2-Atomic Booklet

Physical Chemistry
Module 2
Atomic Structures
Ashwani Tyagi Sir

(Code: ATNEET)
Chemistry Atomic Structures
1. INTRODUCTION
The existence of atoms has been proposed since the time of early Indian and Greek philosophers
(400 B.C.) who were of the view that atoms are the fundamental building blocks of matter. According to
them, the continued subdivisions of matter would ultimately yield atoms which would not be further divisible.
The word ‘atom’ has been derived from the Greek word ‘a-tomio’ which means ‘uncutable’ or ‘non-divisible’.
These earlier ideas were mere speculations and there was no way to test them experimentally. These ideas
remained dormant for a very long time and were revived again by scientists in the nineteenth century.
In this unit we start with the experimental observations made by scientists towards the end of nineteenth
and beginning of twentieth century.
DALTON’S ATOMIC THEORY:
All the objects around you, this book, your pen or pencil and things of nature such as rocks, water
and plant constitute the matter of the universe. Matter is any substance which occupies space and has
mass.
John Dalton developed his atomic theory. According to this theory the Atom is considered to be hard,
dense and smallest particle of matter, which is indivisible, the atoms belonging to a particular element, is
unique. The properties of elements differ because of the uniqueness of the atoms belonging to particular
elements. This theory provides a satisfactory basis for the laws of chemical combination. The atom can
neither be created nor be destroyed i.e., it is indestructible.
Drawbacks: It fails to explain why atoms of different kinds should differ in mass and valency etc.
2. DISCOVERY OF SUBATOMIC PARTICLES
Dalton’s atomic theory was able to explain the law of conservation of mass, law of constant composition
and law of multiple proportions very successfully. However, it failed to explain the results of many
experiments; for example, it was known that substances like glass or ebonite when rubbed with silk or fur
generate electricity. Many different kinds of sub-atomic particles were discovered in the twentieth century.
However, in this section we will talk about three particles, namely electron, proton and neutron.
CATHODE RAYS AND DISCOVERY OF ELECTRON:
Ashwani Tyagi Sir (Code: ATNEET) 2 Champions Batch

Michael Faraday showed that chemical changes occur when electricity is passed though an electrolyte. He
stated that electricity is made up of particles called atoms of electricity. In mid 1850s many scientists mainly
Faraday began to study electrical discharge in partially evacuated tubes, known as cathode ray discharge
tubes. A cathode ray tube is made of glass containing two thin pieces of metal, called electrodes, sealed in
it. The electrical discharge through the gases could be observed only at very low pressures and at very
high voltages. The pressure of different gases could be adjusted by evacuation.
When sufficiently high voltage is applied across the electrodes, current starts flowing as a stream of
particles moving in the tube from the negative electrode (cathode) to the positive electrode (anode). These
were called cathode rays or cathode ray particles.
The results of these experiments are summarized below:
(i) The cathode rays start from cathode and move towards the anode.
(ii) These rays themselves are not visible but their behavior can be observed with the help of certain
kind of materials (fluorescent or phosphorescent) which glow when hit by them. Television picture
tubes are cathode ray tubes and television pictures result due to fluorescence on the television
screen coated with certain fluorescent or phosphorescent materials.
(iii) In the absence of electrical or magnetic field, these rays travel in straight lines
(iv) In the presence of electric or magnetic field, the behavior of cathode rays is similar to that expected
from negatively charged particles, suggesting that the cathode rays consist of negatively charged
particles, called electrons.
(v) The characteristics of cathode rays (electrons) do not depend upon the material of electrodes and
the nature of the gas present in the cathode ray tube. Thus, we can conclude that electrons are
basic constituent of all the atoms.
(vi) Cathode rays produce heating effect. When these rays are made to strike on a metal foil, the latter
gets heated.
(vii) Cathode rays can pass through thin foils of metals like aluminum. However, these are stopped if the
foil is quite thick.
(viii) Cathode rays ionize the gas through which they pass.
Sir J. J. Thomson confirmed these findings in 1897. Thomson performed a series of experiments in
e
which he was able to determine the charge/mass   ratio of the particles that make up the cathode ray
m
by measuring the deflection of the rays with varying magnetic and electric fields. Thomson performed the
same experiments using different metals for the cathode and anode as well as different gases inside the
tube.
e 11
  = 1.76 10 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.

QUANTIZATION OF CHARGE:
R.A. Millikan (1868-1953) devised a method known as oil drop experiment (1906-14), to determine
the charge on the electrons. 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............... That means charge is quantised.
He found that the value of e is –1.6 ×10–19 C. The present accepted value of electrical charge is
– 1.6022 ×10–19 C.
CALCULATION OF MASS OF AN 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)    9.1 1028 g  9.110 31 kg .
e / m (1.76 108 Cg 1 )
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.
DISCOVERY OF PROTONS (GOLDSTEIN):
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.
DISCOVERY OF NEUTRONS (CHADWICK):
The neutral charge particle, neutron was discovered by James Chadwick by bombarding boron or
beryllium with –particles.
9
4 Be  2 4 6 C12  0 n1
Characteristics of the three fundamental particles are:
Electron Proton Neutron
Approximate relative mass 1/1837 1 1
Approximate relative charge –1 +1 No charge
Mass in kg 9.10910–31 1.67310–27 1.67510–27
The electron and proton have equal, but opposite, electric charges while the neutron is uncharged.

3. ATOMIC MODELS
We know the fundamental particles of the atom. Now let us see, how these particles are arranged in
an atom to suggest a model of the atom.
3.1 THOMSON’S MODEL

J.J. Thomson, in 1904, proposed that there was an equal
and opposite positive charge enveloping the electrons in a
matrix. This model is called the plum – pudding model
after a type of Victorian dessert in which bits of plums
were surrounded by matrix of pudding.
This model could not satisfactorily explain the results of

scattering experiment carried out by Rutherford who
worked with Thomson.
3.2 RUTHERFORD’S MODEL

– Particles emitted by radioactive substance were shown to be dipositive Helium ions (He++) having a
mass of 4 units and 2 units of positive charge. Rutherford allowed a narrow beam of –particles to fall on a
very thin gold foil of thickness of the order of 0.0004 cm and determined the subsequent path of these
particles with the help of a zinc sulphide fluorescent screen. The zinc sulphide screen gives off a visible
flash of light when struck by an  particle, as ZnS has the remarkable property of converting kinetic energy
of  particle into visible light.
OBSERVATIONS :
i) Majority of the –particles pass straight

through the gold strip with little or no
deflection.
ii) Some –particles are deflected from their path

and diverge.
iii) Very few –particles are deflected backwards

through angles greater than 90.
iv) Some were even scattered in the opposite

direction at an angle of 180 [ Rutherford was
very much surprised by it and remarked that “It
was as incredible as if you fired a 15–inch shell
at a piece of tissue paper and it came back
and hit you”]. There is far less difference
between air and bullet than there is between
gold atoms and -particles assuming of course
that density of a gold atom is evenly
distributed.

CONCLUSIONS:
1. The fact that most of the  - particles passed straight through the metal foil indicates the most part
of the atom is empty.
2. The fact that few  - particles are deflected at large angles indicates the presence of a heavy
positively charge body , for such large deflections to occur  - particles must have come closer to or
collided with a massive positively charged body.
3. The fact that one in 20,000 have deflected at 180° backwards indicates that volume occupied by
this heavy positively charged body is very small in comparison to total volume of the atom.
POSTULATES OF RUTHERFORD ATOMIC MODEL :
On the basis of the above observation, and having realized that the rebounding -particles had met
something even more massive than themselves inside the gold atom, Rutherford proposed an atomic
model as follows.
i) All the protons (+ve charge) and entire mass of an atom is present in a very small region at the
centre of the atom. The atom’s central core is called nucleus.
ii) The size of the nucleus is very small in comparison to the size of the atom. Diameter of the nucleus
is about 10–13cm while the atom has a diameter of the order of 10–8 cm. So, the size of atom is 105
times more than that of nucleus.
iii) Most of the space outside the nucleus is empty.
iv) The electrons, equal in number to the net nuclear positive charge, revolve around the nucleus with
fast speed in various circular orbits.
v) The centrifugal force arising due to the fast speed of an electron balances the coulombic force of
attraction of the nucleus and the electron remains stable in its path. Thus according to him atom
consists of two parts (A) nucleus and (B) extra nuclear part.
DEFECTS OF RUTHERFORD’S ATOMIC MODEL:
1. Position of electrons: The exact positions of the electrons from the nucleus are not mentioned.
2. Stability of the atom: Bohr pointed out that Rutherford’s atom should
be highly unstable. According to the law of electro–dynamics, any
charged particle under acceleration should continuously lose energy.
The electron should therefore, continuously emit radiation and lose
energy. As a result of this a moving electron will come closer and
closer to the nucleus and after passing through a spiral path, it
should ultimately fall into the nucleus.
3. It was unable to explain the Hydrogen emission spectrum

It was calculated that the electron should fall into the nucleus in less than 10–8 sec. But it is known that
electrons keep moving outside the nucleus. To solve this problem Neils Bohr proposed an improved form
of Rutherford’s atomic model. Before going into the details of Neils Bohr model we would like to introduce
you some important atomic terms.
4. ATOMIC TERMS
(a) Atomic Number (Z): The atomic number of an element is the number of protons contained in the
nucleus of the atom of that element.
(b) Nucleons: Protons and neutrons are present in a nucleus. So, these fundamental particles are
collectively known as nucleons.
(c) Mass Number (A): The total number of protons and neutrons i.e, the number of nucleons present
in the nucleus is called the mass number of the element.
(d) Nuclide: Various species of atoms in general. A nuclide has specific value of atomic number and
mass number.
(e) Isotopes: Atoms of the element with same atomic number but different mass number e.g. 1H1, 1H2,
3
1H . There are three isotopes of hydrogen.
32 32
(f) Isobars: Atoms having the same mass number but different atomic numbers, e.g. 15P and 16S
are called isobars.
(g) Isotones: Atoms having the same number of neutrons but different number of protons or mass
number, e.g. 6C14, 8O16, 7N15 are called isotones.
(h) Isoelectronic: Atoms, molecules or ions having same number of electrons are isoelectronic e.g.
N2,CO, CN–.
(i) Isosters : Molecules having same number of atoms and also same number of electrons are called
isosters. These species are also isoelectronic
e.g., (i) N2 and CO ii) CO2 and N2O iii) HCl and F2
1 12
(j) Atomic mass unit: Exactly equal to   of the mass of 6C atom
 12 
1 amu = 1.66 10–27 kg, If it is converted to energy then E= 931.5 MeV
(k) Isodiapheres: Atoms having same difference between neutrons & protons are called isodiapheres.
They have same value of N - Z or A - 2Z
238 234
Example: i) 92 U & 90Th ii) 13 H & 7
3 Li

5. CHARACTERISTICS OF WAVES
A wave is a sort of disturbance which originates from some vibrating source and travels outward as
a continuous sequence of alternating crests and troughs. Every wave has five important characteristics,
namely, wavelength (), frequency (f), velocity (v), wave number   and amplitude (A)
Wavelength
Crest
Amplitude
Through
One Complete Cycle
Ordinary light rays, X–rays,–rays, etc. are called electromagnetic radiations because similar waves can
be produced by moving a charged body in a magnetic field or a magnet in an electric field. These
radiations have wave characteristics and do not require any medium for their propagation.
i) Wave length ():

The distance between two neighbouring troughs or crests is known as wavelength. It is denoted by  and is
expressed in cm, m, nanometers (1nm=10–9m) or Angstrom (1Å=10–10m); 1 micron (  )  10 6 m, 1 milli
micron (m )  10 9 m 1 pm  1012 m.
ii) Frequency (f):

The frequency of a wave is the number of times a wave passes through a given point in a medium in one
second. It is denoted by (nu) and is expressed in cycles per second (cps) or hertz (Hz) 1Hz = 1cps.
1 v
The frequency of a wave is inversely proportional to its wave length () f  or f =
 
iii) Velocity:
The distance travelled by the wave in one second is called its velocity. It is denoted by v and is expressed
v
in cm sec–1. v = f or  =
f
iv) Wave number   :

It is defined as number of wavelengths per unit length. It is denoted by  and is expressed in cm–1 or m-1
1 f
 = (or)  =
 v
v) Amplitude:
It is the height of the crest or depth of the trough of a wave and is denoted by a. It determines the intensity
or brightness of the beam of light & is also expressed in the unit of length
vi) Intensity of Wave:

The average amount of energy transported by a wave in the direction of wave propagation, per unit area
per unit time.
I ntensity   Amplitude 2

Ex.1 A source of sound  velocity  330 m s  produces waves in the frequency range 500 Hz to 6600 Hz .
Find the wavelength range of sound produced
Ans: V  .  330 m s
V 330 V 330
max    0.66 m min    0.05m
 min 500  max 6600
Ex.2 Find the distance traveled by a wave of frequency 20 KHz in 2 minutes if its wavelength is 1.5 cm
Ans:   
V  .  1.5 102 m  20 103 Hz  300 m s   distance  v  t  300  120 s   36 km
6. PLANCK’S QUANTUM THEORY

When a black body is heated, it emits thermal radiations of different wavelengths or frequency. To explain
these radiations, Max Planck put forward a theory known as Planck’s quantum theory. The main points of
quantum theory are
i) Substances radiate or absorb energy discontinuously in the form of small packets or bundles of
energy.
ii) The smallest packet of energy is called quantum. In case of light the quantum is known as photon.
iii) The energy of a quantum is directly proportional to the frequency of the radiation .E   (or) E = h
were  is the frequency of radiation and h is Planck’s constant having the value 6.626  10–27
erg – sec or 6.626  10–34 J–sec.

iv) A body can radiate or absorb energy in whole number multiples of a quantum. Hence it can be h,
2h,3h………..nh. where n is a positive integer.
nhc
v) Energy of photons can also be represented by Joules . Where,

n : number of photons h : 6.626  1034 J  s . hc = 1.988 X 10-25 Jm (~2 X 10-25 )
C  3  108 m s  : Wavelength in 'm ' .
12400
In eV units, E photon  eV where 1eV  1.6  1019 Joules ; 1ev/atom = 96.4 KJ/mole
 
  in A 
 
7. ELECTROMAGNETIC WAVES
Wave theory was given by C. Huygens. In 1856, James Clark Maxwell stated that light, X-rays,  -rays
and heat etc. emit energy continuously in the form of radiations or waves and the energy is called radiant
energy. These waves are associated with electric and magnetic fields and are, therefore, known as
electromagnetic waves (or radiations). A few important characteristics of these waves are listed:
(i) They emit energy continuously in the form of radiations or waves.

(ii) The radiations consist of electric and magnetic fields which oscillate perpendicular to each other
and also perpendicular to the direction in which the radiations propagate.
(iii) All the electromagnetic waves travel with the velocity of light (3.0  108 ms 1 ) .
(iv) These rays do not require any medium for propagation.
(v) They are not affected by electric or magnetic fields.

WAVELENGTHS OF ELECTROMAGNETIC RADIATIONS:
Electromagnetic radiations Wave length (Å)
Radio waves 31014 to 3 107
Micro waves 3109 to 3 106
Infrared (IR) 6106 to 7600
Visible 7600 (Red) to 3800 (Violet)
Ultra violet (UV) 3800 to 150
X–rays 150 to 0.1
Gamma rays 0.1 to 0.01
Cosmic rays 0.01 to zero
The complete range of the electromagnetic waves is known as electromagnetic spectrum. It may be
defined as: The arrangement of different electromagnetic radiations in order of increasing wavelength or
decreasing frequency.
Ex.3 Find the energy range of photons belonging to the visible region Given:
 
violet  4000 A and Re d  8000 A
Sol: Maximum energy (minimum  )
12400
Emax  eV  3.1 eV
4000
12400
Minimum energy (maximum  ) Emin   1.55eV
8000eV

Ex.4 Two waves differ in frequency by 1015 Hz . If one wave has   2000 A . Find possible  values of
other wave.
 c
Sol: Given, 1  2000 A  1   1.5  1015

 Possible 2 values  0.5  1015 , 2.5  1015 Hz  2 values are:

C  C 
(i)  6000 A (ii)  1200 A
0.5 1015 2.5 1015
Ex.5 Find the number of photons required to raise the temperature of 5 g of water from 20 C to 22 C ,

given that water has a specific heat capacity of 4.2 J g  C and that   5000 A . It is also given that
photon energy is 80% utilized to heat the water
Ans: Heat required  m.s. T

 5 g  4.2 J g C  2 C  42 J
80
i.e 42 J   E photon,total
100
 hc  80
ie  n     42
   100
n

42  100  5000 1010 

80  6.626 1034  3 108 
 1.32  1020 photons
8. BOHR’S ATOMIC MODEL

Bohr developed a model for hydrogen atom and hydrogen like one–electron species (hydrogenic species).
He applied quantum theory in considering the energy of an electron bound to the nucleus.
Important postulates:
 An atom consists of a dense stationary nucleus situated at the centre with the electron revolving
around it in circular orbits without emitting any energy. The force of attraction between the nucleus
and an electron is equal to the centrifugal force on the moving electron.
 Out of many circular orbits around the nucleus, an electron can revolve only in those orbits whose
angular momentum (mvr) is an integral multiple of factor h 2
nh
mvr = ; where, m = mass of the electron
2
v = velocity of the electron ; n = orbit number in which electron is present ; r = radius of the orbit
 As long as an electron is revolving in such an orbit it neither loses nor gains energy. Hence these
orbits are called stationary states. Each stationary state is associated with a definite amount of
energy and it is also known as energy levels. The greater the distance of the energy level from the
nucleus, the more is the energy associated with it. The different energy levels are numbered as
1,2,3,4, (from nucleus onwards) or K,L,M,N etc.
 Ordinarily an electron continues to move in a particular least possible energy stationary state
without losing energy. Such a stable state of the atom is called as ground state or normal state.
 If energy is supplied to an electron, it may jump (excite) instantaneously from lower energy (say 1)
to higher energy level (say 2,3,4, etc.) by absorbing one photon. This new state of electron is called
as excited state. The quantum of energy absorbed is equal to the difference in energies of the two
concerned levels.

Since the excited state is less stable, atom will lose its energy and come back to the ground state.
Energy absorbed or released in an electron jump, (E) is given by  E = E2 – E1 = h 
Where E2 and E1 are the energies of the electron in the first and second energy levels, and  is the
frequency of radiation absorbed or emitted.
RADIUS AND ENERGY LEVELS OF HYDROGEN ATOM:
Consider an electron of mass ‘m’ and charge ‘e’ revolving around a nucleus of charge Ze (where,
Z = atomic number and e is the charge of the proton) with a tangential velocity v. r is the radius of the orbit
in which electron is revolving.
By Coulomb’s Law, the electrostatic force of attraction between the moving electron and nucleus is
KZe 2
Columbic force =
r2
1
K= (where o is permittivity of free space) ; K = 9 109 Nm2 C–2
4 o
In C.G.S. units, value of K = 1 dyne cm2 (esu)–2
mv 2
The centrifugal force acting on the electron is
r
Since the electrostatic force balance the centrifugal force, for the stable electron orbit.
mv 2 KZe 2 KZe 2
= … (1) (or) v2 = … (2)
r r2 mr
nh
According to Bohr’s postulate of angular momentum quantization, we have mvr = ;
2
nh n2h2
i.e. v= ; v2 = … (3)
2 mr 4 2 m 2 r 2
KZe 2 n 2h2
Equating (2) and (3) 
mr 4 2 m 2 r 2
n2h 2
solving for r we get r = , where n = 1,2,3 - - - - - 
4π2 mKZe 2
Hence only certain orbits whose radii are given by the above equation are available for the electron. The
greater the value of n, i.e., farther the energy level from the nucleus, the greater is the radius. The radius of
the smallest orbit (n=1) for hydrogen atom (Z=1) is ro.

ro =
n 2h2
=

12  6.626  10 34  2
= 5.29 10–11 m = 0.529 Å

4 2 me 2 K 2
4  3.14   9  10  31

 1.6  10 
19 2
 9  10 9
Radius of nth orbit for an atom with atomic number Z is simply written as
n2
rn = 0.529  Å
Z
CALCULATION OF VELOCITY :
nh nh
We know that ; mvr = ;v =
2 2mr
2KZe 2
By substituting for r we are getting ; v=
nh
Where excepting n and z all are constants ;
Z
v = 2.18 106 m/sec.
n
CALCULATION OF ENERGY OF AN ELECTRON:
The total energy, E of the electron is the sum of kinetic energy and potential energy.
m v2
Kinetic energy of the electron =
2
 KZe 2
Potential energy =
r
m v 2 KZe 2
Total energy = – … (4)
2 r
mv 2 KZe2 KZe 2
From equation (1) we know that = ;  ½ mv2 =
r r2 2r
Substituting this in equation (4)
KZe2 KZe2 KZe 2
Total energy (E) = – = 
2r r 2r
2π 2mZ 2e 4K 2
Substituting for r, gives us E = where n = 1,2,3……….
n2h2
This expression shows that only certain energies are allowed to the electron. Since this energy expression
consist of so many fundamental constant, we are giving you the following simplified expressions.
Z2 Z2
E = –21.8 10–12  erg per atom = –21.8 10–19  J per atom
n2 n2
Z2
En = –13.6  eV/atom
n2
(1eV = 3.83 10–23 kcal, 1eV = 1.602 10–12 erg, 1eV = 1.602 10–19J)

Z2
E = –313.6  kcal / mole (1 cal = 4.18 J)
n2
The energies are negative since the energy of the electron in the atom is less than the energy of a free
electron (i.e., the electron is at infinite distance from the nucleus) which is taken as zero. The lowest
Energy level of the atom corresponds to n=1, and as the quantum number increases, E become less
negative.
When n = , E = 0, which corresponds to an ionized atom i.e., the electron and nucleus are infinitely
separated.
H  H++ e– (ionisation)
CALCULATION OF FREQUENCY OF REVOLUTION OF ELECTRON IN A ORBIT:
Frequency of revolution is defined as no. of revolution taken by an electron in a unit time.
v Z2
Frequency = fn = 6.56  1015 3
sec-1 .
2 R n
2 R
Time Period =
v
ENERGY LEVELS FOR HYDROGEN ATOM:
Kinetic Energy Potential Energy Total Energy Energy Difference

Shell
(in eV/atom) (in eV/atom) (in eV/atom) (in eV/atom)
n=1 13.6 -27.2 - 13.6 E2 – E1 = 10.2
n=2 3.4 - 6.8 - 3.4
E3 – E2 = 1.9
n=3 1.5 - 3.0 - 1.5
E4 – E3 = 0.65
n=4 0.85 - 1.7 - 0.85
E∞ – E4 = 0.85
n=∞ 0 0 0
FORMULA’S BASED ON BOHR’S MODEL:
S. No. Term Formula
1 Angular Momentum nh
L = mvr =
2
2 Radius n2
rn = 0.529  Å
Z
3 Velocity Z
vn = 2.18 106 m/sec.
n

4 Potential Energy Z2
Un = 2 En = – 27.2  eV/atom
n2
5 Kinetic Energy Z2
KEn = - En = 13.6  eV/atom
n2
6 Total Energy Z2
En = – 13.6  eV/atom
n2
7 Frequency of Revolution Z2
fn = 6.56  1015 3
sec-1
n
Ex.6 Find the distance between 2nd and 4th orbit in He 

n2 
Ans: Required answer  r4, He   r2, He  . Now, radius  0.529 A
Z
0.529 2 2  
 Distance 
2
 
4  2 A  3.174 A
Ex.7 Find the time taken for half a revolution by electron in 3rd orbit of Li 2
distance circumference 1 2 r3 , Li 2
Ans: time =  1 2  
speed velocity 2 V3 , Li 2
0.529  32 
r3 , Li 2   1.587 A
3
Z 
V3 , Li 2  2.18 106    2.18 106 m s
n

  1.587 A
 Time  6
 2.287 1016 s
2.18  10 m s
Ex.8 Find the wavelength of photon absorbed upon transition of an electron from 4th orbit to 6th
orbit in He 
Ans: E photon  E6, He  E4, He
 Z2   1 1 
But, En, Z  13.6  2  eV  E photon  13.6  4   2  2   1.89 eV
n  4 6 
 
12400  
  A  6560 A
1.89
MERITS AND DRAWBACKS OF BOHR’S MODEL
Bohr’s model of the hydrogen atom was no doubt an improvement over Rutherford’s nuclear model,
as it could account for the stability and line spectra of hydrogen atom and hydrogen like ions (for example,
He+, Li2+, Be3+ and so on).

