×10–34 Js Q.30 0.62 Å
Q.31 3.06 V Q.32 20,000 Q.33 10 22
Q.34 28 photons Q.35 0.79 Å Q.36 6.03×10–4 volt

h h h
Q.37 1.05×10–13 m Q.38 0.0826 volts Q.39 0;0; 2 ; 6 ; 2
2 2 2

Q.40 3.3 × 10–18 J Q.41 0.5080 Q.42 6200 Å


Q.43 3 × 1022 Q.44 4.96 × 10–7m Q.45 8.68 %
Q.46 24 Q.47 3.88 pm Q.48 3.68 × 10–65 m
Q.49 1.75 × 10–29 Q.50 0.0144 m

EXERCISE - II

Q.1 3 eV Q.2 Na+, Co2+, Cr2+, Fe3+ Q.3 zero Q.4 photons
Q.5 D Q.6 D Q.7 D Q.8 B Q.9 B Q.10 D Q.11 B
Q.12 B Q.13 A Q.14 A Q.15 B Q.16 D Q.17 A Q.18 B
Q.19 C Q.20 B Q.21 B Q.22 C Q.23 D Q.24 B Q.25 B
Q.26 C Q.27 C Q.28 CD Q.29 BC Q.30 AC Q.31 AC Q.32 BCD
Q.33 CD Q.34 B Q.35 A Q.36 D Q.37 (A) P, (B) P,Q,S, (C) P, R (D) Q, S
Q.38 (A) S, (B) R, (C) Q, (D) P Q.39 A Q.40 C Q.41 A Q.42 A
Q.43 C Q.44 B Q.45 C

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EXERCISE - III (A)

Q.1 6.3 × 106 m/s Q.2 [Ar] 3d1] Q.3 A Q.4 A


Q.5 97.819 KJ Q.6 D Q.7 D Q.8 C Q.9 D
Q.10 (A) Q, (B) P, (C) R, (D) S Q.11 (A) Q,R (B) P, Q, R,S (C) P, Q, R (D) P, Q
Q.12 B Q.13 C Q.14 B Q.15 4 Q.16 9 Q.17 5 Q.18 6
Q19 D Q.20 D Q.21 D Q.22 D

EXERCISE - III (B)

Q.1 A Q.2 C Q.3 A Q.4 D Q.5 B Q.6 C Q.7 D


Q.8 B Q.9 A Q.10 A Q.11 C Q.12 D Q.13 C Q.14 B
Q.15 B Q.16 C Q.17 C Q.18 D Q.19 B Q.20 D Q.21 D
Q.22 D Q.23 D Q.24 A Q.25 A Q.26 C

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