MERITS OF BOHR’S THEORY:
i) The experimental value of radii and energies in hydrogen atom are in good agreement with that
calculated on the basis of Bohr’s theory.
ii) Bohr’s concept of stationary state of electron explains the emission and absorption spectra of
hydrogen like atoms.
iii) The experimental values of the spectral lines of the hydrogen spectrum are in close agreement with
that calculated by Bohr’s theory.
LIMITATIONS OF BOHR’S THEORY:
i) It does not explain the spectra of atoms having more than one electron.
ii) Bohr’s atomic model failed to account for the effect of magnetic field (Zeeman Effect) or electric
field (Stark effect) on the spectra of atoms or ions. It was observed that when the source of a
spectrum is placed in a strong magnetic or electric field, each spectral line further splits into a
number of lines. This observation could not be explained on the basis of Bohr’s model.
iii) De-Broglie suggested that electrons like light have dual character. It has particle and wave
character. Bohr treated the electron only as particle.
iv) Another objection to Bohr’s theory came from Heisenberg’s Uncertainty Principle. According to
this principle “It is impossible to determine simultaneously the exact position and momentum
of a small moving particle like an electron”. The postulate of Bohr, that electrons revolve in well
defined orbits around the nucleus with well defined velocities is thus not tenable.
9. 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 photo graphic plate or it may be viewed directly by eye. A collection of dispersed
light giving its wave length composition is called a spectrum.
9.1 KINDS OF SPECTRUM
1. EMISSION SPECTRA:
The spectrum of radiation emitted by a substance that has absorbed energy is called an emission
spectrum. Atoms, molecules or ions that have absorbed radiation are said to be “excited”. To produce an
emission spectrum, energy is supplied to a sample by heating it or irradiating it and the wavelength (or
frequency) of the radiation emitted, as the sample gives up the absorbed energy, is recorded. If the atom
gains energy the electron passes from a lower energy level to a higher energy level, (energy is absorbed).
That means a specific wave length is absorbed. Consequently, a dark line will appear in the spectrum. This
dark line constitutes the absorption spectrum.

If the atom loses energy, the electron passes from higher to a lower energy level, energy is released and a
spectral line of specific wavelength is emitted. This line constitutes the emission spectrum. There are two
types of emission spectrum.
(I) CONTINUOUS SPECTRUM:

When white light is dispersed a bright spectrum continuously distributed on the dark back ground is
obtained. The colours are continuous during change and there are no sharp boundaries in between various
colours. Colours appear to be merging into each other. Such a spectrum is known as a continuous
spectrum.
VIBGYOR
ght
W hite li Red
orange
Indigo
Violet
(II) DISCONTINUOUS SPECTRUM:
(a) Line Spectrum (For atoms) :
When an electron in excited state makes a transition to lower energy states, light of certain fixed
wave lengths are emitted. When such a light is dispersed we get sharp bright lines in dark back
ground, such a spectrum is line emission spectrum:
+ Energy (Heat)
Electron in Electron in excited state

ground state
Transition
+
Photon of
Specturm wavelength 
(b) Band Spectrum (In molecules):
Band

2. ABSORPTION SPECTRUM:
When white light (composed of all visible photon frequencies) is passed through atomic hydrogen gas,
certain wave lengths are absent. The resulting spectrum consists of bright background with some dark
lines. The pattern of the dark lines is called an absorption spectrum.
Gas
Transmitted
absorbed wave length
wave length
The missing wavelengths are same as the ones observed in the corresponding emission spectrum.
9.2 ATOMIC SPECTRUM
We have seen earlier that when electromagnetic radiation interacts with matter, atoms and molecules may
absorb energy and reach to a higher energy state. With higher energy, these are in an unstable state. For
returning to their normal state (more stable, lower energy states), the atoms and molecules emit radiations
in various regions of the electromagnetic spectrum. These lines constitute the atomic spectrum of the
elements. The atomic spectrum of the elements is a “characteristic property” of the elements and is often
termed as “finger prints” of the elements.
9.3 HYDROGEN SPECTRUM

If an electric discharge is passed through hydrogen gas taken in a discharge tube under low pressure, and
the emitted radiation is analysed with the help of spectrograph, it is found to consist of a series of sharp
lines in the UV, visible and IR regions. This series of lines is known as line or atomic spectrum of hydrogen.
The lines in the visible region can be directly seen on the photographic film.
Each line of the spectrum corresponds to a light of definite wavelength. The entire spectrum consists of six
series of lines, each series known after their discoverer as Lyman, Balmer, Paschen, Brackett, Pfund and
Humphrey series. The wavelength of all these series can be expressed by a single formula which is
attributed to Rydberg.
1  1 1
 = R  2  2 
  n1 n2 
Where,
 = wave number ;  = wave length
RH = Rydberg constant (109678 cm–1) = 10967820 m 1 ~ 1.1 X 107 m-1
R = RH Z2
n1 and n2 have integral values as follows

Series n1 n2 Main spectral lines
Lyman 1 2,3,4, etc Ultra – violet
Balmer 2 3,4,5 etc Visible
Paschen 3 4,5,6 etc Infra – red
Brackett 4 5,6,7 etc Infra – red
Pfund 5 6,7,8, etc Infra – red
Humphrey 6 7, 8, 9 etc Infra – red
n= 
n=6
3.4 eV
Humphery
n=5 (Infrared)
1.5 eV
13.6 eV
Pfund
(Infrared)
0.65 eV
n=4
Bracket
(Infrared)
n=3
1.9 eV
Paschen
(Infrared)
n=2
10.2eV
Balmer
(visible)
n=1
Lyman(ultraviolet region)
 All lines in the visible region are of Balmer series but reverse is not true. i.e., all Balmer lines will not
fall in visible region
n 2  n1
n  n  1
Total possible transitions for jump from n 2 to n1   i
2
, where n  n 2  n1 . This also gives
1
us the number of spectral lines observed under the given circumstances
As discussed earlier, the above pattern of lines in atomic spectrum is characteristic of hydrogen.
 If the energy supplied to hydrogen atom is less than 13.6 eV, it will accept or absorb only those
quanta which can take it to a certain higher energy level i.e., all those photons having energy
different from what is required for a particular transition will not be absorbed by hydrogen atom. But
if energy supplied to hydrogen atom is more than 13.6 eV then all photons are absorbed and
excess energy appears as kinetic energy of emitted photo electron
EXPLANATION FOR HYDROGEN SPECTRUM BY BOHR’S THEORY:
According to the Bohr’s theory electron neither emits nor absorbs energy as long as it stays in a particular
orbit. However, when an atom is subjected to electric discharge or high temperature, and electron in the
atom may jump from the normal energy level, i.e., ground state to some higher energy level i.e. excited

state. Since the life time of the electron in excited state is short, it returns to the ground state in one or
more jumps.
During each jump, energy is emitted in the form of a photon of light of definite wavelength or frequency.
The frequency of the photon of light thus emitted depends upon the energy difference of the two energy
levels concerned (n1, n2) and is given by
 2 2 mZ 2 e 4 K 2  1 1 2 2 mZ 2 e 4 K 2  1 1
h = En  En =
2 1 2  2  2 ; = 3  2  2
h  n 2 n1  h  n1 n 2 
The frequencies of the spectral lines calculated with the help of above equation are found to be in good
agreement with the experimental values. Thus, Bohr’s theory elegantly explains the line spectrum of
hydrogen and hydrogenic species.
Bohr had calculated Rydberg constant from the above equation.
c 22mZ 2e 4K 2  1 1 1 22mZ 2e 4K 2  1 1
= =  2  2 ;   2  2
 h3  n1 n 2   h3c  n1 n 2 
22me 4K 2
where 3
= 1.097  10–7m–1 or 109678 cm–1 i.e., Rydberg constant (R)
hc
Further application of Bohr’s work was made, to other one electron species (Hydrogenic ion) such as He+
and Li2+. In each case of this kind, Bohr’s prediction of the spectrum was correct.
 Now after obtaining the explanation of Rydberg’s equation from Bohr’s theory, can you derive what
could be the equation for other uni-electronic species? What would be the value of Rydberg’s
constant for He+1 , Li+2 ?
Ex.9 Find out the longest wavelength of absorption line for hydrogen gas containing atoms in
ground state.
1 1 1
Solution:  RZ 2  2  2 
  n1 n 2 
for longest wavelength E should be smallest i.e. transition occurs from n = 1 to n = 2
1 1 1 
i.e. = 109678 cm–1  12   2 
 1 2 
1 3
 = 109678  cm–1
 4
4
= 1
= 1.2157  10–5 cm = 121.6 nm
3  109678cm
Ex.10: The series limit for the Paschen series of hydrogen spectrum occurs at 8205.8Å. Calculate.
(A) Ionization energy of hydrogen atom
(B) Wave length of the photon that would remove the electron in the ground state of the
hydrogen atom.
0 12400
Solution: (A) Energy corresponding to 8205.8 A   1.511eV ;
8205.8

1 1
E  E1, H  Z 2  2  2 
 n1 n2 
 1 1  E 1H
1.512 eV = E1,H × (1)2 ×  2  2  ; 1.512 eV =
3   9
E1, H = 13.608 eV
 Ionisation energy of hydrogen atom = 13.6 eV
hc 6.626  10 34  3  10 8 1240
(B)   19
m or in nm = 91.6 nm
E 13.6  1.602  10 13.6
Ex.11 Calculate frequency of the spectral line when an electron from 5th Bohr orbit jumps to
the second Bohr orbit in a hydrogen atom
1 1 1 1 1
Solution: = R  2  2  = 109678  2  2  => 2.304 106 m–1
  n1 n 2  2 5 
C
  = = 2.304  106 m–1  2.998 108 m/s = 6.906  1014 Hz

Ex.12: Calculate the energy of an electron in 3rd Bohr orbit.
13.6 13.6
Solution: En =  2 eV =  2 = – 1.51 eV = – 2.42  10–19 J
n 3
Ex.13: Calculate the energy in kJ per mole of electronic charge accelerated by a potential of
1 volt.
Solution: Energy in joules = charge in coulombs  potential difference in volt
= 1.6 10–19  6.02  1023  1 ; = 9.632  104 J or 96.32 kJ
Ex.14: What is highest frequency photon that can be emitted from hydrogen atom? What is
wavelength of this photon?
Solution: Highest frequency photon is emitted when electron comes from infinity to 1st energy level.
13.6 Z 2
E=  = – 13.6eV
12
or 13.6  1.6  10–19 Joule = 2.176  10–18 Joule
18
E 2.176  10 J C
E = h   = = = 0.328  1016 Hz ;  =
h 6.626  1034 Js 
3  10 8
= = 9.146  10–8 m
0.328  10 16
Ex.15: Calculate the longest wavelength transition in the Paschen series of He+.
 1 1
Solution:   RH  Z 2  2  2  ; For He; Z = 2; For Paschen series n1 = 3
 n1 n 2 
For longest wavelength n2 = 4
1 2 1 1 1 1  7
 109678  2   2  2  = 109678×4×    = 109678 × 4 ×
 3 4   9 16  144
 = 4689 Ao
Ex.16: Calculate the ratio of the wavelength of first and the ultimate line of Balmer series of
Li2+?

 1 1  5  9R 5R
Solution: wave number of first line of Balmer,  1 = RZ 2  2  2   
2 3  36 4
4
wave length of first line of Balmer =
5R
 1 1 9R
wave number of ultimate line of Balmer,  2 = RZ 2  2   =
2  4
4 9
wave length of ultimate line of Balmer = Ratio =
9R 5
10. PHOTO ELECTRIC EFFECT

Sir J.J. Thomson observed that when a light of certain frequency strikes the surface of a metal, electrons
are ejected from the metal. This phenomenon is known as photoelectric effect and the ejected electrons
are called photoelectrons. A few metals, which are having low ionisation energy like Cesium, show this
effect under the action of visible light but many more show it under the action of more energetic ultraviolet
light.
THE EXPERIMENTAL FINDINGS ARE SUMMARIZED AS BELOW:
i) Electrons come out as soon as the light (of sufficient frequency) strikes the metal surface.
ii) Light of any random frequency will not be able to cause ejection of electrons from a metal surface.
There is a minimum frequency, called the threshold (or critical) frequency, which can just cause the
ejection. This frequency varies with the nature of the metal. The higher the frequency of the light,
the more energy the photoelectrons have. Blue light results in faster electrons than red light.
iii) Photoelectric current is increased with increase in intensity of light of same frequency, if emission is
permitted i.e., a bright light yields more photoelectrons than a dim one of the same frequency, but
the electron energies remain the same.
Light must have stream of energy particles or quanta of energy (h). Suppose, the threshold frequency of
light required to eject electrons from a metal is o, when a photon of light of this frequency strikes a metal it
imparts its entire energy (ho) to the electron.

E = ho E > ho
K.Emax = h – ho
K. E = 0
Metal
“This energy enables the electron to break away from the atom by overcoming the attractive influence of
the nucleus”. Thus each photon can eject one electron. If the frequency of light is less than o there is no
ejection of electron. If the frequency of light is higher than o (let it be ), the photon of this light having
higher energy (h), will impart some energy to the electron that is needed to remove it away from the
atom. The excess energy would give a certain velocity (i.e, kinetic energy) to the electron.
h = ho + (K.E)max ; h = ho + ½ mv2 ;
½ mv2 = h (–o)
Where,  = frequency of the incident light
o = threshold frequency
THRESHOLD ENERGY OR WORK FUNCTION:
ho is the threshold energy (or) the work function denoted by  = ho (minimum energy of the photon to
liberate electron). It is constant for particular metal and is also equal to the ionization potential of gaseous
atoms.
The kinetic energy of the photoelectrons increases linearly with the frequency of incident light. Thus, if the
energy of the ejected electrons is plotted as a function of frequency, it result in a straight line whose slope
is equal to Planck’s constant ‘h’ and whose intercept is ho.
K;Emax of
Threshold frequency
Photoelectrons
tan  h


0
It is important to note that the expression involves (KE)max. In reality e- have K.E lesser than this.
Total energy falling on plate =nhv
n
Photon intensity =
At
nhv
Intensity of energy falling on the metal surface =
At

STOPPING POTENTIAL:
An evacuated tube contains two electrodes connected to a source of variable voltage, with the metal plate
whose surface is irradiated as the anode. Some of the photoelectrons that emerge from this surface have
enough energy to reach the cathode despite its negative polarity, and they constitute the measured current.
The slower photoelectrons are repelled before they get to the cathode. When the voltage is increased to a
certain value Vo, of the order of several volts, no more photoelectrons arrive, as indicated by the current
dropping to zero. This extinction voltage is also referred as stopping potential corresponds to the maximum
photoelectron kinetic energy i.e.,
eVo = ½ mv2
Variation of P.E current vs voltage for different photon intensities I1, I2, I3
Photoelectric
current
I1
I2
I3
V0 V (Potential)
Stopping Potential

Ex.17: A photon of wavelength 5000 A strikes a metal surface, the work function of the
metal being 2.20 eV. Calculate (i) the energy of the photon in eV (ii) the kinetic
energy of the emitted photo electron and (iii) the velocity of the photo electron.
Solution: i) Energy of the photon
E = h =
hc
=

6.6  10 34 Js 3  108 ms 1  
= 3.96  10–19 J (1 eV = 1.6  10–19 J)
 5  10 7 m
3.96 1019 J
Therefore E = = 2.475 eV
1.6 1019 J / eV
ii) Kinetic energy of the emitted photo electron

Work function = 2.20 eV
Therefore, KE = 2.475 – 2.20 = 0.275 eV = 4.4  10–20 J
1
iii) Velocity of the photo electron ; KE = mv 2 = 4.4  10–20 J
2
2  4.4  10 20
Therefore, velocity (v) =  31
= 3.11  105 ms–1
9.1 10

Ex.18: When photons of wavelength 1240 A strikes a metal surface, the photoelectrons of
maximum KE has thrice as much KE as the fastest electrons ejected by a source of

wavelength 2480 A from the same metal surface.
(a) Find work function of the metal
(b) Find threshold wavelength of the metal


(c) Find stopping potential when light of wavelength 3100 A is incident on this metal.
Solution:
(a) KE  E     work function 
1240 A photon ,1240 A
KE  E  
2480 A photon ,2480 A
 
Given, KE  3  KE
 

1240 A  2480 A 
12400  12400 
ie    3  
1240  2480 
or 10    eV  3  5    eV
or 2  15  10  eV    2.5eV
12400 
(b) 0   4960 A

12400
(c) KEmax     1.5eV
3100
 Stopping potential  1.5volts
11. PARTICLE-WAVE DUALITY OF MATTER AND RADIATION

In case of light some phenomenon like diffraction and interference can be explained on the basis of its
wave character. However, the certain other phenomenon such as black body radiation and photoelectric
effect can be explained only on the basis of its particle nature. Thus, light is said to have a dual character.
Such studies on light were made by Einstein in 1905.
Louis de Broglie, in 1924 extended the idea of photons to material particles such as electrons and he
proposed that matter also has a dual character-as wave and as particle.
11.1 DE-BROGLIE EQUATION

The wavelength of the wave associated with any material particle was calculated by analogy with photon.
In case of photon, if it is assumed to have wave character, its energy is given by
E = h ------------------ (i) (according to the Planck’s quantum theory)
Where  is the frequency of the wave and ‘h’ is is is Planck’s constant. If the photon is supposed to have
particle character, its energy is given by
E = mc2 ------------------ (ii) (according to Einstein’s equation)
where ‘m’ is the mass of photon, ‘c’ is the velocity of light.
c
By equating (i) and (ii) h = mc2 ; But  = c/ ; h = mc2 ;
(or)  = h /mc

The above equation is applicable to material particle if the mass and velocity of photon is replaced by the
mass and velocity of material particle. Thus for any material particle like electron

h
 = h/mv or =
p
Where, mv = p is the momentum of the particle.
Although the de Broglie equation is applicable to all material objects but it has significance only in case of
microscopic particles. Since, we come across macroscopic objects in our everyday life, de Broglie
relationship has no significance in everyday life.
FOR AN ELECTRON HAVING ACCELERATED BY V VOLTS:
Kinetic Energy = eV = 1.6V X 10-19 Joules
Wavelength associated with e- is given by
150
 (in Å)=
KE (in eV / atom)
Ex.19: Two particles A & B are in motion. If the wavelength associated with particle A is 5 10–8 m,
calculate the wavelength associated with particle B if its momentum is half of A.
Solution: According to de Broglie equation

h h A p
A = and B = = B
pA pB B pA
But pB = ½ pA (given)
A 1/ 2p A
= =1/2 B = 2A = 2  510–8 m = 10–7 m
B pA
Ex.20: Calculate the de Broglie wavelength of a ball of mass 0.1kg moving with a speed of 60ms–1.
h 6.6  10 34
Solution:  =
mv 0.1  60
 = 1.1  10–34 m.
11.2 EXPLANATION OF QUANTIZATION OF ANGULAR MOMENTUM

According to Bohr’s model, the electron revolves around the nucleus in circular orbits. According to de
Broglie concept, the electron is not only a particle but has a wave character also.
If the wave is completely in phase, the circumference of the orbit must be

equal to an integral multiple of wave length () .Therefore 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 = n h/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”.

Alternatively
2r 2r 2mvr

Number of waves ‘n’ = = =
 h mv h
Where, v and r are the velocity of electron and radius of that particular Bohr orbit in which number of waves
are to be calculated, respectively.
11.3 HEISENBERG’S UNCERTAINTY PRINCIPLE

All moving objects that we see around us e.g., a car, a ball thrown in the air etc., move along definite paths.
Hence their position and velocity can be measured accurately at any instant of time. Is it possible for
subatomic particle also?
As a consequence of dual nature of matter, Heisenberg, in 1927 gave a principle about the uncertainties in
simultaneous measurement of position and momentum (mass  velocity) of small particles.
This principle states that “It is impossible to measure simultaneously the position and momentum of
a small microscopic moving particle with absolute accuracy or certainty” i.e., if an attempt is made to
measure any one of these two quantities with higher accuracy, the other becomes less accurate. The
product of the uncertainty in position (x) and the uncertainty in the momentum (p = m.v where m is the
mass of the particle and v is the uncertainty in velocity) is equal to or greater than h/4 where h is the
Planck’s constant.
Thus, the mathematical expression for the Heisenberg’s uncertainty principle is simply written as
h
x . p 
4
EXPLANATION OF HEISENBERG’S UNCERTAINTY PRINCIPLE:

Suppose we attempt to measure both the position and momentum of an electron, to pinpoint the position of
the electron we have to use light so that the photon of light strikes the electron and the reflected photon is
seen in the microscope. As a result of the hitting, the position as well as the velocity of the electron is
disturbed. The accuracy with which the position of the particle can be measured depends upon the
wavelength of the light used. The uncertainty in position is . The shorter the wavelength, the greater is
the accuracy. But shorter wavelength means higher frequency and hence higher energy. This high energy
photon on striking the electron changes its speed as well as direction. But this is not true for macroscopic
moving particle. Hence Heisenberg’s uncertainty principle is not applicable to macroscopic particles.
Ex.21: If the uncertainty in the position of an electron is 0.33 pm, what will be uncertainty in
its velocity?
h
Solution:  x  0.33  1012 m x  p 
4
h
 0.33  10 12  9.1 10 31  v 
4
6.6  1034
 v   1.75  108 m/sec.
4  3.14  .33  1012  9.1 1031

132
Ex.22 Calculate the uncertainty in velocity of a ball of mass gms if the uncertainty in

position is of the order of 1 Ao.
h
Solution: x.m.v 
4
6.6  1034
v   2.5  1023 m / sec
4  132  10 3  1 1010
12. QUANTUM MECHANICAL MODEL OF ATOM

The atomic model which is based on the particle and wave nature of the electron is known as wave or
quantum mechanical model of the atom. This was developed by Ervin Schrödinger in 1926. This model
describes the electron as a three dimensional wave in the electronic field of positively charged nucleus.
Schrödinger derived an equation which describes wave motion of
an electron. The differential equation is
d2  d2  d2  8 2m
   (E  V )  0
dx 2 dy 2 dz2 h2

where x, y, z are certain coordinates of the electron, (r, , )
(0, 0, 0)
m = mass of the electron 
E = total energy of the electron.
V = potential energy of the electron;
h = Planck’s constant
 (psi) = wave function of the electron.
When Schrödinger equation is solved for hydrogen atom, the

solution gives the possible energy levels the electron can occupy and the corresponding wave function ()
of the electron associated with each energy level.
Actual view and properties of quantum mechanical model can be better understood in polar coordinates
instead of normal Cartesian coordinate.In a polar coordinate any point in space can be represented in
terms of r,  and ; where r = distance from the origin;  and  = angles from any of two Cartesian
coordinates
  Amplitude of electronic wave inside the atom. It can change if any of r,  and changes. So  has to
be the function of r,  and . i.e.
Where,
x = R sinθ cosФ y = R sinθ sinФ z = R cosθ
 = f(r, , Ф)
Fortunately this whole function can be written as multiplication of two different functions as
(r, , ) = R(r) × A (, )
Total Wave Radial Wave Angular Wave

function function function
Where R(r), Radial Wave function is dependent only on distance from the nucleus and A(, ), Angular Wave
function depends only on the two angles.

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 value of coordinates. The
main aim of Schrödinger equation is to give solution for probability approach. When the equation is solved,
it is observed that for some regions of space the value of  is negative. But the probability must be always
positive and cannot be negative, it is thus, proper to use 2 instead of .
SIGNIFICANCE OF 2:
2 gives us probability density. 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 the wave equation is that it provides a set of numbers called quantum numbers which
describe energies of the electron in atoms, information about the shapes and orientations of the most
probable distribution of electrons around nucleus.
IMPORTANT FEATURE’S OF WAVE MODEL:
• The energy of the electrons in atoms is quantized, i.e., they can have only specific values. The
existence of quantized electronic energy level is a direct result of the wave like properties of
electrons.
• This model provides the most probable regions in the atom where there is maximum probability of
finding electrons. These regions are termed as atomic orbitals. This model does not specify the exact
position or momentum of the electron. This is in accordance with the Heisenberg’s uncertainly
principle.
• An atomic orbital is described by a wave function. Since many such wave functions are possible for
an electron, there are many atomic orbitals in an atom. In each orbital, the electron has a definite
energy. An orbital cannot have more than two electrons. In a multi-electron atom, the electrons are
filled in various orbitals depending on the increasing energy.
• The probability of the finding the electron at a point with in an atom is proportional to the square of
the wave function, i.e., is known as electron density and is always positive. It is possible to predict
the region within an atom by finding the value of at different points where the electron will most
probably be found.
• A wave mechanical model provides three constants n, l and m which are known as quantum
numbers. These specify the position, energy and orientation of the electron in an atom.
• The information about the exact shape of various atomic orbitals has been provided by this model.
12.1 QUANTUM NUMBERS

An atom contains large number of shells and subshells. These are distinguished from one another on the
basis of their size, shape and orientation (direction) in space. The parameters are expressed in terms of
different numbers called quantum numbers.
Quantum numbers may be defined as a set of four numbers with the help of which we can get complete
information about all the electrons in an atom. It tells us the address of the electron i.e., location, energy,
the type of orbital occupied and orientation of that orbital.

1. PRINCIPAL QUANTUM NUMBER (n):
It tells the main shell in which the electron resides and the approximate distance of the electron from the
nucleus. This value determines to large extent energy of the orbital. It also tells the maximum number of
electrons a shell can accommodate is 2n2, where n is the principal quantum number.
Shell K L M N
Principal quantum number (n) 1 2 3 4
Maximum number of electrons 2 8 18 32
Permissible values of n => all positive integers.
2. AZIMUTHAL OR ANGULAR MOMENTUM QUANTUM NUMBER (  ):
This represents the number of subshells present in the main shell. These subsidiary orbits within a shell
will be denoted as s,p,d,f… This tells the shape of the sub shells. The orbital angular momentum of the
electron is given as:
Orbital Angular Momentum =     1 h (or)     1  for a particular value of '  '

2
For a given value of n, possible values of  vary from 0 to n – 1. This means that there are 'n ' possible
th
shapes in the n shell.
3. MAGNETIC QUANTUM NUMBER (m):
An electron due to its angular motion around the nucleus generates a magnetic field. Under the influence of
external magnetic field, the electrons of a subshell can orient themselves in certain preferred regions of
space around the nucleus called orbitals. The magnetic quantum number determines the number of
preferred orientations of the electron present in a subshell. The values allowed depends on the value of  ,
the angular momentum quantum number, m can, assume all integral values between –  to +  including
zero. Thus m can be –1, 0, +1 for  = 1. Total values of m associated with a particular value of  are
given by 2  + 1.
4. SPIN QUANTUM NUMBER (s):

Just like earth not only revolves around the sun but also spins about its own axis, an electron in an atom
not only revolves around the nucleus but also spins about its own axis. Since an electron can spin either in
clockwise direction or in anticlockwise direction, therefore, for any particular value of magnetic quantum
number, spin quantum number can have two values, i.e., +1/2 and –1/2 or these are represented by two
arrows pointing in the opposite directions, i.e.,  and . When an electron goes to a vacant orbital, it can
have a clockwise or anticlockwise spin. This quantum number helps to explain the magnetic properties of
the substances.
h
Spin angular momentum s  s(s  1)  where s = ½.
2
Another term, defined as multiplicity is given as 2|S|+1 where |S| is total spin = no. of unpaired e- × 1/2.
NODES:
The region where the probability of finding an electron is zero or the probability density function reduces to
zero is called a nodal surface or simply nodes. Nodes are classified as radial nodes and angular nodes.
In general, an orbital with principal quantum number = n and azimuthal quantum number = l, has

2
At Nodes,  =0, =0
Total nodes =n–1
Radial nodes =n–  –1
Angular nodes = 
FORMULA’S FOR WAVE MECHANICAL MODEL:
S. No. Term Formula

h
1. Orbital Angular momentum of an electron l (l  1)
2
2. Magnetic moment of an electron n(n  2) B.M.
h
3. Spin Angular momentum of an electron s ( s  1)
2
4. No. of orbitals in the nth shell n2
5. No. of subshells in nth shell n
6. No. of orbitals in a subshell 2l + 1
7. Max. no. of electrons in a subshell 2(2l + 1)
12.2 SHAPES 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 (B > 90%). The shape of this region (electron cloud) gives the shape of the
orbital. It is basically determined by the azimuthal quantum number  , while the orientation of orbital
depends on the magnetic quantum number (m). Let us now see the shapes of orbitals in the various
subshells.
s–ORBITALS:
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.
p–ORBITALS (  =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.
d–ORBITALS (  =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 dz 2
and d x 2  y 2 lie along the axis.
12.3 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
f(, ) 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 probability of finding the electron with radial distance (r), termed as
radial probability distribution curves, and
(ii) one which give the variation of probability of finding the electron with angle keeping the radial
distance same (θ & ). Let us understand each of them separately.
RADIAL PROBABILITY DISTRIBUTION CURVES:
We had earlier studied that ψr2 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 4πr2dr) is given by 4πr2ψr2dr. Sometimes, ψr2 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 dr
Volume of spherical shell of thickness dr  (r  dr)3   r 3
3 3 r
4
  r 3  (dr)3  3rdr(r  dr)  r 3 
3
4
   (dr)3  3r 2dr  3r(dr) 2 
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’
= R 2 (r)  4r 2 dr ; = 4r 2R2 (r)dr
Radial Probability Density curves are between ψr2 vs r whereas Radial Probability Distribution
curves which would be more useful are between 4πr2ψr2 vs r.

COMPARISON BETWEEN 3 s, 3 p AND 3d ORBITALS:
3s
rmax
3p
2 2
4 r R
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 
(rm ax )3 s  (rm ax )3 p  (rm ax )3 d
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3 p3d
 D        
e c r e a s i n g o r d e r o f p e n e t r a ti o n p o w e r
IMPORTANT POINTS TO NOTE ABOUT THE 4r2R2 VS. r PLOTS:
i) Radial probability is ALWAYS SMALL near the nucleus (4r2 small near the nucleus).
ii) The maximum in the 4r2R21s vs. r plot occurs at 0.529Å - just the radius of the n=1 orbit of the Bohr
model.
iii) On average a 2s electron spends its most time at a greater distance from the nucleus than the 1s
electron which is 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   .)
i.e., (r2p)max < (r2s)max ; (r3d) max < (r3p)max < (r3s)max ; (r2p) max < ( r3p) max

RADIAL PROBABILITY DENSITY AND RADIAL PROBABILITY DISTRIBUTION CURVES:
Orbital Radial Function Radial Probability Density Radial Probability Distribution

2 2
2 4 r R (r)
R(r) R (r)
1s
r r r
Bohr radius =0.529Å
R(r) 2
R (r)
2
4 r R (r)
2
2s node node node
r r
r
2 2 2
R(r) R (r) 4 r R (r)
2p
r r r
R(r) 2
R (r)
2 2
4  r R (r)
2
3s
nodes
r r r
R(r)
R2(r) 4 r2R2(r)
3p
r r
r
R(r) R2(r) 4 r2R2(r)
3d
r r r

PLOTS OF ANGULAR WAVE FUNCTIONS:
Angular probability density f 2 (, ) 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.
z
 Elengated  Spherical
two lobes two lobes

f 2 (, ) f 2 (, )
ANGULAR NODES (NODAL PLANES): y
Total no. of angular nodes for any orbital =  nodal planes

For s orbital there will be no angular node. x
px orbital : no. of angular nodal = 1 (yz plane)

py orbital : nodal plane (xz plane)
pz orbital : nodal plane (xy plane)
dxy orbital :  = 2 therefore 2 nodal planes, nodal planes: xz & yz planes
dyz orbital : xy & xz planes are nodal planes.
dzx orbital : xy & yz planes are nodal planes.
 Can you guess where will be the two angular nodes for dz2 located?
No. of radial nodes =n-  -1

No. of angular nodes = 
Total no. of nodes = n -  - 1 +  = (n – 1)
No. of peaks in  r2 vs r curve = (n -  )
13. ELECTRONIC CONFIGURATION

The electron configuration of an atom is the particular distribution of electrons among available shells. It is
described by a notation that lists the subshell symbols, one after another.
Each symbol has a superscript on the right giving the number of electrons in that subshell. For example, a
configuration of the lithium atom (atomic number 3) with two electrons in the 1s subshell and one electron
in the 2s subshell is written 1s22s1. The notation for electron configuration gives the number of electrons in
each subshell.

13.1 RULES FOR FILLING OF ELECTRONS IN VARIOUS ORBITALS

The atom is built up by filling electrons in various orbitals according to the following rules:
1. AUFBAU PRINCIPLE:
This principle states that the electrons are added one by one to the various orbitals in order of their
increasing energy starting with the orbital of lowest energy. The increasing order of energy of various
orbital is
1s, 2s, 2p, 3s, 3p, 4s, 3d, 4p, 5s, 4d, 5p, 6s, 4f, 5d, 6p, 5f, 6d, 7p … … … … … … ……
To make it simple, write the increasing order of the orbitals.

Starting from the top, the direction of the arrows gives the order of 1s
filling of orbitals.
2s 2p
Alternatively, the order of increasing energies of the various
orbitals can be calculated on the basis of (n+l) rule. The energy of
an orbital depends upon the sum of values of the principal 3s 3p 3d
quantum number (n) and the azimuthal quantum number (l). This
is called (n+ l) rule. According to this rule, 4s 4p 4d 4f
“In neutral isolated atom, the lower the value of (n+ l) for an
orbital, lower is its energy. However, if the two different 5s 5p 5d
types of orbitals have the same value of (n+ l), the orbitals
with lower value of n has lower energy’’. 6s 6p
7s
ILLUSTRATION OF (n + l) RULE:
Type of
Value of n Values of l Values of (n+ l) Relative energy
orbitals
1s 1 0 1+0=1 Lowest energy
2s 2 0 2+0=2 Higher energy than 1s orbital
2p 2 1 2+1=3 2p orbital (n=2) have lower
3s 3 0 3+1=3 energy than 3s orbital (n=3)
 (n +  ) rule is applicable for multi electronic systems only. For uni-electronic system like H, order of
energy of orbitals is not “significantly influenced” by  . Now can you write the order of energy of
orbitals for uni-electronic system?
2. PAULI’S EXCLUSION PRINCIPLE:
According to this principle, No two electrons can have all quantum no. same. An orbital can contain a
maximum number of two electrons and these two electrons will have all quantum (n, l and m) same, but
they must have opposite spin(s). Two electrons in an orbital can be represented by  or 

3. HUND’S RULE OF MAXIMUM MULTIPLICITY:
This rule deals with the filling of electrons in the equal energy (degenerate) orbitals of the same sub shell
(p,d and f). According to this rule,
“Electron pairing in p,d and f orbitals cannot occur until each orbital of a given subshell contains
one electron each or is singly occupied & that too with the same spin.”
This is due to the fact that electrons being identical in charge, repel each other when present in the same
orbital. This repulsion can, however, be minimized if two electrons move as far apart as possible by
occupying different degenerate orbitals. All the electrons in a degenerate set of orbitals will have same
spin. Multiplicity is given by 2|S| + 1.
13.2 ELECTRONIC CONFIGURATION OF ELEMENTS

Electronic configuration is the distribution of electrons into different shells, subshells and orbitals of atom.
Number of electrons in the

subshell
x
nl
Principal quantum number Symbol of subshell or
orbitals (s,p,d,f)
Alternatively:
Orbital can be represented by a box and an electron with its direction of spin by arrow. To write the
electronic configuration, we need to know (i) the atomic number (ii) the order in which orbitals are to be
filled (iii) maximum number of electrons in a shell, sub–shell or orbital.
 Each orbital can accommodate two electrons
 The number of electrons to be accomodated in a subshell is 2  number of degenerate orbitals.

Subshell Maximum number of electrons
s 2
p 6
d 10
f 14
 The maximum number of electron in each shell (K,L,M,N…) is given by 2n2. Where n is the principal
quantum number.
 The maximum number of orbitals in a shell is given by n2 where n is the principal quantum number.
Ex. 23 Write the electronic configuration of nitrogen (atomic number= 7)
Solution:
1s2 2s2 2p3
    

EXCEPTIONAL CONFIGURATIONS:
(Extra stability of half-filled and fully-filled sub shell)
24Cr: 1s2, 2s2 2p6, 3s2 3p6 3d5, 4s1 47Ag : 1s2, 2s2 2p6, 3s2 3p6 3d10, 4s2 4p6 5s1
29Cu: 1s2, 2s2 2p6, 3s2 3p6 3d10, 4s1 42Mo: 1s2, 2s2 2p6, 3s2 3p6 3d10, 4s2 4p6 4d5, 4s1
The electronic configuration of most of the atoms follow the Aufbau’s rule. However, in certain elements
such a Cr, Cu etc. electron fills in 3d in preference to 4s provided the subshell become either half-filled or
fully filled.
5 1 4 2 10
24Cr  [Ar] 3d , 4s and not [Ar] 3d , 4s ; 29Cu  [Ar] 3d 4s1 and not [Ar] 3d9, 4s2
It has been found that there is extra stability associated with these electronic configurations. This
stabilization is due to the following two factors
1. SYMMETRICAL DISTRIBUTION OF ELECTRON:
It is well known that symmetry leads to stability. The completely filled or half-filled subshells have
symmetrical distribution of electrons in them and are therefore more stable. This effect is more dominant in
d and f-orbitals.
This means three or six electrons in p-subshell, 5 or 10 electrons in d-subshell, and 7 or 14 electrons in f
subshell forms a stable arrangement.
2. EXCHANGE ENERGY:
This stabilizing effect arises whenever two or more electrons with the same spin are present in the
degenerate orbitals of a subshell. These electrons tend to exchange their positions and the energy
released due to this exchange is called exchange energy. The number of exchanges that can take place is
maximum when the subshell is either half-filled or full filled. As a result the exchange energy is maximum
and so is the stability.
(1) (2) (3) (4)
4-exchanges by 3-exchanges by 2-exchanges by 1-exchanges by

electron 1 electron 2 electron 3 electron 4
Total exchanges = 10
If n is the number of electron with parallel spins then can you calculate total number of possible
exchanges?
e.g. Total exchanges possible are = 6
e.g. 24Cr : Total exchanges possible are = 6

Total exchanges possible are = 10
The stabilation due to exchange energy will compensate for the energy required for excitation from
4s to 3d.
However in case of carbon (6C): 1s2, 2s2 2p

The stabilization due to exchange energy will not be able to compensate for the energy required for
excitation from 2s to 2p.
ELECTRONIC CONFIGURATION OF IONS :
Note that while filling electrons in various orbitals they are filled according to the three laws – Aufbau, Pauli
and Hund’s. For removing electrons to form cations, electrons are removed from outermost shell as they
are bound to the nucleus by lesser forces of attraction because of shielding effect.
For example for iron,

2 2 6 2 6 6 2
26Fe  1s , 2s 2p , 3s 3p 3d , 4s & the configuration of ions would be
Fe2+  1s2, 2s2 2p6, 3s2 3p6 3d6 & Fe3+  1s2, 2s2 2p6, 3s2 3p6 3d5
Similarly for copper

2 2 6 2 6 10 1
29Cu  1s , 2s 2p , 3s 3p 3d , 4s & for its ions
Cu+  1s2, 2s2 2p6, 3s2 3p6 3d10 & Cu2+  1s2, 2s2 2p6, 3s2 3p6 3d9
The anions are formed by adding electrons to the vacant orbital of lowest energy [follow (n +l) rule]
For example 9F  1s2, 2s2 2p5 & that of its ion F-  1s2, 2s2 2p6
Similarly for Chlorine 17Cl  1s2, 2s2 2p6, 3s2 3p5 & that of its ion Cl-  1s2, 2s2 2p6, 3s2 3p6
Applications of electronic configuration:
(1) Calculation of Magnetic Moment (µ) :    n  n  2  Bohr Magneton

e.h
Where n  no. of unpaired electrons & 1 BM (Bohr Magneton) =
4me
When  = 0 (Diamagnetic repelled, by magnetic field)
If   0 , paramagnetic attracted by magnetic field.
(2) Colour: It has been observed that the species having unpaired e- generally impart colour.

SOLVED PROBLEMS (OBJECTIVE)
Problem 1: For a p-electron, orbital angular moment is

(A) 2 (B)  (C) 6 (D) 2
h
Solution: Orbital angular momentum L = (   1) where  
2
 L for p electron = 1(1  1)  2  (A)
Problem 2: For which of the following species, Bohr theory doesn’t apply
(A) H (B) He+ (C) Li2+ (D) Na+
Solution: Bohr theory is not applicable to multi electron species  (D)
Problem 3: If the radius of 2nd Bohr orbit of hydrogen atom is r2. The radius of third Bohr orbit will
be
4 9
(A) r2 (B) 4r2 (C) r2 (D) 9r2
9 4
n 2h 2 r2 2 2 9
Solution: r 2 2
   r3  r2 (C)
4 mZe r3 3 2 4
Problem 4: Number of waves made by a Bohr electron in one complete revolution in 3rd orbit is
(A) 2 (B) 3 (C) 4 (D) 1
Solution: Circumference of 3rd orbit = 2r3

According to Bohr, angular momentum of electron in 3rd orbit is
h h 2r3
mvr3 = 3 or  by De-Broglie equation
2 mv 3
h 2r3
= =  2r3 = 3
mv 3
i.e. circumference of 3rd orbit is three times the wavelength of electron or number of waves
made by Bohr electron in one complete revolution in 3rd orbit is three. (B)
RH
Problem 5: The degeneracy of the level of hydrogen atom that has energy equivalent to  is
16
(A) 16 (B) 4 (C) 2 (D) 1
RH RH R
Solution: En =     H i.e. for 4th shell
n2 n 2
16
1 2 3
n= 4
l = 0

m=0 -1 0 +1 -2 –1 0 +1 +2 –3 –2 –1 0 +1 +2 +3
one s three p five d Seven f
i.e. 1 + 3 + 5 + 7 = 16  degeneracy is 16
Problem 6: An electron is moving with a kinetic energy of 4.55 10–25 J. What will be de Broglie
wave length for this electron?
(A) 5.28 10–7 m (B) 7.28 10–7 m (C) 2 10–10 m (D) 3 10–5 m

1 2  4.55  10 25
Solution: KE = mv2 = 4.55  10–25 ; v2 =  31
 1 10 6 ; v = 103 m/s
2 9.1 10
h 6.626  10 34
De Broglie wave length = =  31 3
= 7.28 10–7 m  (B)
mv 9.1 10  10
Problem 7: Suppose 10–17J of energy is needed by the interior of human eye to see an object.
How many photons of green light (=550 nm) are needed to generate this minimum
amount of energy?
(A) 14 (B) 28 (C) 39 (D) 42
Solution: Let the number of photons required = n

17
hc 10   10 17  550  10 9
n  10 17 ; n = = = 27.6 = 28 photons
 hc 6.626  10 34  3  108
 (B)
Problem 8: Photoelectric emission is observed from a surface for frequencies 1 and 2 of the
incident radiation (1>2). If the maximum kinetic energies of the photoelectrons in
two cases are in ratio 1:K then the threshold frequency 0 is given by
 2  1 K1   2 K 2  1  2  1
(A) (B) (C) (D)
K 1 K 1 K 1 K
KE1 1
Solution: KE1 = h1 – ho ; KE2 = h2–ho It is given that ; =
KE2 K
h 1  h o 1 K 1   2
 ; K1   2    o K  1 ; o =  (B)
h 2  h o K K 1
Problem 9: The velocity of electron in the ground state hydrogen atom is 2.18  106 ms–1. Its
velocity in the second orbit would be
(A) 1.09 106 ms–1 (B) 4.38 106 ms–1 (C) 5.5 105 ms–1 (D) 8.76 106 ms–1-
Solution: We know that velocity of electron in nth Bohr’s orbit is given by

Z 2.18  106
 = 2.18  106 m/s ; for H, Z = 1 ;  v1 = m/s
n 1
2.18  106
 v2 = m/s = 1.09 106 m/s ; (A)
2
Problem 10: The ionization energy of the ground state hydrogen atom is 2.1810–18J. The energy of
an electron in its second orbit would be
(A)–1.09 10–18 J (B) –2.18 10–18J (C) –4.36 10–18J (D) –5.45 10–19J
Solution: Energy of electron in first Bohr’s orbit of H–atom

 2.18  1018  2.18  1018
E= J ( ionization energy of H = 2.18 10–18J) ; E2 = J
n2 22
= –5.45 10–19J ;  (D)
Problem 11: Magnetic moments of V (Z = 23), Cr (Z = 24) and Mn (Z = 25) are x, y, z. Hence
(A) z  y  x (B) x = y = z (C) x  z  y (D) x  y  z
Solution: Magnetic moments = n(n  2)B.M. where n is the number of unpaired electron

V ( Z = 23) (Ar) 3d34s2 n = 3, 15 BM = x

Cr (Z = 24) (Ar) 3d5 4s1 n = 6, 48 BM = y
Mn (Z = 25) (Ar) 3d5 4s2 n = 5, 35 BM = z  (C)
Problem 12: The speed of a proton is one hundredth of the speed of light in vacuum. What is the
de Broglie wavelength? Assume that one mole of protons has a mass equal to one
gram.
h = 6.626  10–27 erg sec
(A) 3.31  10–3Å (B) 1.33  10–3 Å (C) 3.13  10–2 Å (D) 1.31 10–2Å
1 h 6.626  10 27
Solution: m= g ; = =  6.023  1023
6.023  10 23 mv 1 3  10 8 cm sec 1
= 1.33  10–11 cm ;  (B)
Problem 13: The wave number of first line of Balmer series of hydrogen atom is 15200 cm–1. What
is the wave number of first line of Balmer series of Li2+ ion.
(A) 15200 cm–1 (B) 6080 cm–1 (C) 76000 cm–1 (D) 1,36800 cm–1
Solution: For Li+2 v  v for H Z2 = 15200  9 = 1, 36,800
 (D)
Problem 14: The speed of the electron in the 1st orbit of the hydrogen atom is
[C is the velocity of light]

C C C C
(A) (B) (C) (D)
1.37 1370 13.7 137
h C
Solution: V= = 2.189  108 cm sec–1 ; C = 3  1010 cm/s, = 137  (D)
2mr v
Problem 15: The quantum number not obtained from the Schrödinger’s wave equation is
(A) n (B) l (C) m (D) s
Solution: n, l and m quantum numbers can be obtained from Schrodinger equation. s is obtained
from spectral evidence.  (D)
Problem 16: Which of the following sets of quantum numbers is not allowed
(A) n = 3, l = 1, m = +2 (B) n = 3, l = 1, m = +1
(C) n = 3, l = 0, m = 0 (D) n = 3, l = 2, m =  2
Solution: If n = 3 l = 0,1,2
for l = 0, m = 0 l = 1, m = –1, 0, +1 l = 2, m = –2, –1, 0, +1, +2

If l = 1, the value of m can not be 2
 (A)
Problem 17: Assuming that a 25 watt bulb emits monochromatic yellow light of wave length
0.57 m.The rate of emission of quanta per sec. will be

(A) 5.89  1015 sec–1 (B) 7.28  1017 sec–1 (C) 5  1010 sec–1 (D) 7.18  1019 sec–1
Solution: Let n quanta are evolved per sec.

 hc 
n   = 25 J sec–1
 
6.626  10 34  3  10 8
n = 25
0.57  10 6
n = 7.18  1019 sec–1
 (D)
Problem 18: The binding energy of an electron in the ground state of the He atom is equal to
24.6 eV. The energy required to remove both the electrons from the atom will be
(A) 59 eV (B) 81 eV (C) 79 eV (D) None of these
Solution: Ionization energy of He+

z2 22
=  13.6 = 13.6 = 54.4 eV
n2 12
Energy required to remove both the electrons
= binding energy + ionization energy = 24. 6 + 54.4 = 79 eV  (C)
Problem 19: The shortest wave length transition in Balmer series of atomic hydrogen will be:
(A) 4215Å (B) 1437 Å (C) 3942 Å (D) 3647 Å
1  1 1 
Solution: = RZ2  2  2 
 shortest n 
 1 n2 
 1 1 
= 109678  12   2  2   = 3.647  10–5 cm
2  
= 3647 Å  (D)
SOLVED PROBLEMS (SUBJECTIVE)
Problem 1: Which electronic transition in Balmer series of hydrogen atom has same frequency as
that of n = 6 to n = 4 transition in He+.
1 1  36  16  5R
Solution:  He  RZ2  2  2  = 4R  =
4 6   36  16  36
1 1
H = R  1 2  2
 2
 2 n 
 He  H
5R R R
= 
36 4 n2
On solving above equation
n2 = 9 n=3
Or corresponding transition from 3  2 in Balmer series of hydrogen atom has same
frequency as that of 6  4 transition in He+.
Problem 2: Calculate ionisation potential in electron volts of (A) He+ and (B) Li2+
13.6 Z 2
Solution: I.E. =
n2

13.6  Z 2
= [Z =2 for He+] = 13.6  4 = 54.4 eV
12
13.6  3 2
Similarly for Li2+ = = 13.6  9 = 122.4 eV
12
Problem 3: What fraction of the volume of an atom of radius 10–8 cm is occupied by its nucleus if
nuclear radius is 10–12 cm?
Solution: Assuming atom to be spherical having definite boundary its volume can be given by
4 3 4
r (where r is atomic radius). Similarly volume of nucleus can be given by r  3 where r
3 3
is radius of nucleus.
4
   r 3
Volume of nucleus 3

r 3
= 3 
10 12 3
=

10 36
= 10–12
4 8 3
Volume of atom 3 r (10 ) 10  24
 r
3
Problem4: Calculate the ratio of K.E and P.E of an electron in the Bohr orbit?
KZe 2
Solution: K.E. =
2r
 KZe 2
P.E. =  P.E. = –2K.E
r
K.E 1
 
P.E 2
Problem 5: How many spectral lines are emitted by atomic hydrogen excited to nth energy level?
Solution: n
n-1
n-4
n-3
n-2
n-1
n-1 n-2
Thus the total number of lines will be equal to
Number of lines coming to 1st level + number of lines coming to 2nd level + number of lines
coming to 3rd level + …….. number of lines to n-1 level.
= (n -1) + (n - 2) + (n – 3) + ( n – 4) +……. +3 + 2 + 1
= sum of first ( n – 1) natural numbers.
=
n  1n  1  1 =
n  1n 
2 2
Number of spectral lines that appear in hydrogen spectrum when an electron de excites
nn  1
from nth energy level =
2

 These total lines can be observed only if there is sufficiently large number of Hydrogen atoms in the
sample so that all the possible transitions can take place.
Problem 6: Calculate (A) the de Broglie wavelength of an electron moving with a velocity of 5.0 
105 ms–1 and (B) ratio of de Broglie wavelength of an atom of hydrogen and atom of
oxygen moving with the same velocity (h = 6.63  10–34 kg m2 s–1)
34 2 1
h 6.63  10 kgm s
Solution: (A) = =  Wavelength  = 1.46  10–9m
mv  
9.11 1031 kg 5.0 105 ms 1 
(B) An atom of oxygen has approximately 16 times the mass of an atom of hydrogen. In
h
the formula   , h is constant while the conditions of problem make v, also
mv
constant. This means that  and m are variables and  varies inversely with m.
Therefore,  for the hydrogen atom would be 16 times greater than  for oxygen
atom.
Problem 7: In photoelectric effect, an absorbed quantum of light results in the ejection of an

electron from the absorber. The kinetic energy of the electron is equal to the
energy of the absorbed photon minus the energy of the longest wavelength that
causes the effect. Calculate the kinetic energy of an electron produced in cesium by
400 nm light. The critical (maximum) wavelength for the photoelectric effect in cesium
is 660 nm.
hc hc
Solution: Kinetic energy of electron = h – hcritical = -
  critical
1240nm eV 1240 nm eV
KE =  = 1.22 eV
400 nm 660nm
Problem 8: It has been found that gaseous Iodine molecules dissociate into separated atoms
after absorption of light at wavelengths less than 4995Å. If each quantum is
absorbed by one molecule of I2, what is the minimum input in kcal/mole, needed to
dissociate I2 by this photo chemical process?
Solution: E (per mole) = NAh
E = NA
hc

 
6.022  1023 mol 1 6.626  10 34 Js  3  108 ms 1 
 4995  1010 m
 1 kcal 
= 239.5 kJ/mol   = 57.1 kcal/mole
 4.184kJ 
Problem 9: What is the wavelength associated with 150 eV electron
h
Solution: =
2  m  K.E.
6.626  1034 Js 6.626  10 34
= = = 10–10 m = 1Å
31 19 4368  10  50
2  9.1 10 kg  150  1.6  10 J
Problem 10: The energy of electron in the second and third Bohr orbit of the hydrogen atom is –
5.42  10–12 erg and –2.41  10–12 erg, respectively. Calculate the wavelengths of
emitted radiation when the electron drops from third to second orbit.

hc 6.626  10 27  3  1010

Solution: E3 – E2 = h = ; – 2.41  10–12 – (– 5.42  10–12) =
 
6.626  10 27  3  1010
= = 6.604  10–5 cm = 6604 Å
3.01 10 12
Problem 11: Show that frequencies of emitted photons are additive but their wavelengths are not.
n=3
Solution:
E2  3
n=2 X
E
E1  3 E1  2
n=1
 E1  3 = E1  2 + E2  3 ; h1  3 = h1  2 + h2  3

1  3 = 1  2 + 2  3 ; i.e. frequencies like energies are additive, on the other hand
 E1  3 = E1  2 + E2  3
hc hc hc 1 1 1
   ;  
 1 3  1 2  2  3  1 3  1 2  2  3
1  23   12  12  23
  ;   13 
 13  12  23  12   23
i.e. wavelengths are not additive.
Problem 12: O2 undergoes photochemical dissociation into one normal oxygen and one excited
oxygen atom, where the excited atom is 1.967 eV more energetic than normal. The
dissociation of O2 into two normal atoms of oxygen atoms requires 498 KJ mole–1.
What is the maximum wavelength effective for photochemical dissociation of O2?.
Solution: O2  ON + Oexcited ;
O2  ON + ON
498  10 3
E = 498 103 J / mole = 23
J per molecule = 8.268 10–19 J
6.023  10
Energy required for excitation = 1.967 eV = 3.146 10–19J
Total energy required for photochemical dissociation of O2 = 8.268 10–19 + 3.146 10–19
hc
= 11.414  10–19 J ; = 11.414 10–19 J

6.626  10 34  3  10 8
= 19
= 1.7415 10–7 m = 1741.5 Å
11.414  10
Problem 13: Compare the wavelengths for the first three lines in the Balmer series with those
which arise from similar transition in Be3+ ion.
1 1   1 1 
Solution: H  R 12  2  2  ; Be3  R  42  2  2 
2 n  2 n 
 3 
 Be  H = 16
H  Be3

FOUNDATION BUILDER (OBJECTIVE)

ATOMIC TERMS
1. In the following reaction 3Li6 + ?  2He4 + 1H3, the missing particles is
(A) Neutron (B) Proton (C) Electron (D) Deuterium
2. The increasing order (lowest first) for the magnitude of e/m (charge/mass) for electron (e), proton
(p), neutron (n) and alpha particle () is
(A) e,p,n, (B) n,p,e, (C) n,p,,e (D) n,,p,e,
3. X 2― has 56 electrons, the atomic number X is

(A) 56 (B) 58 (C) 28 (D) 54
23
4. 11Na and 12Mg24 are
(A) Isotopes (B) Isobars (C) Isodiaphers (D) Isotones
5. Particle in cathode ray has same charge/ mass ratio as

(A) α particle (B) β particle (C) γ particle (D) proton
6. During Muliken’s oil drop experiment, out of the following, which is not a possible charge on oil
droplet?
(A) 1.6×10−19 C (B) 2.4×10−19 C (C) 3.2×10−19 C (D) 4.8×10−19 C
ELECTROMAGNETIC WAVES & PLANCK’S QUANTUM THEORY
7. In a time period of 2 sec., the following wave pattern is observed:
Then the frequency of wave in Hz is

(A) 1 (B) 2 (C) 3 (D) 4
8. Yellow light is more energetic than

(A) Violet (B) blue (C) Indigo (D) Red
9. Rutherford’s experiment on scattering of  -particles showed for the first time that the atom has
(A) electrons (B) protons (C) nucleus (D) neutrons
10. The wave number of radiation of wavelength 500 nm is

(A) 5  10–7 m–1 (B) 2  107 m–1 (C) 2  106 m–1 (D) 500  10–9 m–1
11. The ratio of the energy of a photon of 2000Å wavelength radiation to that of 4000Å radiation is
(A) ¼ (B) ½ (C) 2 (D)4
12. Radio city broadcasts on a frequency of 5,090 KHz. What is the wavelength of electromagnetic
radiation emitted by the transmitter?
(A)10.3 m (B) 58.9 m (C) 60.5 m (D) 75.5 m

13. A 1000 watt radio transmitter operates at a frequency of 880 kilocycle/sec. How many photons per
sec does it emit?
(A) 2.01×1029 (B) 1.72×1030 (C) 1.51×1029 (D) 1.77×1031
14. The eyes of certain members of reptile family pass a visual signal to the brain when the visual
receptors are struck by photons of wavelength 890 nm. If a total energy of 3.15×10−14 J is required
to trip signal, what is the minimum number of photons that must strike the receptor?
(A) 3.05×1019 (B) 1.72×109 (C) 1.41×105 (D) 2.75×1010
15. A certain dye absorbs light of wavelength 4500 Ao and then fluorescence light of 5000 Ao. Assuming
that, under given conditions 50% of the absorbed energy is re-emitted out as fluorescence.
Calculate the ratio of quanta emitted to the number of quanta absorbed?
(A) 0.55 (B) 2.1 (C) 1.8 (D) 0.75
BOHR MODEL
x
16. An electron in an atom jumps in such a way that its kinetic energy changes from x to .
4
The change in potential energy will be:
(A)  3 x (B)  3 x (C)  3 x (D)  3 x
2 8 4 4
17. The potential energy of an electron in the Hydrogen atom is – 6.8 eV. Indicate in which excited
state, the electron is present?
(A) first (B) second (C) third (D) fourth
18. What is the potential energy of an electron present in N-shell of the Be3+ ion?
(A) – 3.4 eV (B) – 6.8 eV (C) – 13.6 eV (D) – 27.2 eV
19. The kinetic and potential energy (in eV) of electron present in third Bohr’s orbit of hydrogen atom
are respectively:
(A) – 1.51, – 3.02 (B) 1.51, – 3.02 (C) – 3.02, 1.51 (D) 1.51, – 1.51
20. The distance between 4th and 3rd Bohr orbits of He+ is:
(A) 2.645  10 10 m (B) 1.322  10 10 m (C) 1.851  10 10 m (D) None
21. For what value of Z, the 4th orbit of that atom would fit inside the 1st Bohr orbit of H-atom?
(A) 3 (B) 4 (C) 16 (D) 25
22. The ratio of velocity of the electron in the third and fifth orbit of Li2+ would be:
(A) 3 : 5 (B) 5 : 3 (C) 25 : 9 (D) 9 : 25
23. 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) 2.25 R
24. Which state of Be3+ has the same orbit radius as that of the ground state of hydrogen atom?
(A) 3 (B) 2 (C) 4 (D) 5

1
25. Select the incorrect graph for velocity of e  in an orbit Vs. Z , and n:
n
v
v v v
(A) (B) (C) (D)

n 1/n Z n
26. What is the frequency of revolution of electron present in 2nd Bohr’s orbit of H-atom?
(A) 1.016  1016 s 1 (B) 4.065  1016 s 1
(C) 1.626  1015 s 1 (D) 8.13  1014 s 1
27. The number of photons of light having wave number ‘x’ in 10 J of energy source is:
(A) 10hcx (B) hc (C) 10 (D) None of these
10 x hcx
28. The ionization potential for an electron in ground state of the hydrogen atom is 13.6 eV. What would
be the ionization potential for the electron in the first excited state of H atom?
(A) 13.6 eV (B) 6.8 eV (C) 3.4eV (D) 27.2 eV
29. According to Bohr’s theory, angular momentum of electron in any orbit of Hydrogen is directly
proportional to
(A) 1 (B) 1 (C) rn 2 (D) rn
rn rn
30. If the revolutions per second by the electron in 3rd orbit of H is , then the revolutions per second by
the electron in 2nd orbit of He+ is
(A)  (B) 13.5 (C) 1.5 (D) 0.07
31. If the kinetic energy of electron moving in 4th orbit of hydrogen is €, then the total energy in 1st orbit
of Li2+ is
(A) –144 € (B) –0.0069 € (C) –(27/9) € (D) – €
32. If same energy is supplied to electron in ground state of Hydrogen as well as He+, electron jump to
5th main shell in Hydrogen, then final orbit of electron in He+ is
(A) 2nd (B) 1st (C) 3rd (D) 4th
33. If force of attraction between the electron and nucleus in 2nd orbit of Li2+ is, force of attraction if
electron present in 1st orbit of H is
(A) 6  (B) 12  (C) 8  (D) 16 
49 25 81 27
34. If acceleration of electron in 1st orbit of He+ is, acceleration of electron 2rd orbit of Be3+ is
(A)  (B) 2 (C) 1  (D) 1 
2 4
35. The spacing between the orbits in terms of distance is maximum in the case of
(A) 1st and 2nd (B) 2nd and 3rd (C) 3rd and 4th (D) 4th and 5th
36. The spacing between the orbits in terms of energy is maximum in the case of
(A) 1st and 2nd (B) 2nd and 3rd (C) 3rd and 4th (D) 4th and 5th

HYDROGEN SPECTRUM
37. Transition of an electron from n = 2 to n = 1 level results (for a H - atom) in

(A) IR spectrum (B) UV spectrum
(C) Visible spectrum (D) X - ray spectrum
38 The emission spectrum of He+ ion is the consequence of transition of electron from orbit n2 to orbit
n1. Given that 2n2 + 3n1 = 18 and 2n2 – 3n1 = 6, then what will be the maximum number of spectral
lines in atomic spectrum when electron transits from n2 to orbit n1?
(A) 10 (B) 15 (C) 20 (D) 21
39. Find the value of wave number (v ) in terms of Rydberg’s constant, when transition of electron takes
place between two levels of He+ ion whose sum is 4 and difference is 2.
(A) 8R (B) 32R (C) 3R (D) None of these
9 9 4
40. When an electron makes a transition from (n + 1) state to nth state, the frequency of emitted
radiations is related to n according to (n >> 1):
2 2 2 2
(A) v  2cRZ
3
(B) v  cRZ (C) v  cRZ (D) v  2cRZ
2
4 2
n n n n
41. What is the shortest wavelength line in the Paschen series of Li2+ ion?
(A) R (B) 9 (C) 1 (D) 9R
9 R R 4
42. What is the longest wavelength line in the Lyman series of He+ ion?
(A) 3R (B) 1 (C) 1 (D) None of these
3R 4R
43 An excited state of H atom emits a photon of wavelength  and returns to the ground state, the
principal quantum number of excited state is given by:
(A) R (R  1) (B) R (C) R(R  1) (D) (R  1)
(R  1) R
44. A dye absorbs a photon of wavelength  and re-emits the same energy into two photons of
wavelength  1 and  2 respectively. The wavelength  is related with  1 and  2 as:
(A)   1  2 (B)   1 2
12 1  2
2 2
(C)   1 2 (D)   12
1  2 (1  2 ) 2
45. Which electronic transition in a hydrogen atom, starting from the orbit n = 7, will produce infrared
light of wavelength 2170 nm?
(A) n = 7 to n = 6 (B) n = 7 to n = 5
(C) n = 7 to n = 4 (D) n = 7 to n = 3
46. A hydrogen atom in the ground state is excited by monochromatic radiation of wavelength  A . The
resulting spectrum consists of maximum 15 different lines. What is the wavelength  ?
(A) 937.3 Ao (B) 1025 Ao (C) 1236 Ao (D) None of these

47. The emission spectra are observed by the consequence of transition of electron from higher energy
state to ground state in Li2+ ion. Six different types of photons are observed during the emission
spectra, and then what is the excitation state of Li2+ ion?
(A) 3rd (B) 4th (C) 2nd (D) 5th
48 If 1, 2, and 3, is wave length of photon corresponding to 1st, 2nd Lyman series and 1st Balmer
series respectively, which of the following statement is correct?
(A) 2 = 1 + 3 (B) 2 = 13/(1+3)
(C) 1 + 2 +3 =0 (D) 22 = 12 + 32
49. If the shortest wavelength of H atom in Lyman series is x, then longest wavelength in Balmer series
of He+ is
(A) 9x (B) 36x (C) x (D) 5x
5 5 4 9
HEISENBERG UNCERTAINTY PRINCIPLE AND DE BROGLIE
50. Uncertainty in position and momentum are equal. Uncertainty in velocity is:
h h 1 h
(A) (B) (C) (D) none
 2 2m 
51. Wavelength associated with Virar-F local train having mass 100 × 103 Kg moving with the speed of
23.76 kms/hr is: (plank’s constant =6.6× 10-34 Js)
(A) 10−31 Ao (B) 10−35 Ao (C) 10−29 Ao (D) 10−40 Ao
52. If E1, E2 and E3 are kinetic energy of electron, alpha particle and proton having same De-Broglie
wave length, then
(A) E1 E2 E3 (B) E1< E2< E3 (C) E2< E3< E1 (D) E1 =E2 =E3
53. If the radius of first Bohr orbit is x, then de Broglie wavelength of electron in 3rd orbit is nearly.
x
(A) 2x (B) 6x (C) 9x (D)
3
54. A ball of mass 200 g is moving with a velocity of 10ms–1. If the error in measurement of velocity is
0.1%, the uncertainty in its position is:
(A) 3.310–3 m (B) 3.310–27 m
(C) 5.310–25 m (D) 2.64 10–32 m
55. If the uncertainty x in the position is along X-axis, then uncertainty in the momentum is along
(A) X-axis (B) Y-axis (C) Z-axis (D) Any axis
56. When applied, the uncertainty principle has significance in case of

(A) Moving train (B) Spinning cricket ball
(C) Moving α- particle (D) All the above
PHOTOELECTRIC EFFECT
57. The kinetic energy of the electron emitted when light of frequency 3.5  1015 Hz falls on a metal
surface having threshold frequency, 1.5  1015 Hz is (h = 6.6  10-34 Js):
(A) 1.32  10-18 J (B) 3.3  10-18 J (C) 6.6  10-19 J (D) 1.98  10-19J

58.  0 is the threshold wavelength of a metal for photoelectron emission. If the metal is exposed to the
2h
light of wavelength  , then the velocity of ejected electron will be   0    K . The value of K
m
is:
C 1
(A) Speed of light (B) 1 (C) (D)
0   0
59. When photons of energy 4.25 eV strike the surface of a metal A. The ejected photoelectrons have
maximum kinetic energy (T(A) (expressed in eV) and de-Broglie wavelength ((A). The max kinetic
energy of photoelectrons liberated from another Metal B by photons of enegy 4.2 eV is TB.Where
TB= (TA1.5). If De-Broglie wave length of these photoelectrons B (B =2A), then which of the
following is not correct
(A) The work function of A is 2.25 eV. (B) The work function of B is 3.7 eV
(C) TA = 2.0 eV, (D) TB =0 .75 eV
60. Work function WA for a photoelectric material A is 2 eV & WB for another photoelectric material B is
4 eV. If the photons of energy EA strike with surface of A the ejected photoelectrons have minimum
de-Broglie wavelength A and photons of energy EB strike the surface of B, the ejected
photoelectrons have minimum de-Broglie wavelength B. Where EB= (EA+0.5) eV and B =2A, VA
and VB are respective stopping potentials then which of the following is not correct
(A) EA = 4 eV (B) EA = 4.5 eV (C) VA = 2 Volts (D) VB =0 .5 Volts
QUANTUM WAVE MECHANICAL MODEL AND ORBITALS
61. The number of nodal planes in a px orbital is

(A) one (B) two (C) three (D) zero
62. For a 4d electron the orbital angular momentum is: (   h )

2
(A) 6 (B) 12  (C) 2 (D) zero
63. If travelling at equal speeds, the longest wavelength of the following matter waves is that of
(A) electron (B) proton (C) neutron (D) alpha particle
64. Which subshell doesn’t exist?

(A) 7s (B) 3d (C) 3f (D) 5d
65. The quantum number not obtained from the Schrodinger’s wave equation is
(A) n (B) l (C) m (D) s
66. The orbital angular momentum of an electron in 2s orbital is

1 h h h
(A) + . (B) zero (C) (D) 2.
2 2 2 2
67. Which quantum number determines shape of the orbital?

(A) Principal (B) Angular (C) Magnetic (D) Spin
68. Radial nodes are maximum in:

(A) 4s (B) 4p (C) 3d (D) 5f
69. Total number of electrons in any orbit is:

l =n l =n 1 l =n 1 l =n 1
(A)  2(2 l +1) (B)  2(2 l +1) (C)  2(2 l +1) (D)  2(2 l +1)
l 1 l 1 l 0 l 0
70. Which of the following relates to photons both as wave motion and as a stream of particles?
(A) Interference (B) E = mc2 (C) diffraction (D) E = h
71. Probability of finding the electron in the orbital is?

(A) 100% (B) 5-10% (C) 90-95% (D) 50-60%
72. The Wave mechanical model of atom is based upon

(A) De Broglie concept of dual nature (B) Heisenberg’s uncertainty principle
(C) Schrodinger wave equation (D) All of these
73. Select the correct statement from following:

A: Splitting of spectra line occurs when placed in a magnetic field or in an electric field.
B: In case of 1s- orbital, the density of the electron cloud is the greatest near the nucleus and falls
off with the distance.
C: Electron – density is concentrated along a particular direction in case of 2p-orbital
D: A p-orbital can take maximum of six electrons
(A) A, B, D (B) A, B, C (C) B, C, D (D) A, C, D
74. The Magnetic quantum number signifies

(A) Size of the orbital (B) Shape of the orbital
(C) Orientation of orbital in space (D) Nuclear stability
75. The quantum number which specifies the location as well as energy is
(A) n (B) l (C) m (D) s
76. Which of the following sets of quantum numbers is not allowed?

(A) n = 3, l = 1, m = +2 (B) n = 3, l = 1, m = +1
(C) n = 3, l = 0, m = 0 (D) n = 3, l = 2, m =  2
77. Which set of quantum numbers is not possible for electron in 3rd shell?
(A) n = 3, l = 2, m = – 1, s= +1/2 (B) n = 3, l = 2, m = – 1, s= –1/2
(C) n = 3, l = 2, m =0, s= +1/2 (D) n = 3, l = 3, m = 0, s= –1/2
78. Out of the following which sub shell has maximum energy?
(A) 3d (B) 4s (C) 5s (D) 4p
79. Which two orbitals are located along the axes, and not between the axes?
(A) d xy , d z 2 (B) d xy , p z (C) d yz , p x (D) p z , d x 2  y 2

80. Which series of subshells is arranged in the order of increasing energy for multi-electron atoms?
(A) 6s, 4f, 5d, 6p (B) 4f, 6s, 5d, 6p (C) 5d, 4f, 6s, 6p (D) 4f, 5d, 6s, 6p
81. The subshell that arises after f is called the g subshell. How many electrons may occupy the g
subshell?
(A) 9 (B) 7 (C) 5 (D) 18

PROBABILITY DISTRIBUTION CURVES AND WAVE FUNCTION
82. Miss Ritika has two correct information from Mr. Gupta and Mr. Agarwal about a particular
orbital of hydrogen atom. Identify the orbital
1/ 2
 1 
 
Mr. Gupta:  (angular) of orbital is  4 
Mr. Agarwal: The orbital has two radial nodes.

(A) 's' orbital with any principal quantum number
(B) any orbital with principal quantum number 3
(C) 3s orbital
(D) Information from Mr. gupta & Mr. Agarwal cannot predict the orbital.
83. Which of the following is the correct representation of plot radial probability (4r2R2) in Y-axis vs
distance from the nucleus in X-axis for 1 electron of 4d-atomic orbital?
Y Y
(A) 2 2 2 2
4r R (B) 4 r R
r X r X
Y Y
(C) 2 2 (D) 2 2
4 r R 4 r R
r X r X
84. If the nodes at infinity are not neglected, then what is the total number of radial and angular nodes
of 5f-orbitals?
(A) 4 (B) 3 (C) 5 (D) infinity
85. The distance of maximum probability for 3s, 3p, 3d are given in the order
(A) ( rmax )3 d  ( rmax ) 3 p  ( rmax ) 3 s (B) ( rmax )3 d  ( rmax ) 3 s  ( rmax )3 p
(C) ( rmax )3 s  ( rmax ) 3 p  ( rmax ) 3d (D) None of these
86. The number of local maxima in the Radial distribution curve of 5d orbital is
(A) Zero (B) 1 (C) 2 (D) 3
87. Out of the following, which is the correct match for radial probability of finding the electron of 2s
orbital?
Y A B
4pr 2 R 2 2
r X
(A) A-H, B-He+, C-Li2+ (B) A- He+, B-H, C-Li2+

(C) A- Li2+, B-He+, C-H (D) Can’t say

3/ 2
88. For a 3s-orbital,  (3s)  1  1  (6  6   2 )e  /2 ; where   2r.Z

9 3  a0  3a0
What is the maximum radial distance of node from nucleus?
2a 0
(A) (3  3 )a 0 (B) a 0 (C) 3 (3  3 ) a 0 (D)
Z Z 2 Z Z
89. The Schrödinger wave equation for hydrogen atom is

3/ 2
1 Z
 (radial)    [(  1)( 2  8  12)] e  / 2
16 4  a0 
Where a0 and Z are the constant in which answer can be expressed and   2 Zr . Minimum and
a0
maximum positions of radial nodes from nucleus are……respectively.
(A) a0 , 3a 0 (B) a 0 , a0 (C) a0 , 3a0 (D) a 0 , 4a 0
Z Z 2Z Z 2Z Z 2Z Z
ELECTRONIC CONFIGURATION AND APPLICATION
90. Which of the following electronic configurations is correct for Iron, (atomic number 26)?
(A) [ Kr ] 4 s1 3d 6 (B) [ Kr ] 4 s 1 3d 7 (C) [ Ar ] 4s 2 3d 6 (D) [ Kr ] 4 s 2 3d 6
91. Which of the following representation of excited states of atoms is impossible?

(A) 1s 1 2 s 1 (B) [ Ne] 3s 2 3 p 3 4s 1 (C) [ Ne] 3s 2 3 p 6 4 s1 3d 6 (D) 1s 2 2s 2 2 p 7 3s 2
92. Which of the following has the maximum number of unpaired electrons?
(A) Mn (B) Ti (C) V (D) Al
93. The magnetic moment of isolated Fe2+ ion is

(A) 2 6 BM (B) 15 BM (C) 3 BM (D) 35 BM
94. Total spin resulting from a d5 configuration is

(A) 1 (B) ½ (C) 5/2 (D) 3/2
95. Electronic configuration of Ni is [Ar]3d8,4s2. The electronic configuration of next element is

(A) [Ar]3d104s1 (B) [Ar]3d9 4s2 (C) 3d84s24p1 (D) None
96. Which of the following is having the maximum number of unpaired electrons?
(A) Mg2+ (B) Ti3+ (C) V3+ (D) Fe2+
97. Which of the following violates the Pauli Exclusion Principle?
(A) (B)
(C) (D)
98. The value of the magnetic moment of a particular ion is 2.83 Bohr magneton. The ion is
(A) Fe2+ (B) Ni2+ (C) Mn2+ (D) Co3+

99. If an ion of 25Mn has a magnetic moment of 3.873 B.M. Then Mn is in which state.
(A) + 2 (B) + 3 (C) + 4 (D) + 5
100. A compound of vanadium has a magnetic moment ( ) of 1.73 BM. If the vanadium ion in the
compound is present as Vx+, then, the value of x is?
(A) 1 (B) 2 (C) 3 (D) 4
101. The ratio of magnetic moments of Fe (III) and Co (II) is:

(A) 5: 7 (B) 35 : 15 (C) 7 : 3 (D) 24 : 15
FOUNDATION BUILDER (SUBJECTIVE)
ELECTROMAGNETIC WAVES, LIGHT AND PLANCKS QUANTUM THEORY
1. A monochromatic source of light operating at 600 watt emits 2 1022 photons per second. Find
the wavelength of the light.
h
2. The dissociation of I2   2I utilizes one photon per iodine molecule dissociated. The
maximum  which can cause this dissociation is 4995 Å. Calculate number of moles of I2
dissociated per KJ of photon energy.
3. Calculate the wavelength, frequency and wave number of a light wave whose period is
2.0  10 –10 s .
4. Infrared lamps are used in restaurants and cafeterias to keep food warm. The infrared radiation is
strongly absorbed by water raising its temperature and that of the food in which it is incorporated.
How many photons per second of infrared radiation are produced by an infrared lamp that
consumes energy at the rate of 100 watt (100 J/s and is 12% efficient in converting this energy to
infrared radiation? Assume that the radiation has a wavelength of 1500 nm.
HYDROGEN SPECTRUM/ ATOMIC SPECTRUM
5. Find the wavelength of the radiation emitted by hydrogen in the following transitions.
(a) n= 3 to n=2, (b) n = 5 to n = 4 and (c) n = 10 to n = 9.
6. Calculate the wavelength of first line for hydrogen atom of the (i) Lyman series and (ii) Balmer
series (iii) Paschen series assuming the Rydberg constant as 109, 678 cm–1
7. Find the wavelength of the radiation required to excite the electron in Li + 2 from the first to the
third Bohr orbit. How many spectral lines are observed in the emission spectrum of the above
excited system?
8. What electron transition in a hydrogen atom, starting from the orbit n=7, will produce infrared
light of wavelength 2170nm? Given: RH=1.09677×107/m.
9. Whenever a photon is emitted by hydrogen in Balmer series, it is followed by another photon in

Lyman series. What wavelength does this latter photon correspond to?

10. A sample of hydrogen atoms is exposed to electromagnetic radiation of 1028 Å which causes
emission of induced radiations. Calculate  of induced radiations.
11. Calculate the energy emitted when electrons of 1.0 g atom of hydrogen undergo transition giving the
spectral line of lowest energy in the visible region of its atomic spectrum.
12. The hydrogen atom in the ground state is excited by means of monochromatic radiation of
wavelength x Å. The resulting spectrum consists of 15 different lines. Calculate the value of x.
13. The wave number of the first line in the Balmer series of hydrogen is 15200 cm–1. What is the wave
number of the first line in the Balmer series of Be3+?
14. One of the series of the hydrogen spectrum can be represented by the equation in terms of wave

number  = 1.09603  10  (1  n )  m (where n = 2,3,…..)
7 2 1
i) Calculate the maximum and minimum wavelength of lines in this series.

ii) In what portion of the electromagnetic spectrum will this series be found?
15. What transition in the hydrogen spectrum would have the same wavelength as the Balmer transition
n = 4 to n = 2 of He+ spectrum?
16. Calculate the wave number for the shortest wavelength transition in the Balmer series of atomic
hydrogen.
BOHR’S MODEL
17. Show that the speed of the electron revolving in a Bohr`s orbit of the hydrogen atom is Inversely
proportional to the quantum number of the orbit. Calculate this speed for n=2 and the time taken
by the electron to complete 107 revolutions in the orbit.
18. The electron in a hydrogen atom revolves in the third orbit. Calculate (i) the energy of the electron in
this orbit (ii) the radius of the third orbit and (iii) the frequency and wavelength of the spectral line
emitted when the electron jumps from the third orbit to the ground state.
19. Calculate the radii of the I, II and III permitted electron Bohr orbits in a hydrogen atom. What are
the corresponding values in the case of a singly ionized helium atom?
20. Calculate energy in kcal/mole necessary to remove an electron in a hydrogen atom from fourth
Bohr’s orbit
21. An electron collides with a hydrogen atom in its ground state and excites it to a state of n = 3.
How much energy was given to the hydrogen atom in this inelastic collision?
22. The electron energy in hydrogen atom is given by E = – 21.7  10–12/n2 erg. Calculate the
energy required to remove an electron completely from n = 2 orbit. What is the longest
wavelength (in cm) of light that can be used to cause this transition?
23. Ionisation energy of hydrogen atom is 13.6 eV. Calculate the energy of electron for Li2+ and
Be3+ in the first excited state.

24. A bulb emits light of wave length 4500Å. The bulb is rated as 150 watt and 8% of the energy is
emitted as light. How many photons of lights are emitted by bulb per second?
25. Calculate  of the radiations when the electron jumps from III to II orbit of hydrogen atom. The
electronic energy in II and III Bohr orbit of hydrogen atoms are – 5.42 10–12 and –2.41 10–12
ergs respectively.
26. Calculate velocity of an electron placed in the third orbit of the hydrogen atom. Also calculate the
number of revolutions per second that this electron makes around the nucleus.
8
27. Average lifetime of a hydrogen atom excited to n = 2 state is 10 s. find the number of
revolutions made by the electron on the average before it jumps to the ground state.
28. Estimate the difference in energy between Ist and 2nd 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 atom – like species does this atomic number
correspond to?
29. Find out the number of waves made by a Bohr electron in one complete revolution in its 3rd orbit.
PHOTO ELECTRIC EFFECT
30. The photoelectric effect consists of the emission of electron from the surface of the metal when
the metal is irradiated with light. A photon with a minimum energy of 3.97 10–19J is necessary to
eject an electron from barium.
(A) What is frequency of the radiation corresponding to this value?
(B) Will the blue light with wave length 450 nm be able to eject the electron?
31. Find the threshold wavelengths for photoelectric effect from a copper surface, a sodium surface
and a cesium surface. The work function of these metals are 4.5 eV, 2.3 eV and 1.9 eV
respectively.
32. Energy required to stop the ejection of electrons from Cu plate is 0.24 eV. when radiation of  =
253.7 nm strikes the plate Calculate the work function.
33. Calculate the threshold frequency of metal if the binding energy is 180.69 KJ /mole
34. Calculate the minimum & maximum kinetic energy in eV of photoelectrons produced in cesium by
400 nm light, when the potential difference is 2V is applied as accelerating voltage .The critical
(maximum) wavelength for the photoelectric effect in cesium is 660 nm,
35. A stationary He+ ion emitted a photon corresponding to a first line of the Lyman series. The
photon liberated a photoelectron from a stationary H atom in ground state. What is the velocity
of photoelectron?
36. The minimum energy necessary to overcome the attractive force between the electron and the
surface of silver metal is 7.52  10–19 J. What will be the maximum kinetic energy of the
electrons ejected from silver which is being irradiated with ultraviolet light having a wavelength
360Å?

DUAL NATURE AND HEISENBERG UNCERTAINITY PRINCIPLE
37. Find wavelength for 100 g particle moving with velocity 100 ms–1.
38. A moving electron has 4.55 10-25 joules of kinetic energy. Calculate its wavelength
39. Calculate the de-Broglie wavelength of electron accelerated through 100 volt.
1
40. Calculate de-Broglie wavelength of an electron moving with a speed of nearly th that of light
20
41. What is uncertainty in velocity of an electron if uncertainty in its position is 1Å?
42. A proton is accelerated to one- tenth of the velocity of light. If its velocity can be measured with a
accuracy of 0.01 times velocity of proton. What must be its uncertainty in position.
43. An electron beam can undergo diffraction by crystals. Through what potential should a beam of
0
electron accelerated so that its wavelength becomes equal to 1.54 A .
QUANTUM NUMBERS AND ELECTRONIC CONFIGURATION
44. Give reasons why the ground state outermost electronic configuration of silicon is:
3s 3p
and not -
45. What is the maximum number of electrons that may be present in all the atomic orbitals with
principle quantum number 3 and azimuthal quantum number 2?
46. Predict the magnetic moment for S2–, Co3+
WAVE MECHANICAL MODEL & PROBABLITY DISTRIBUTION CURVES
47. The wave function of 2s electron is given by

12 r
1 1  r  2a 0
 2s  .  2   e
2 2  a 0   a0 
If it has a node at r = r0, find relation between r0 and a0.

GET EQUIPPED FOR JEE MAIN
1. Which has highest specific charge ?

(A) Na+ (mass no. = 23) (B) Mg2+ (mass no. = 24)
(C) Al3+ (mass no. = 27) (D) Si4+ (mass no. = 28)
2. A certain laser transition emits 6.00 × 1015 quanta per sec square meter. What is the power output
in joule per sec per square meter ? Given,  = 600 nm
(A) 1.9878 × 10-3 (B) 6.626 × 10-4
(C) 1.9878 × 103 (D) 6.626 × 10-12
3. The wave numbers of two electromagnetic radiation are 2.4 × 105 m-1 and 1.2 × 104 cm-1,
respectively. The ratio of their frequencies is
(A) 20 : 1 (B) 5:1 (C) 1 : 20 (D) 1:5
4. In order to increase the kinetic energy of ejected photoelectrons, there should be an increase in
(A) Intensity of radiation
(B) Wavelength of radiation
(C) Frequency of radiation
(D) Both wavelength and intensity of radiation
5. Which among the following graphs explain the photoelectric effect ?
 
(A) (B)
K.E. of emitted e K.E. of emitted e
(C) (D)
6. The potential energy of the electron in an orbit of H-atom would be

(A) −mv2 (B) −e2/r (C) –mv2/2 (D) −e2/2r
7. The ratio of the areas within the electron orbits for the first excited state to the ground state for the
hydrogen atom is
(A) 2:1 (B) 1:2 (C) 4:1 (D) 16 : 1

8. When an electron jumps from 2nd orbit to 4th orbit, its distance from nucleus increase by 2.116 Å.
The atom or ion should be
(A) H-atom (B) He+ ion (C) Li2+ ion (D) None of these
9. The force of attraction on electron by the nucleus is directly proportional to

n3 z3 n4 z2
(A) (B) (C) (D)
z4 n4 z2 n4
10. The binding energy for the third electron in the ground state of Li – atom should be
(A) 108.8 e V (B) 122.4 e V (C) 30.6 e V (D) 27.2 e V
11. For which transition in H-atom, the amount of energy released will be maximum ?
(A) n = 4 to n = 2 (B) n = 5 to n = 2 (C) n = 2 to n = 1 (D) n = 7 to n = 2
12. An electron is moving with a KE of 4.55×10−25J .What will be the de Broglie wavelength for this
electron
(A) 5.28×10−7m (B) 7.27×10−7m (C) 2×10−10m (D) 3×10−5m
13. The number of orbitals in a sub shell is equal to

(A) n2 (B) 2l (C) 2l +1 (D) m
14. The ratio of the energy of the electron in ground state of hydrogen atom to that of the electron in the
first excited state of Be3+ is
(A) 1:4 (B) 1:8 (C) 1:16 (D) 16:1
15. The electronic transition from n=2 to n=1 will produce the shortest wavelength in
(A) H-atom (B) D-atom (C) He+ ion (D) Be3+ ion
16. The ratio of potential energy and total energy of an electron in a Bohr orbit of hydrogen like species
(A) 2 (B) −2 (C) 1 (D) −1
17. Three atomic states of a hydrogen like atom are shown in

the figure. The transition from C to B yields a photon of
wavelength 364.6 nm and the transition from B to A yields
a photon of wavelength 121.5 nm, Then the transition
from C to A will yield a photon of wavelength.
(A) 91.13 nm (B) 243.1 nm (C) 486.1 (D) None of these
18. In a discharge tube, there are only two hydrogen atoms. If the electrons in both atoms are de-
exciting from 4th orbit, the minimum and maximum number of spectral lines should respectively be
(A) 1,4 (B) 4, 1 (C) 3, 4 (D) 1, 6
19. When electrons are de-exciting from nth orbit of hydrogen atoms, 15 spectral lines are formed. The
shortest wavelength among these will be
11 900 35 36
(A) R (B) (C) (D)
900 11R 36R 35R

20. The number of radial nodes of 3s, 3p and 3d electrons are respectively
(A) 0, 1, 2 (B) 2, 1, 0 (C) 1, 3, 5 (D) 3, 2, 0
3/2
1  1 
21. The 1s orbital of H atom is of the form, =   e - r/0 , where 0 = Bohr radius. The
  0 
probability of finding the electrons at a distance r from the nucleus is given by
(A)  =  2 d r (B)   4πr2 d r (C)  2 4πr2 d r (D) .dV
22. An electron that has the quantum numbers n = 3 and m =2

1
(A) Must have spin value, + (B) Must have l =2, 3 or 4
2
(C) Must have l = 0 ,1 or 2 (D) Must have l = 2
23. In which of the following orbital, electron will be more closer of the nucleus ?
(A) 6s (B) 4f (C) 5d (D) 6p
24. If the number of orbitals of a particular type were (3l + 1), but spin quantum numbers only + ½ and -
1/2, then a d-type orbital will contain a maximum of _ electrons.
(A) 10 (B) 14 (C) 2 (D) 5
25. How many electrons in an atom may have the following quantum numbers? n = 4, s = -1/2
(A) 9 (B) 32 (C) 16 (D) 7
26. The maximum number of electrons in parallel spin in ground state of nitrogen atom is
(A) 3 (B) 5 (C) 7 (D) 4
27. An orbital that has no radial node but two angular node is
(A) 1s (B) 2p (C) 3s (D) 3d
28. Which of the following element will have same number of electrons in s-as well as p-type of orbitals?
(A) Fe(Z = 26) (B) Mg(Z = 12) (C) Ne(Z = 10) (D) none of these
29. Which of the following will have magnetic moment, about 4.9 B.M.?
(A) Cr+(Z = 24) (B) Ti4+ (Z = 22) (C) Fe2+ (Z = 26) (D) Cu2+ (Z =29)
30. The frequency of first line of Balmer series in hydrogen atom is o. The frequency of corresponding
line emitted by singly ionized helium atom is
(A) 2o (B) 4o (C)o/2 (D)o/4
31. If the velocity of an electron in the first Bohr orbit of a hydrogen atom is V, then its velocity in the
third Bohr orbit will be
(A) V/9 (B) V/3 (C)9 V (D)3 V
32. The difference in angular momentum associated with the electron in two successive orbits of
hydrogen atom is
(A) h/ (B) h/2 (C)h/2 (D)(n 1) h/2
33. The missing fission product in the reaction 92U235 + 0n1  57La
146
+ ….. + 3 0n1
(A) 35Br86 (B) 35Br87 (C) 35Fe89 (D) 32Ge89

34. With increasing quantum number, the energy difference between adjacent orbits of hydrogen atom
(A) increases (B) decreases
(C) remains constant (D) first increases followed by a decrease
35. A 3p orbital has

(A) 2 non-spherical nodes (B) 2 spherical nodes
(C) one spherical and one non-spherical node (D) one spherical and 2 non-spherical nodes
36. If the spin quantum number‘s’ has three possible values (-1/2, 0, +1/2), then electronic configuration
of K(19) will be
(A) 1s32s32p93s33p1 (B) 1s22s22p63s23p64s1 (C) 1s22s22p93s23p4 (D) none of these
37. Non - directional orbital is

(A) 3s (B) 4f (C) 4d (D) 4p
38. Assuming Rydberg’s constant (RH) to be 109670 cm–1, the longest wavelength line in the Lyman
series of the hydrogen spectrum is
(A)1215.8 Å (B) 1025.8 Å (C) 972.6 Å (D) 949.8 Å
39. The magnetic quantum number for valence electron of sodium is

(A) 3 (B) 2 (C) 1 (D) zero
40. If kinetic energy of a proton is increased nine times the wavelength of the de-Broglie wave
associated with it would become
(A) 3 times (B) 9 times (C)1/3 times (D)1/9 times
41. Which of the following represents the correct set of four quantum numbers of a 4d electron?
(A) 4, 3, 2, + ½ (B) 4, 2, 1, 0 (C) 4, 3, -2, + ½ (D) 4, 2, 1, - ½
42. A photon of 300 nm is absorbed by a gas and then emits two photons. One photon has a
wavelength 496 nm then the wavelength of second photon is
(A) 759 (B) 857 (C) 957 (D) 657
43. If electrons are excited to 4th shell in He+ ion, the number of wavelengths emitted by electrons during
deexcitation are
(A) 4 (B) 5 (C) 6 (D) 7
44. An electron of mass ‘m’ and charge ‘e’, is accelerated from rest through a potential difference V in
vacuum. Its final speed will be :
(A) (eV / m) (B) 2eV / m (C) (eV / 2m) (D) (2eV / m)
45. Which of the following transitions have the wave number ratio as 108 : 7 in atomic spectra of
hydrogen?
(A) First Lyman and first Brackett (B) First and second Lyman
(C) First Lyman and first Balmer (D) First Lyman and first Paschen
46. Threshold frequency of a metal is f 0 . When light of frequency v  2 f 0 is incident on the metal plate,
maximum velocity of e- emitted is v1 . When frequency of incident radiation is 5 f 0 , maximum
v1
velocity of emitted e- is v2 . Find ratio of :
v2
(A) 1:4 (B) 1:2 (C) 2:1 (D) None of these
47. The calculated value of magnetic moment of 26Fe3+ is

(A) 3.89 B.M (B) 1.73 B.M (C) 4.90 B.M (D) 5.92 B.M
48. Difference between nth and (n + 1)th Bohr’s radius of ‘H’ atom is equal to it’s (n-1)th Bohr’s radius.
The value of n is
(A) 1 (B) 2 (C) 3 (D) 4
4E
49. The energy of a I, II and III energy levels of a certain atom are E , and 2E respectively. A photon
3
of wavelength  is emitted during a transition from III to I. What will be the wavelength of emission
for transition II to I?

(A) (B)  (C) 2  (D) 3 
2
50. Potential energy of electron present in He+ is:

e2 3e 2  2e 2  e2
(A) (B) (C) (D)
2 0 r 4 0 r 4 0 r 4 0 r 2
GET EQUIPPED FOR JEE ADVANCE

( ONLY ONE OPTION CORRECT )
1. What is the series limit for Paschen series of the He+ ion in Å?
(A) 2502 (B) 2520 (C) 2250 (D) 2052
2. The time taken by an electron for one complete revolution in the nth Bohr orbit of the hydrogen atom
is
(A) inversely proportional to n 2 (B)directly proportional to n3
(C) directly proportional to n (D) directly proportional to (n/h)2
3. The ionization potential difference is 2.55eV for two of the Bohr orbits of the atomic hydrogen of
quantum numbers n1 and n2, [n1<n2]. What are the values of n1 and n2?
(A) 2, 3 (B) 3, 4 (C) 2, 4 (D) 3, 5
4. Which of the following statements is correct?

(A) The 4p orbital has three nodes
(B) 3s orbital has no node
(C) Orbital angular momentum of the electron in the 1s orbital of the hydrogen atom is h/2π
(D) The theoretically derived value of Rydberg constant is 109678m-1
5. An electron in a hydrogen atom in its ground state absorbs 1.5 times as much energy as the
minimum required escape from the atom. What is the wavelength of the emitted electron?
(A) 4.7 Å (B) 4.7nm (C) 9.4 Å (D) 9.4nm
6. A one dimensional electron trap has an extension of 1nm. What is the uncertainty in its momentum
in kgm/s?
(A) 1.551×10−24 (B) 1.055×10−25 (C) 1.115×10−23 (D) 5.2×10−26
7. Calculate the mass of the photon with a wavelength corresponding to the series limit of Balmer
transitions of the He+ ion in kg?
(A) 4.22×10−36 (B) 2.24×10−34 (C) 2.42×10-35 (D) 4.22×10−36
8. The wavelength of a certain electron transition in the hydrogen spectrum is 4864Å. Identify the
Transition;
(A) 3rd line Balmer (B) 1st line Lyman (C) 1st line Paschen (D) 2nd line Balmer
9. What according to the Bohr model would be the radius of the electron orbit in the first excited state
of the Li+2 ion??
(A) 0.751Å (B) 0.705Å (C) 0.925Å (D) 0.952Å
10. Photo-electrons are ejected from a metal surface using photons of energy 4×10-20J .The de Broglie
wavelength of the electron emitted with maximum K.E. =59Å . What is the photoelectric threshold in
joules.
(A) 3.313×10−20 (B) 1.131×10−20 (C) 1.331×10−20 (D) 1.673×10−20
11. The series limit values are 8208Å and 22800 Å for the quantum numbers n1 and n2 in the atomic
spectrum of the hydrogen .What is the wavelength for the radiation emitted for the transition n2→n1
in Å?
(A) 15282 (B) 12258 (C) 12825 (D) 15822
12. An electron, practically at rest is initially accelerated through a potential difference of 100V .It then
has a de Broglie wavelength = λ1 Å .It then get retarded through 19 V and then has a wavelength λ2
Å. A further retardation through 32 V changes the wavelength to λ3Å.What is
(λ3― λ2 ) / λ1?
(A) 20/41 (B) 10/63 (C) 20/63 (D) 10/41
13. Wave function vs distance from nucleus graph of an orbital is shown.
The number of nodal sphere of this orbital is

(A) 1 (B) 2 (C) 3 (D) 4
14. For an electron in a hydrogen atom the wave function ψ is proportional to e− (r/(a) where a is Bohr`s
radius . What is the ratio of probability of finding the electron at the nucleus to the probability of
finding the electron at a
(A) e (B) e2 (C) 1/ e2 (D) Zero
15. The angular momentum of electron in Bohr’s orbit is J. What will be the K.E. of electron in that
Bohr’s orbit ?
1 Jv Jv J2 J2
(A) (B) (C) (D)
2 r r 2m 2r
16. If the mass of electron is doubled , the radius of first orbit of H-atom become about
(A) 0.529 Å (B) 0.265 Å (C) 1.058 Å (D) 0.32 Å
17. 400 units of energy is required to take away an electron from the lowest energy state to infinity in a
H-like atom. What is the amount of energy released when an electron jumps from infinity to the
second orbit in that atom ?

(A) 400 units (B) 100 units (C) 1600 units (D) 200 units
18. Which of the following transition in He+ ion emits light of wavelength equal to the longest wavelength
emitted in the Paschen series of H-atom ?
(A) 96 (B) 86 (C) 84 (D) 63
kn2
19. Rydberg gave the equation for all visible radiation in the hydrogen spectrum as  . The value
n2  4
of k in terms of Rydberg constant is
R 4
(A) 4R (B) (C) (D) R
4 R
20. The figure indicates the energy level diagram of an atom and the
origin of six spectral lines in emission (e.g. , line no. 5 arises from
the transition from level B to Y). Which of the following spectral
lines will also occur in the absorption spectrum ?
(A) 4, 5, 6 (B) 1, 2, 3, 4, 5, 6 (C) 1, 4, 6 (D) 1, 2, 3
21. The electron in a hydrogen atom makes transition from M shell to L, the ratio of magnitude of initial
to final acceleration is
(A) 9:4 (B) 81:16 (C) 4:9 (D) 16:81
22. The nucleus of an atom is located at x = y = z = 0 .If the probability of finding an s-orbital electron in
a tiny volume assumed x = a, y = 0 = z is 10−5, what is the probability of finding the electron in the
same sized volume around x = z = 0, y = a?
(A) 10−5 (B) 10−5a (C) 10−5a2 (D) 10−5a−1
23. Suppose it is taken as a working hypothesis that an electron finds itself inside a typical nucleus with
an uncertainty in momentum, Δp≈10-20kgm/s, what is an approximate estimate of the size of the
nucleus?
(A) 1.058×10−13m (B) 8.53×10−15 m (C) 3.58×10−16m (D) 5.27×10−15m
24. Energy will be absorbed for the process of separating

(A) a proton from a proton (B) an electron from proton
(C) an electron from an electron (D) a neutron from a neutron
25. Principal, azimuthal and magnetic quantum numbers are respectively related to
(A) size, orientation and shape (B) size, shape and orientation
(C) shape, size and orientation (D) none of these
26. In the hydrogen atoms, the electrons are excited to the 5th energy level. The number of the lines
that may appear in the emission spectrum will be
(A) 4 (B) 8 (C) 10 (D) 12
27. Light of wavelength λ shines on a metal surface with intensity x and the metal emits y electrons per
second of average energy Z , what will happen to y and Z if x is doubled
(A) y will be doubled and Z will become half
(B) y will remain same and Z will be doubled
(C) Both y and Z will be doubled
(D) y will be increased but Z will remain same

28. If λ1 and λ2 denotes the de Broglie wavelength of two particles with same masses but charges in the
ratio of 1:2 after they are accelerated from rest through the same potential difference then
(A) λ1 > λ2 (B) λ1 = λ2 (C) λ1 < λ2 (D) None
MORE THAN ONE OPTION CORRECT
1. When α-particle are sent through a thin metal foil, most of them go straight through the foil,
because:
(A) α-particle are much heavier than electrons (B) α-particle are positively charged
(C) most part of the atom is empty space (D) α-particle move with high velocity
2. Rutherford`s α-scattering experiment led to the following conclusions

(A) Atom has largely empty space
(B) The centre of the atom has positively charged nucleus
(C) The size of the nucleus is very small as compared to the size of the atom
(D) The electrons revolve around the nucleus
3. The probability of finding the electron in Px orbital is

(A) Maximum at two opposite sides of the nucleus along the x-axis (B) Zero at nucleus
(C) Maximum at nucleus (D) Along the x-axis
4. Which of the statements is(are) correct?
(A) Electrons in motion behave as if they are waves
(B) s-orbital is non directional
(C) An orbital can accommodate a maximum of the two electrons with parallel spins
(D) The energies of the various sub-levels in the same shell are in order s>p>d>f
5. Which concerning Bohr`s model are true?

(A) Predicts that probability of electron near the nucleus is more
(B) Angular momentum of electron in H-atom =nh/2π
(C) Introduces the idea of stationary states
(D) Explains line spectrum of hydrogen
6. Which sets of quantum no. are consistent with the theory
n l m s
(A) 2 1 0 -1/2
(B) 4 3 -2 -1/2
(C) 3 2 -3 1/2
(D) 4 3 -3 1/2
7. Heisenberg uncertainty principal is not significant for

(A) Moving electrons (B) Motor car
(C) Stationary particles (D) All of the above
8. Consider the electronic configuration for neutral atoms

1) 1s22s22p63s1 2) 1s22s22p64s1. Which of the following statements is/are false?
(A) Energy is required to change 1 to 2
(B) 1 represents Na atom
(C) 1 and 2 represent different elements
(D) More energy is required to remove one electron from 1 than 2

9. For the energy levels in an atom which one of the following statements is/are correct?
(A) 4f subshell has maximum 14 electrons.
(B) The 2nd principal energy level can have 4 sub energy levels and contains a maximum of 8e
(C) The M energy level can have a maximum of 32 electrons
(D) The 4s sub energy level is at lower energy than the 3d sub energy level
10. Which of the following statements are correct for an electron that has n = 4 and m =−2?
(A) The electron may be in a d orbital
(B) The electron is in the fourth principal electronic shell
(C) The electron may be in a p-orbital
(D) The electron may have the spin quantum number =0.5
11. Which of the following statement is/are correct??

(A) There is no probability of finding a p –electron exactly at the nucleus.
(B) The orbital d2z has two lobes of electron density directed along the z-axis and a ring of electron
density (called dough nut) centered in the xy-plane
(C) The orientation of p-orbital and d-orbital minimize electron-electron repulsion in many e- atoms
(D) None is correct
12. Which of the following is/are correct??

(A) For all values of n the p-orbitals have the same shape but the overall size increases as n
increases, for a given atom
(B) The fact that there is a particular direction, along which each p-orbital has maximum electron
density, plays an important role in determining molecular geometries
(C) The charge cloud of a single electron in 2px atomic orbital consists of two lobes of electron
density
(D) None is correct
13. Which of the following is the correct set of four quantum numbers for each of the electrons in the 3d
sub shell when it is fully occupied?
(A) n=3;  =2; m=0,1,─1,2, ─2 and s = ±0.5, ±0.5, ±0.5, ±0.5 and ±0.5
(B) n=3;  =1; m=0,1,─1,2,─2 and s = ±0.5, ±0.5, ±0.5, ±0.5 and ±0.5
(C) n=4;  =2; m=0,1,─1,2,─2 and s=±0.5, ±0.5, ±0.5, ±0.5 and ±0.5
(D) None is correct.
14. Which of the following statements is/are correct??

(A) The energy of an electron in a many electron atom generally increases with an increase in the
value of n, but for a given (n+l), the lower the value of l, the lower is the energy.
(B) An electron close to the nucleus experiences a large electrostatic attraction
(C) For a given value of n, a s-electron penetrates the nucleus more than a p-electron which
penetrates more than a d-electron and so on
(D) None is correct

(A) All substances are diamagnetic
(B) There are substances in which all electron spins are paired
(C) There are substances in which one or more electrons have unpaired spins
(D) The greater the number of unpaired electrons, the greater is Paramagnetism per mole of
substance

16. The mathematical expression for the uncertainty principal is

(A) Δ x Δp ≥ h/4π (B) Δ EΔt ≥ h/4π (C) Δ x Δp ≥ h/p (D) ΔEΔt ≥ h/p
17. Choose the correct relations on the basis of Bohr`s theory

(A) Velocity of electron α1/n (B) Frequency of revolution α 1/n3
(C) Radius of orbit α n2Z (D) Force on electron α 1/n4
18. Which of the following statements is/are correct?

(A) A photon is a positively charged nuclear particle
(B) A photon is a particle of light energy
(C) A photon is a quantum of light
(D) A photon is a bundle of energy of definite magnitude.
19. Which of the following statements is/are correct?

(A) Stark effect is the splitting lines when source is placed in electric field
(B) Beyond a certain limit a spectrum of an atom there is continuum
(C) The number of spectral line in line spectrum decreases with increase in the value of n(final
energy level)
(D) Shielding effect is possible in H-atom
20. Which statements is/are true regarding white lights?

(A) It is a form of energy
(B) It can be deflected by a magnet
(C) It consists of photons of same energy
(D) It is part of electromagnetic spectrum
21. An electron jumps nth level to 1st level , the fact which is/are correct about H atoms is/are
(A) Number of spectral lines =n(n-1)/2
(B) Number of spectral lines =∑(n-1)
(C) If n=4, the number of spectral lines =6
(D) Number of spectral lines =n(n-1)
22. Photoelectric effect supports quantum nature of light because

(A) There is a minimum frequency below which no emission of photoelectron is possible
(B) Maximum KE of photo electrons depends only on frequency of light and not on intensity
(C) Even when the metal surface is faintly illuminated the photoelectron leave the surface
immediately
(D) Electric charge of the photoelectrons is quantized

(A) If the value of l=0, the electron distribution is spherical
(B) The shape of the orbital is given by magnetic quantum number
(C) Orbital angular momentum of 1s, 2s, 3s electrons are equal
(D) In an atom, all electrons travel with the same velocity
COMPREHENSION TYPE
COMPREHENSION – 1:
Rutherford proposed the atomic model after his most striking experiment on   scattering leading to
discovery of nucleus. Bohr later on modified the atomic model on the basis of Planck’s quantum theory of
nh
light and proposed the concept of stationery circular orbit of quantized angular momentum . The
2
collection of the line spectrum led Sommerfeld to give the idea of elliptical orbits. He successfully explained
the existence of subshells and their number in a shell. The orbital angular momentum of subshells was
h
proposed as l  l  1 . . the emission of a spectral line in atomic spectra was supposed to be due to the
2
jump of electron from one energy level to other.
1. The orbital angular momentum of electron in 2p orbital is:

h h h 
(A) (B) (C) (D)
2 2 2 2
2. The volume occupied by the nucleus is about …… times of volume of atom:

(A) 10 – 15 (B) 1015 (C) 10 ─12 (D) 10 – 10
3. Non – directional orbital is

(A) 3s (B) 4f (C) 4d (D) 4p
14
4. The total number of fundamental particles in 6 C is
(A) 6 (B) 8 (C) 14 (D) 20
5. The minimum energy is given out when an electron jumps from one orbit to other from:
(A) 2 to 1 (B) 3 to 2 (C) 4 to 3 (D) 5 to 4
6. An oil drop has ─6.39 x 10─19 coulomb charge. The number of electrons in this oil drop is:
(A) 4 (B) 3 (C) 2 (D) 1
COMPREHENSION – 2 :
Bohr proposed his atomic model based on Classical Physics and derived following relations for one
electron system:
E1 u
For H – atom rn  n 2  r1 , E n  2
, u n  1 ; r1  0.529A; u1  2.19 108 cm sec,; E1  13.6eV
n n
For 1 electron systems, other than H
n 2  r1H E1H  Z 2 u1H  Z
rn  ; En  2
; un 
Z n n
Later on de Broglie proposed the dual nature of electron and put forward his wave concept. The
wavelength of electron in an orbit was given by   h / mu .
1. The number of waves made by a Bohr electron in H – atom for one complete revolution in its 3rd
orbit are:
(A) 1 (B) 2 (C) 3 (D) 4
2. The circumference (in m) of third Bohr orbit in H – atom is :

(A) 3.0 10 7 (B) 3.0 10 8 (C) 3.0 10 6 (D) 3.0 10 9
3. The wavelength (in m ) of moving electron in 3rd orbit of H – atom is :

(A) 1.0 10 9 (B) 2.0 10 9 (C) 1.0 10 7 (D) 1.0 10 8
4. The potential energy of electron in 3rd Bohr orbit of H – atom is:

(A) - 2.42 10 12 erg (B) -4.84 10 12 erg (C) +4.84 10 12 erg (D) 2.42 10 12 erg
5. The momentum of electron in 3rd Bohr orbit of H – atom is :

(A) 6.65 10 25 kg m sec 1 (B) 6.65 10 28 kg m sec 1
(C) 6.65 10 29 kg m sec 1 (D) 6.65 10 20 kg m sec 1
h
De Broglie proposed dual nature for electron by putting his famous equation   . Later on
mu
 h 
Heisenberg proposed uncertainly principle as x.p     . On the contrary particle nature
2 2 
of electron was established on the basis of photoelectric effect. When a photon strikes the metal
surface, it gives up its energy to the electron. Part of this energy (say W) is used by the electrons to
escape from the metal and the remaining imparts the kinetic energy (1/2 mu2) to the photoelectron.
The potential applied on the surface to reduce the velocity of photoelectron to zero is known as
stopping potential.
1. With what velocity must an electron travel so that its momentum is equal to that of photon of
wavelength is   5200 A :
(A) 800 m s- 1 (B) 1400 m s- 1 (C) 400 m s- 1 (D) 200 m s-1
2. With what potential should a beam of electron be accelerated so that its wavelength becomes equal
to 1.54 A .
(A) 63.3 V (B) 6.33 V (C) 633 V (D) None of these
3. The binding energy of electron in a metal is 250 kJ mol – 1 . The threshold frequency of metal is:
(A) 6  10 12 sec 1 (B) 6  1014 sec 1 (C) 6  1010 sec 1 (D) 6  1012 sec 1
4. If uncertainties in position and momentum of an electron are same, then uncertainty in its velocity
can be given by:
h u 
(A)  2
(B)  (C)  (D) Either of these
4m 4m 2m 2
5. The wavelength of a golf ball weighing 200g and moving at a speed of 5 meter /hr is of the order:
(A) 10 – 10 m (B) 10 – 20 m (C) 10 – 30 m (D) 10 – 40 m
The electrons in a poly – electronic atom are filled one by one in order of increasing energy level.
The energy of subshells and orientation of orbitals depends upon the values of three quantum
numbers (i.e. n , l and m respectively) derived from Schrodinger wave equation. The different
orbitals of a subshells however posses same energy level and are called degenerate orbitals but
their energy level changes in presence of magnetic field and the orbitals are non – degenerate. A
spectral line is noticed if an electron jumps from one level to other. The paramagnetic nature of
element is due to the presence of unpaired electron.
1. P3- is isoelectronic with:
(A) N 3- (B) As3+ (C) Cl- (D) F-
2. The number of unpaired electrons in Cr atom is:

(A) 2 (B) 3 (C) 5 (D) 6
3. The element which has as many ‘s’ electrons as ‘p’ electrons but belong to III period is :
(A) O (B) Mg (C) Al (D) C
4. The total magnetic moment of Ni2+ ion is :

(A) 6 BM (B) 8 BM (C) 15 BM (D) 12 BM
5. The number of spherical and angular nodes in 2p orbitals are:

(A) 1, 1 (B) 2, 1 (C) 1, 0 (D) 0, 1
6. The possible number of spectral lines when an electron can jump from 5th shell to 2nd shell is:
(A) 4 (B) 2 (C) 3 (D) 6
7. The correct order for energy levels in H – atom is (Bohr’s theory)
(A) 3s = 3p = 3d > 2s (B) 3d > 3p > 3s > 2s
(C) 3d > 3p = 3s > 2s (D) 3d > 3p > 3s = 2s
MATRIX MATCH
Column-I and Column-II contains four entries each. Entries of Column-I are to be matched with some
entries of Column-II. One or more than one entries of Column-I may have the matching with the same
entries of Column-II.
1. If in Bohr’s model, for unielectronic atom following symbols are used rn , z  Radius of n th orbit with
atomic number Z; U n, z  Potential energy of e  ;
K n, z  Kinetic energy of e  : Vn, z  Velocity of e  ;
Tn, z  Time period of revolution
Column-I Column-II
(A) U1,2 : K1,1 (P) 1 : 8
(B) r2,1 : r1,2 (Q) – 8 : 1
(C) V1,2 : V2,4 (R) 1 : 1
(D) T1,2 : T2,2 (S) 8 : 1
2. Column-I Column-II
(A) The number of radial node of 5s atomic orbital is (P) 1
(B) The number of angular node of 3d yz atomic orbital is (Q) 4
(C) The sum of number of angular node and radial (R) 2
node of 4d xy atomic orbital
(D) The number of angular node of 3p atomic orbital is (S) 3
h
(A) Orbital angular momentum of an electron (P) s ( s  1)
2
(B) Angular momentum of an electron in an orbit (Q) n( n  2)
nh
(C) Spin angular momentum of an electron (R)
2
h
(D) Magnetic moment of atom (in B.M.) (S) l (l  1)
2
(A) No. of orbitals in the nth shell (P) 2(2l + 1)
(B) Max. no. of electrons in a subshell (Q) n
(C) No. of subshells in nth shell (R) 2l + 1
(D) No. of orbitals in a subshell (S) n2
1
(A) (P) 4s
r
4  r 2 2
(B) (Q) 5px
Distance from nucleus
(C) Angular probability is dependent on  and  (R) 3s

(D) No angular node is present (S) 6dxy
6. Column - I Column - II
(A) m= 1 (P) p- subshell
(B) l = 2 (Q) f- subshell
(C) n = 3 (R) d- subshell
(D) Angular nodes (S) s- subshell
7. Column - I Column - II (Bohr’s model)

2
(A) Total Energy of e− (P)  Z
3
(B) Revolution frequency of e− (Q)  Z
(C) Acceleration of e− (R) Decreases as orbit number increases
(D) Radius of orbit (S) Increases as orbit number increases
WINDOW TO JEE MAIN
1. The energy required to dislodge an electron from excited isolated H-atom is ( IE1  13.6 eV )
(a) < 13.6 and > 3.4 eV (b)  13.6 eV (c) > 13.6 eV (d) Equal to 13.6 eV
(DCE 2000)
2. Electromagnetic radiation with maximum wavelength is (DCE 2000)
(a) Infrared (b) X-Ray (c) Radiowave (d) Ultraviolet ray.
3. Which of the following sets of quantum numbers, represents the 19th electron of chromium?
n l m s
(a) 4 1 1 1/ 2
(b) 4 0 0 1/ 2
(c) 3 2 2 1/ 2
(d) 3 2 0 1/ 2
(DCE 2001)
4. The ionization potential of hydrogen from ground state to the first excited state is
(a) 3.4 eV (b) - 3.4 eV (c) 10.2 eV (d) - 13.6 eV
(DCE 2001)
5. The mass of the proton is 1840 times of electron, its accelerated by a potential difference is 1 kV.
The kinetic energy of proton will be
1
(a) 920 keV (b) keV (c) 1 keV (d) 1840 keV
1840
(DCE 2001)
6. The presence of 3 unpaired electrons in N atom can be explained by
(a) Hund’s rule (b) Uncertainty principle
(c) Aufbau principle (d) Pauli’s exclusion principle.
(DCE 2002)
7. A cricket ball of 0.5 kg is moving with a velocity of 100 m/sec. The wavelength associated with its
motion is
(a) 1.32  1035 m (b) 6.6  1034 m (c) 1/100 cm (d) 6.6  1028 m .
(DCE 2004)
8. The number of radial nodes in 5d is
(a) 1 (b) 2 (c) 3 (d) 4.
(DCE 2005)
9. The H-spectrum shows
(a) Heiseberg’s uncertainly principle (b) Diffraction
(c) Polarisation (d) Presence of quantized energy level.
(DCE 2005)
10. Which of the following statements does not form a part of Bohr’s model of hydrogen atom?
(a) Energy of the electrons in the orbit is quantised
(b) The electron in the orbit nearest to the nucleus has the lowest energy
(c) Electrons revolve in different orbits around the nucleus
(d) The position and velocity of the electrons in the orbit cannot be determined simultaneously.
(DCE 2005)
11. Electrons will first enter into the set of quantum numbers n = 5, l = 0 or n = 3, l = 2
(a) n = 5, l = 0 (b) Both possible (c) n = 3, l = 2 (d) Data insufficient.
(DCE 2005)
12. Which of the following is non-permissible?
(a) n = 4, l = 3, m = 0 (b) n = 4, l = 2, m = 1
(c) n = 4, l = 4, m = 1 (d) n = 4, l = 0, m = 0
(DCE 2005)

13. The following quantum numbers are possible for how many orbitals? n = 3, l = 2, m = +2.
(a) 3 (b) 2 (c) 1 (d) 4 (DCE 2006)
14. The number of nodal planes in a p x orbital is

(a) One (b) Two (c) Three (d) Zero
(DCE 2006)
15. In Bohr series of lines of hydrogen spectrum, the third line from the red end corresponds to which
one of the following inter-orbit jumps of the electron for Bohr orbits in an atom of hydrogen?
(a) 2  5 (b) 3  2 (c) 5  2 (d) 4  1 (DCE 2006)
16. A body of mass 10 mg is moving with a velocity of 100 ms 1 . The wavelength of the de-Broglie
wave associated with it would be
(a) 6.63 X 10-7 m (b) 6.63 X 10-31 m (c) 6.63 X 10-34 m (d) 6.63 X 10-35 m
(DCE 2006)
th
17. According to Bohr’s theory, the angular momentum of an electron in 5 orbit is
h h h h
(a) 25 (b) 1.0 (c) 10 (d) 2.5
   
(AIEEE2006)
31
18. Uncertainty in the position of an electron (mass = 9.1 10 kg ) moving with a velocity 300 ms 1 ,
accurate upto 0.001% will be ( h  6.6  10 34 Js )
(a) 19.2  10 2 m (b) 5.76  10 2 m (c) 1.92  10 2 m (d) 3.84  10 2 m
(AIEEE 2005)
19. Which of the following is correctly matched ?
3Rh
(a) Momentum of H – atom when electrons return from n = 2 to n = 1 :
4
(b) Momentum of proton : Independent of wavelength of light
(c) e/m ratio of anode rays : Independent of gas in the discharge tube
1/ 2
(d) Radius of nucleus :  Mass no.
(DCE 2007)
20. In which of the following orbital diagrams are both Pauli’s exclusion principle and Hund’s rule
violated?
(a) (b)
(c) (d)
(DCE 2007)
21. Imagine an atom made up of a proton and a hypothetical particle of double the mass of the electron
but having the same charge as the electron. Apply the Bohr atomic model and consider all possible
transitions of this hypothetical particle to the first excited level. The largest wavelength ;photon that
will be emitted has wavelength  (given in terms of Rydberg constant R for the hydrogen atom) is
equal to
9 36 18 4
(a) (b) (c) (d)
5R 5R 5R R
(DCE 2007)

22. Which of the following sets of quantum numbers represents the highest energy of an atom?
(a) n = 3, l = 0, m = 0, s = +1/2 (b) n = 3, l = 1, m = 1, s = +1/2
(c) n = 3, l = 2, m = 1, s = +1/2 (d) n = 4, l = 0, m = 0, s = +1/2
(AIEEE 2007)
23. 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
(a) 9.84  105 J mol1 (b) 8.51105 J mol 1
(c) 6.56  105 J mol1 (d) 7.56  105 J mol1
(AIEEE 2008)
24. In an atom, an electron is moving with a speed of 600 m/s with an accuracy of 0.005%. certainty
with which the the position of the electron can be located is ( h  6.6  10 34 kgm 2s 1 , mass of
electron, e m  9.1 10 31 kg )
(a) 1.52  104 m (b) 5.10  10 3 m (c) 1.92  103 m (d) 3.84  10 3 m
(AIEEE 2009)
25. Calculate the wavelength (in nanometre) associated with a proton moving at 1.0  103 ms 1 . (Mass
of proton = 1.67  1027 kg and h  6.63  10 34 Js )
(a) 0.032 nm (b) 0.40 nm (c) 2.5 nm (d) 14.0 nm
(AIEEE 2009)
WINDOW TO JEE ADVANCED
OBJECTIVE QUESTIONS I
1. Rutherford’s experiment on scattering of α-particles showed for the first time that the atom has
(JEE 1981)
(a) electrons (b) protons (c) nucleus (d) neutrons
2. Any p-orbital can accommodate up to (JEE 1983)

(a) Four electrons (b) six electrons

(c) two electrons with parallel spins (d) two electrons with opposite spins
3. The principal quantum number of an atom is related to the (JEE 1983)

(a) size of the orbital (b) spin angular momentum
(c) Orientation of the orbital in space (d) Orbital angular momentum
4. Rutherford’s scattering experiment is related to the size of the (JEE 1983)

(a) nucleus (b) atom (c) electron (d) neutron
5. The increasing order (lowest first) for the values of e/m (charge/mass) for electron (e), proton(p),
neutron (n) and alpha particle (α) is (magnitude only) (JEE 1984)
(a) e,p,n,a (b) n,p,e,α (c) n,p,α,e (d) n,α,p,e
6. Correct set of four quantum numbers for the valence (outermost) electron of rubidium (Z=37) is
(JEE 1984)
1 1 1 1
(a) 5,0,0,+ (b) 5,1,0,+ (c) 5,1,1,+ (d) 6,0,0,+
2 2 2 2
7. Which electronic level would allow the hydrogen atom to absorb a photon but not to emit a photon?
(JEE 1984)
(a) 3s (b) 2p (c) 2s (d) 1s
8. Bohr’s model can explain (JEE 1985)

(a) the spectrum of hydrogen atom only
(b) spectrum of an atom or ion containing one electron only
(c) the spectrum of hydrogen molecule
(d) the solar spectrum
9. The radius of an atomic nucleus is of the order of (JEE 1985)

(a) 10-10cm (b) 10-13cm (c) 10-15cm -8
(d) 10 cm
10. Electromagnetic radiation with maximum wavelength is (JEE 1985)

(a) ultraviolet (b) radio wave (c) X ray (d) infrared
11. Rutherford’s alpha particle scattering experiment eventually let to the (JEE 1986)
(a) Mass and energy are related
(b) electrons occupy space around the nucleus
(c) neutrons are buried deep in the nucleus
(d) the point of impact with matter can be precisely determined.
12. Which one of the following sets of quantum numbers represents an impossible arrangement?
(JEE 1986)
n l m s
1
(a) 3 2 -2
2
1
(b) 4 0 0
2

1
(c) 3 2 -3
2
1
(d) 5 3 0 
2
13. The ratio of the energy of a photon of 2000Åwavelength radiation to that of 4000 Å radiation is
1 1
(a) (b) 4 (c) (d) 2 (JEE 1986)
4 2
14. The wavelength of a spectral line for electronic transition is inversely related to (JEE 1988)
(a) the number of electrons undergoing the transition.
(b) the nuclear charge of the atom
(c) the difference in the energy of the energy levels involved in the transition
(d) the velocity of the electron undergoing the transition.
15. The orbital diagram in which the aufbau principle is violated (JEE 1988)
(a) (b)
(c) (d)
16. The outermost electronic configuration of the most electronegative elements is (JEE 1988,90)
2 3 2 4 2 5
(a) ns np (b) ns np (c) ns np (d) ns np6
2
17. The correct ground state electronic configuration of chromium atom is (JEE 1989)
(a) [Ar]3d5 4s1 (b) [Ar]3d4 4s2 (c) [Ar]3d5 4s0 (d) [Ar]4d5 4s1
18. The correct set of quantum numbers for the unpaired electron of chlorine atom is (JEE 1989)
n l m
(a) 2 1 0
(b) 2 1 1
(c) 3 1 1
(d) 3 0 0
19. Which of the following does not characterise X – rays? (JEE 1992)
(a) The radiation can ionise gases
(b) It causes ZnS to fluorescence
(c) Deflected by electric and magnetic fields
(d) Have wavelengths shorter than ultraviolet rays
20. Which of the following relates to photons both as wave motion and as a stream of particles?
(JEE 1992 )
(a) Interference (b) E = mc2
(c) Diffraction (d) E = hv
21. The orbital angulr momentum of an electron in 2s orbital is (JEE 1996)

1 h
(a) + .
2 2
(b) zero
h
(c)
2
h
(d) 2.
2
22. Which of the following has the maximum number of unpaired electrons? (JEE 1996)
(a) Mg2+ (b) Ti3+ (c) V3+ (d) Fe2+
23. The first use of quantum theory to explain the structure of atom was made by (JEE 1997)
(a) Heisenberg (b) Bohr (c) Planck (d) Einstein
24. For a d-electron, the orbital angular momentum is (JEE 1997)

 h   h   h   h 
(a) 6   (b) 2  (c)   (d) 2  
 2   2   2   2 
25. 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) (JEE 1998)
(a) -3.4eV (b) -4.2eV (c) -6.8 eV (d) + 6.8 eV
26. The electrons, identified by quantum numbers n and l, (i) n = 4, l = 1 (ii) n = 4, l = 0 (iii) n=3, l = 2 (iv)
n = 3, l = 1 can be placed in order of increasing energy, from the lowest to highest ,as (JEE 1999)
(a) (iv)<(ii)<(iii)<(i) (b) (ii)<(iv)<(i)<(iii)
(c) (i)<(iii)<(ii)<(iv) (d) (iii)<(i)<(iv)<(ii)
27. The electronic configuration of an element is 1s2, 2s22p6, 3s23p63d5, 4s1. This represents its.
(JEE 2000)
(a) excited state (b) ground state (c) cationic form (d) anionic form
28. The number of nodal planes in a px orbital is (JEE 2000)

(a) one (b) two (c)three (d) zero.
29. The wavelength associated with a golf ball weighing 200g and moving at a speed of 5m/h is of the
order (JEE 2001)
(a) 10-10m (b) 10-20m (c) 10-30m (d) 10-40m
30. The quantum numbers +1/2 and -1/2 for the electron spin represent (JEE 2002)
(a) rotation of the electron in clockwise and anticlockwise direction respectively.
(b) rotation of electron in anticlockwise and clockwise direction respectively
(c) magnetic moment of electron pointing up and down respectively
(d) two quantum mechanical spin states which have no classical analogue
31. If the nitrogen atom had configuration 1s7, it would have energy lower than that of the normal ground
state configuration 1s2 2s2 2p3, because the electrons would be closer to the nucleus, yet 1s7 is not
observed because it violates (JEE 2002)
(a) Heisenberg uncertainty principle
(b) Hund’s rule
(c) Pauli exclusion principle
(d) Bohr postulate of stationary orbits

32. Rutherford’s experiment , which established the nuclear model of the atom, used a beam of
(JEE 2002)
(a) β-particles , which impinged on the metal foil and got absorbed
(b) γ–rays which impinged on a metal foil and got scattered
(c) helium atom which impinged on metal foil and got scattered
(d) helium nuclei which impinged on metal foil and got scattered
33. Which hydrogen like atom have similar radius as that of Bohr orbit of hydrogen atom? (JEE 2004)
(a) n=2, Li2+ (b) n=2, Be3+ (c) n=2, He+ (d) n=3, Li2+
34. The number of radial nodes in 3sand 2p respectively are (JEE 2005)
(a) 2 and 0 (b) 0 and 2 (c) 2 and 1 (d) 1 and 2
35. The kinetic energy of an electron in the second Bohr of a hydrogen atom is [ a 0 is Bohr radius]
[JEE 2012]
2 2 2 2
h h h h
(a) (b) (c) (d)
42 ma 20 162 ma 02 32 2 ma 02 642 ma 02
Objective Questions II [One or more than one correct option]
76
1. An isotone of Ge is
32 (JEE 1984)
77 77 77 78
(a) 32 Ge (b) 33 As (c) 34 Se (d) 34 Se
2. Many elements have non integaral atomic masses because (JEE 1984)
(a) they have isotopes
(b) their isotopes have non-integral masses
(c) their isotopes have different masses
(d) the constituents, neutrons, protons and electrons, combine to give fractional masses
3. When alpha particles are sent through a thin metal foil, most of them go straight through the foil because
(a) alpha particles are much heavier than electrons (JEE 1984)
(b) alpha particles are positively charged
(c) most part of the atom is empty space
(d) alpha particles move with high velocity
4. The sum of the number of neutrons and proton in the isotope of hydrogen (JEE 1986)
(a) 6 (b) 5 (c) 4 (d) 3
5. The atomic nucleus contains (JEE 1986)

(a) protons (b) neutrons (c) electrons (d) photons
6. Which of the following statement (s) is (are) correct? (JEE 1998)
5 1
(a) The electronic configuration of Cr is [Ar] 3d 4s . (Atomic number of Cr=24).
(b) The magnetic quantum number may have a negative value
(c) In silver atom, 23 electrons have a spin of one type and 24 of the opposite type. (Atomic number of
Ag = 47)
(d) The oxidation state of nitrogen in HN3 is -3.
7. The ground state electronic configuration of nitrogen atom can be represented by

(JEE 1999)
(a) (b)
(c) (d)
ASSERTION AND REASON:
Read the following questions and answer as per the direction given below:
(a) Statement I is true; Statement II is true, Statement II is the correct explanations of Statement I.
(b) Statement I is true; Statement II is true ,Statement II is NOT the correct explanations of Statement I.
(c) Statement I is true; Statement II is false.
(d) Statement I is false; Statement II is true.
1. Statement I: The first ionization energy of Be is greater than that of B.

Statement II: 2p orbital is lower in energy than 2s. (JEE 2000)
COMPREHENSION BASED QUESTIONS:
The hydrogen – like species Li2+ is in a spherically symmetric 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)
1. The state S1 is
(a) 1s (b) 2s (c) 2p (d) 3s
2. 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
3. The orbital angular momentum quantum number of the state S2 is

(a) 0 (b) 1 (c) 2 (d) 3
MATCH THE COLUMNS:
1. According to Bohr’s theory

En = Total energy
Kn= Kinetic energy
Vn= Potential energy
rn = Radius of nth orbit
Match the following: (JEE 2006)
Column I Column II
(A) Vn/Kn= ? (p) 0
(B) If radius of nth orbit ∝

x (q) -1
E ,x ?
n
(r) -2
(C) Angular momentum in lowest orbital
(D) 1/rn∝zy, y= ?

(s) 1
2. Match the entries in Column I with the correctly related quantum number (s) in column II. (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 obeying Pauli’s principle
(C) Shape, size and orientation of (r) Magnetic quantum number
hydrogen – like atomic orbital
(D) Probability density of electron at the
nucleus in hydrogen – like atom (s) Electron spin quantum number
FILL IN THE BLANKS:
1. The mass of hydrogen is _____kg. (JEE 1982)

2. Isotopes of an element differ in the number of ____ in their nuclei (JEE 1982)
3. When there are two electrons in the same orbital, they have _____spins (JEE 1983)
4. Elements of the same mass number but of different atomic number are known as _____.(JEE 1983)
5. The uncertainty principle and the concept of wave nature of matter were proposed by ____ and ____
respectively (JEE 1988)
6. The light radiations with discrete quantities of energy are called _____. (JEE 1993)
7. Wave functions of electrons in atoms and molecules are called _____. (JEE 1993)
8. The 2px, 2py and 2Pz orbitals of atom have identical shapes but differ in their____. (JEE 1993)
9. The outermost electronic configuration of Cr is ______. (JEE 1994)
TRUE OR FALSE:
1. The outer electronic configuration of the ground state chromium atom is 3d44s2. (JEE 1982)
-6 -5
2. Gamma rays are electromagnetic radiations of wavelengths of 10 cm to 10 cm. (JEE 1983)
3. The energy of the electron in the 3d-orbital is less than that in the 4s-orbital in the hydrogen atom.
According to Bohr’s theory . (JEE 1983)
4. The electron density in the XY plane in 3d x2  y 2 orbital is zero. (JEE 1986)
5. In a given electric field, β-particles are deflected more than α – particles in spite of α-particles having
larger charge. (JEE 1993)
INTEGER TYPES QUESTION:
1. The maximum number of electrons that can have principal quantum number, n = 3 and apin quantum
1
number, ms = - , (JEE 2011)
2
2. The work function (  ) of some metals is listed below. The number of metals which will show
photoelectric effect when light of 300nm 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
SUBJECTIVE QUESTION:
1. Give reason why the ground state outermost electronic configuration of silicon is :
(JEE 1985)
3s 3p 3s 3p
and not
2. What is the maximum number of electrons that may be present in all the atomic orbital with principal
quantum number 3 and azimuthally quantum number 2? (JEE 1985)
3. According to Bohr’s theory, the electronic energy of hydrogen atom in the nth Bohr’s orbit is given by:
(JEE 1990)
21.7  1019
En  J
n2
What is the longest wavelength for He+ (n=3).
4. Estimate the difference in energy between 1st and 2nd Bohr’s 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
l = 3.0×10-8m? Which hydrogen atom-like species does this atomic number correspond to?(JEE 1993)
5. What transition in the hydrogen spectrum would have the same wavelength as the Balmer transition n=4
to n = 2 of He+ spectrum? (JEE 1993)
6. Find out the number of waves made by a Bohr’s electron in one complete revolution in its 3rd orbit.
(JEE 1994)
7. Iodine molecule dissociates into atoms after absorbing light to 4500Å. If one quantum of radiation is
absorbed by each molecule, calculate the kinetic energy of iodine atoms. (Bond energy of I2 = 240kJ
mol-1). (JEE 1995)
8. Calculate the wave number for the shortest wavelength transition in the Balmer series of atomic
hydrogen. (JEE 1996)
9. Consider the hydrogen atom to be proton embedded in a cavity of radius a (Bohr’s radius) whose
charge is neutralised by the addition of an electron to the cavity in vacuum, infinitely slowly. Estimate
the average total energy of an electron in its ground state in a hydrogen atom as the work done in the
above neutralisation process. Also, if the magnitude of the average kinetic energy is half the magnitude
of the average potential energy, find the average potential energy. (JEE 1996)
10. With what velocity should anα-particle travel towards the nucleus of a copper atom so as to arrive at a
distance 10-13m from the nucleus of the copper atom? (JEE 1997)

11. An electron beam can undergo diffraction by crystals. Through what potential should a beam of
electrons be accelerated so that its wavelength becomes equal to 1.54 Å.
(JEE 1997)
12. Calculate the energy required to excite 1L of hydrogen gas at 1 atm and 298 k to the first excited sate of
atomic hydrogen. The energy for the dissociation of H – H bond is 436kJ mol-1. (JEE 2000)
13. The wavelength corresponding to maximum energy for hydrogen is 91.2nm. Find the corresponding
wavelength for He+ion. (JEE 2003)
14. (a) The Schrodinger wave equation for hydrogen atom is;
3
r
1  1 2  r   2a0
Ψ1s= 1   2  e
a
 0  a 
4  2  2 0
Where, a 0 is Bohr’s radius. Let the radial node in 2s be at r0 . Then r0 in terms of a 0

(b) A baseball having mass 100g moves with velocity 100 m/s. Find out the value of wavelength of
baseball. (JEE 2004)
15. (a) Calculate velocity of electron in first Bohr orbit of hydrogen atom (Given, r = a 0 )
(b) Find de-Broglie wavelength of the electron in first Bohr orbit.
(c) Find the orbital angular momentum of 2p orbital in terms of h/2π units. (JEE 2005)
EXPERTISE ATTAINERS
1. Light from a discharge tube containing hydrogen atoms falls on the surface of a piece of sodium.
The kinetic energy of the fastest photo electrons emitted from sodium is 0.73 eV. The work
function for sodium is 1.82 eV. Find
i) The energy of the photons causing the photo electric emission.
ii) The quantum numbers of the two levels involved in the emission of these photons.
2. An electron in order to have a wavelength of 500Å, through what potential difference it must
pass?
3. The photo electric emission requires a threshold frequency 0 for a certain metal. 1 = 2200Å
and 2 = 1900 Å, produce electrons with a maximum kinetic energy KE1 & KE2. If KE2 = 2KE1
calculate 0 and corresponding 0.
4. The absorption of energy by an atom of hydrogen in ground state ,results in the ejection of the
electron with the de Broglie wavelength λ= 4.7×10-10m. Given that the ionization energy is 13.6
ev, Calculate the energy of the photon which caused the ejection of electron.
5. What lines of atomic hydrogen spectrum fall within the wavelength range from 94.5 to 130.0nm?
Given: RH=1.1×107/m
6. Light of the prominent mercury line 2357Å ejects from a metal surface, electrons that have
stopping potential of 2.6 volts. The stopping potential of electrons ejected from the same metal
by the other prominent mercury line 1849Å is 4.04 volts.
a) Calculate the value of Planck`s constant
b) Calculate the value of threshold frequency using these data.

7. If the kinetic energy of an e- is given as “K” Joules with an uncertainty of 6  106 , then calculate the
expression of uncertainty in velocity, uncertainty in position. Express your answers in terms of “K”
only.
8. An electron already accelerated through a potential drop of V1 volts is further accelerated

through a potential drop of V2 volts .Its de Broglie wavelength λ1 before the second acceleration
and λ2 after it. The change Δλ is 47.48% of λ1. Calculate the ratio V1:V2.
3/ 2
 z 
9. It is known that  (radial) 1, 0  2  e (zr / a 0 ) for hydrogen like species. What will be the distance
 a0 
(from the nucleus) where there is maximum probability of finding a 1 s electron in terms of a0 & z.
10. 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 13.6 eV . Calculate
(i) No. of atoms present in III & II energy level.
(ii) Total energy evolved when all the atoms return to ground state.
11. The energy of an excited H-atom is –3.4 eV. Calculate angular momentum of e–.
12. The eyes of certain member of the reptile family pass a single visual signal to the brain when the
visual receptors are struck by photons of wavelength 850 nm. If a total energy of 3.15 X 10-14 J is
required to trip the signal, what is the minimum number of photons that must strike the receptor.
13. To what series does the spectral lines of atomic hydrogen belong if its wave number is equal to the
difference between the wave numbers of the following two lines of the Balmer series 486.1 and
410.2 nm. What is the wavelength of this?
14. The dye uriflarine, when dissolved in water has its maximum light absorption at 4530Å and its
maximum fluorescence emission at 5080Å. The number of fluorescence quanta is, on the
average 53% of the number of quanta absorbed. Using the wavelengths of maximum absorption
and emission, what percentage of absorbed energy is emitted as fluorescence?
15. The ionisation energy of a H like Bohr atoms in terms Rydberg’s constant is 4RH.
18
[ 1R H  2.18  10 J ]
(A)Calculate the wavelength radiated when electron jumps from the first excited state to ground
state.
(B) What is radius of 1st orbit of this atom?
16. A hydrogen like atom (atomic no. Z) is in a higher excited state of quantum number ‘n’. This
excited atom can make a transition to the first excited state by successively emitting two
photons of energies 10.2 eV and 17.00 eV respectively. Alternatively, the atom from the same
excited state can make a transition to the second excited state by successively emitting two
photons of energy 4.25 eV and 5.95 eV respectively. Determine the values of n and Z.
17. A single electron species has nuclear charge +Ze where Z is atomic number and e is electronic
charge. It requires 17 eV to excite the electron from the second Bohr orbit to third Bohr orbit.
Find :

i) The atomic no. of element

ii) The energy required for transition of electron from first to third orbit.
iii) Wavelength required to remove electron from first Bohr orbit to infinity.
iv) The kinetic energy of electron in first Bohr orbit.
18. A light beam of wavelength 400 nm is incident on a metal plate of work function 2.2 eV
(a) A particular electron absorbs a photon and makes two collisions before coming out of the
metal. Assuming that 10% of the initial extra energy is lost to the metal in each collision,
find the kinetic energy of this electron as it comes out of the metal.
(b) Under the same assumptions, find the maximum number of collisions the electron can
suffer before it becomes unable to come out of the metal.
19. A certain series in the atomic spectrum of hydrogen like ion is observed to have a series limit of
2052 Å. Suggest the simplest possible solution identifying the nature of the ion and name of the
series.
20. An unknown orbital is having the following equation for the radial component of its wave function.
3/2
2 z   2zr 2z2r 2   zr / 3a0
    3   2 
e
3  3a0   a 0 9a 0 
(a) identity the type of orbital. Justify
(b) Number, location & shape of angular node
(c) Number of radial nodes, the distance of the radial nodes & shapes of radial nodes.
21. Show that for large value of principal quantum number the frequency of an electron rotating in
adjacent energy levels of H-atom and the radiant frequency for transition between these all
approach the same value.
22. 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 lowest excitation state.
23. The energy needed for the reaction Li  g   Li g3  3e is 20000 KJ/ mole. If the first ionization
energy of lithium is 520KJ/ mole, calculate its second & third ionization energy

ANSWER KEY
ANSWERS TO FOUNDATION BUILDER (OBJECTIVE)
1. A 2. D 3. D 4. D 5. B 6. B 7. B
8. D 9. C 10. C 11. C 12. B 13. B 14. C
15. A 16. A 17. A 18. D 19. B 20. C 21. D
22. B 23. D 24. B 25. D 26. D 27. C 28. C
29. D 30. B 31. A 32. B 33. D 34. C 35. D
36. A 37. B 38. A 39. B 40. A 41. C 42. B
43. B 44. B 45. C 46. A 47. A 48. B 49. A
50. C 51. C 52. C 53. B 54. D 55. D 56. C
57. A 58. C 59. D 60. B 61. A 62. A 63. A
64. C 65. D 66. B 67. B 68. A 69. D 70. D
71. C 72. C 73. B 74. C 75. A 76. A 77. D
78. C 79. D 80. A 81. D 82. C 83. D 84. C
85. C 86. D 87. C 88. C 89. C 90. C 91. D
92. A 93. A 94. C 95. A 96. D 97. C 98. B
99. C 100. D 101. B
ANSWERS TO FOUNDATION BUILDER (SUBJECTIVE)

1. 6630 nm
2. 4.17  10–3 3. 6.0 × 10–2 m, 5.0 × 109 s–1 and 16.66 m–1
4. N 9.06  1019 photons s –1 5. (a) 6564Å (b) 40253Å (c) 388701Å
6. 1215 Å, 6564 Å, 18756 Å 7. 11.39nm, 3
8. n2 = 7 to n1=4 9. 121.56 nm or 1215.6Å
10. 1028Å, 1216 Å, 6568 Å 11. 1.82 × 10 5 J/mol
12. 937.8 Å 13. 243200 cm - 1
-7 -7
14. 1.216 x 10 m, 0.912 x 10 m, Ultraviolet region.
15. n2 = 2 to n1 = 1 16. 27419.25 cm – 1
17. 1.09 x 106 m/sec, 1.219 x 10-8 sec
18. – 1.51eV, 4.761 Å, 2.905 x 1015 s-1, 1.03211 x 10-7 m
19. 0.529 Å, 2.11 Å, 4.76 Å, 0.2645 Å, 1.058 Å, 2.38 Å.
20. 19.6 Kcal/mol 21. 12.09 eV
22. 5.425 x 10 – 12 erg, 3.6 x 10-5 cm 23. 30.6 ev, 54.4 ev
19
24. 2.717 x 10 25. 6603 Å
6 14 -1
26. 0.73 x 10 m/sec, 2.42 x 10 Sec 27. 8.2 x 106
28. 10.2eV, He+. 29. 3
15
30. 0.599 x 10 , Yes 31. 2.76 x 10-7m, 5.4 x 10-7m, 6.54 x 10-7m
32. 4.65 eV 33. 4.5 ×1014 s–1
34. [2 eV, 3.22 eV] 35. 3.09 × 108 cm/sec
36. 4.8 x 10-18 J 37. 6.626 × 10–35 m
38. 7.3  10–7m 39. 1.2247Å
40. 4.854 x 10-11 m 41. 5.8 x 105 m/sec
42. 1.05×10-13 m 43. 63.248 volt
44. Hunds Rule 45. 10
46. Zero, 4.89 B.M. 47. (i) r0 = 2a0,

ANSWERS TO GET EQUIPPED TO JEE MAIN
1. A 2. A 3. A 4. C 5. B 6. A 7. D
8. C 9. B 10. B 11. C 12. B 13. C 14. A
15. D 16. A 17. A 18. A 19. D 20. B 21. C
22. D 23. B 24. C 25. C 26. B 27. D 28. B
29. C 30. B 31. B 32. B 33. B 34. B 35. C
36. A 37. A 38. A 39. D 40. C 41. D 42. A
43. C 44. D 45. D 46. B 47. D 48. D 49. D
50. C
ANSWERS TO GET EQUIPPED FOR JEE ADVANCE
ONLY ONE OPTION CORRECT

1. D 2. B 3. C 4. A 5. A 6. D 7. C
8. D 9. B 10. A 11. C 12. C 13. A 14. D
15. A 16. B 17. B 18. B 19. C 20. D 21. D
22. A 23. D 24. B 25. B 26. C 27. D 28. A
MORE THAN ONE OPTION CORRECT
1. A, C, D 2. A, B, C, D 3. A, B, D 4. A, B 5. B, C, D 6. A, B, D 7. B, C
8. C 9. A, D 10. A, B, D 11. A, B, C 12. A, B, C 13. A 14. B, C
15. B, C, D 16. A, B 17. A, B, D 18. B, C, D 19. A, B, C 20. A, D 21. A, B, C
22. A, B, C 23. A, C
ANSWERS (COMPREHENSION TYPE; ASSERTION & REASONS)
COMPREHENSION -1
1. (B) 2.(A) 3.(A) 4.(D) 5. (D) 6. (A)
COMPREHENSION -2
1. (C) 2. (D) 3. (A) 4. (B) 5. (A)
COMPREHENSION -3
1. (B) 2. (A) 3. (B) 4. (D) 5. (C)
COMPREHENSION -4
1. (C) 2. (D) 3. (B) 4. (B) 5. (D) 6. (D)
7. (A)

MATRIX MATCH
1. A  Q; B  S; C  R; D  P
2. A  Q; B  R; C  S; D  P
3. A  S; B  R; C  P; D  Q
4. A  S; B  P; C  Q; D  R
5. A  P; B  P, Q, S; C  Q, S; D  P, R
6. A  P, Q, R; B  R; C  P, R, S; D  P, Q, R
7. A  P, S; B  P, R; C  Q, R; D  S
ANSWERS KEY - WINDOW TO JEE MAINS
1. b 2. c 3. b 4. c 5. c 6. a 7. a
8. b 9. d 10. d 11. c 12. c 13. c 14. a
15. c 16. b 17. d 18. c 19. a 20. d 21. c
22. c 23. a 24. c 25. b
ANSWER KEY – WINDOW TO JEE ADVANCE
Objective Questions - I
1. (C) 2. (D) 3. (A) 4. (A) 5. (D) 6. (A) 7. (D)
8. (B) 9. (B) 10. (B) 11. (B) 12. (C) 13. (D) 14. (C)
15. (B) 16. (C) 17. (A) 18. (C) 19. (C) 20. (A) 21. (B)
22. (D) 23. (B) 24. (A) 25. (A) 26. (A) 27. (B) 28. (A)
29. (C) 30. (D) 31. (C) 32. (D) 33. (B) 34. (A) 35. (C)
Objective Questions - II
1. (B,D) 2. (A,C) 3. (A,C) 4. (D) 5. (A,B) 6. (A,B,C) 7. (A,D)
Assertion and Reason

1. (c)
Comprehension Based Questions
1. (b) 2. (c) 3. (b)
Match the Columns
A → r; B→q; C→p; D→s
A→q; B→p,q,r,s C→p,q,r D→p,q,r

Fill in the Blanks
1. 1.66×10-27 2. neutrons 3. Opposite 4.isobars 5. Heisenberg, de-Broglie

6.photons 7. orbital 8. Orientation in space 9. Cr = [Ar]3d5, 4s1
True/False
1. F 2. F 3. T 4. F 5. T

Integer Type Questions

1. (9) 2. (4)
Subjective Questions:
1. The 2nd configuration is against Hund’s rule of maximum multiplicity which states that the singly
occupied degenerate atomic orbitals must have electrons of like spins.
2. Ten
3. 471 nm
4. 1.635 x 10 -18 J , Z=2 (He+)
5. n1= 1 and n2 = 2
6. Number of complete waves formed in one complete revolution of electron in any Bohr orbit is equal to
orbit number, hence three.
7. 2.165× 10-20 J/atom
8. 2.725 106 m1
e 2
9. V  2 E 
2  r
10. 6.33 × 106 ms-1
11. 63.3 V.
12. 98.39kJ.
13. 22.8nm
14.
(a) r0  2a
(b) 6.625 1025 Å(negligible small)
 h 
15.(a)2.18 × 106 ms-1 (b) 3.3Å (c) 2     1 for p orbital 
 2 
ANSWERS TO EXPERTISE ATTAINERS
1. (i) 2.55 eV (ii) n = 2, 4 2. 6  10-4 V

   1.148  1015 sec 1
3. 0  2613A 4. 20.4 eV
0
5. 5  1, 4  1, 3  1, 2  1 6. (a) 6.6  10-34 (SI units) (b) 6.4  1014 sec

h 2K 6.29  109
7. x  V  8. 0.381
4 5.73 1021 2K
a0
9.
z
10. 292.68 ×1021 atoms, 162.60 ×1021 atoms, 832 KJ
11. h/π 12. 1.35×105
13. Brackett; 2.63 ×10–4 cm
14. 47.26% 
15. (a) 303.89 A 
(b) 0.2645 A
16. Z = 3, n = 6
17. (i) Z = 3 (ii) 108.8 eV 
(iii) 101.3 A (iv) 122.4 eV
18. (a) 0.311 eV (b) 3
a0  9  1  a0  9  1 
19. n = 3, Z = 2 20. (a) 3s (b) 0 (c) 2 , Spherical.   1     1  
z  2  3 z  2  3
22. 3.3 × 10–18 J 23. [7690, 11790 KJ]

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Physical Chemistry

Ashwani Tyagi Sir

DALTON’S ATOMIC THEORY:

2. DISCOVERY OF SUBATOMIC PARTICLES

CATHODE RAYS AND DISCOVERY OF ELECTRON:

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The results of these experiments are summarized below:

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CALCULATION OF MASS OF AN ELECTRON:

e (1.60 10 19 C )

DISCOVERY OF PROTONS (GOLDSTEIN):

DISCOVERY OF NEUTRONS (CHADWICK):

Electron Proton Neutron

Approximate relative mass 1/1837 1 1

Approximate relative charge –1 +1 No charge

Mass in kg 9.10910–31 1.67310–27 1.67510–27

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3.1 THOMSON’S MODEL

This model could not satisfactorily explain the results of

3.2 RUTHERFORD’S MODEL

i) Majority of the –particles pass straight

ii) Some –particles are deflected from their path

iii) Very few –particles are deflected backwards

iv) Some were even scattered in the opposite

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POSTULATES OF RUTHERFORD ATOMIC MODEL :

DEFECTS OF RUTHERFORD’S ATOMIC MODEL:

3. It was unable to explain the Hydrogen emission spectrum

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i) Wave length ():

ii) Frequency (f):

iv) Wave number   :

vi) Intensity of Wave:

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6. PLANCK’S QUANTUM THEORY

erg – sec or 6.626  10–34 J–sec.

(i) They emit energy continuously in the form of radiations or waves.

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WAVELENGTHS OF ELECTROMAGNETIC RADIATIONS:

Electromagnetic radiations Wave length (Å)

Radio waves 31014 to 3 107

Micro waves 3109 to 3 106

Infrared (IR) 6106 to 7600

Visible 7600 (Red) to 3800 (Violet)

Ultra violet (UV) 3800 to 150

X–rays 150 to 0.1

Gamma rays 0.1 to 0.01

Cosmic rays 0.01 to zero

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Ans: Heat required  m.s. T

8. BOHR’S ATOMIC MODEL

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Energy absorbed or released in an electron jump, (E) is given by  E = E2 – E1 = h 

RADIUS AND ENERGY LEVELS OF HYDROGEN ATOM:

In C.G.S. units, value of K = 1 dyne cm2 (esu)–2

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= 5.29 10–11 m = 0.529 Å

CALCULATION OF ENERGY OF AN ELECTRON:

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CALCULATION OF FREQUENCY OF REVOLUTION OF ELECTRON IN A ORBIT:

Frequency of revolution is defined as no. of revolution taken by an electron in a unit time.

ENERGY LEVELS FOR HYDROGEN ATOM:

Kinetic Energy Potential Energy Total Energy Energy Difference