ATOMIC STRUCTURE

Contents
1. Dalton's Atomic Theory......................................................................................... 1
2. Different Types of Atomic Species ...................................................................... 2
3. Electromagnetic Radiations ................................................................................. 3
4. Planck’s Quantum Theory .................................................................................... 4
5. Various Atomic Models .......................................................................................... 6
6. Atomic Spectra ...................................................................................................... 10
7. Hydrogen Spectrum............................................................................................. 10
8. Derivation of Rydberg Equation ...................................................................... 12
9. Wave Particle Duality ......................................................................................... 16
10. Heisenberg’s Uncertainty Principle ................................................................ 17
11. Photoelectric Effect ............................................................................................. 20
12. Quantum Numbers .............................................................................................. 21
13. Rules for filling of electrons .............................................................................. 23
14. Nodal Plane and Nodal Surface ........................................................................ 25
15. Electronic Configurations of Elements ........................................................... 27
16. Level – 1 (Main) .................................................................................................... 29
17. Level – 2 (Main) .................................................................................................... 31
18. Level – 3 (Advanced) ........................................................................................... 34
19. Level – 4 (Comprehension & Match the Column) ........................................ 39
20. Level – 5 (Single Integer Subjective Type) .................................................... 44
21. Level – 6 (Previous Years Main & Advanced)............................................... 45
22. Level – 7 (NCERT Corner)................................................................................... 49
23. Answer Sheet ......................................................................................................... 52
 ATOMIC STRUCTURE
1. Dalton's Atomic Theory
Dalton proposed the atomic theory on the basis of the law of conservation of mass and law of definite proportions.
He also proposed the law of multiple proportions as a logical consequence of this theory. The salient features of
this theory are as follows:
(a) Each element is composed by extremely small particles called atoms.
(b) Atoms of a particular element are all alike but differ with the atoms of other elements.
(c) Atom of each element is an ultimate particle, and has a characteristic mass but is structure less.
(d) Atom is indestructible i.e. it can neither be destroyed nor created by simple chemical reactions.
(e) Atom of an element takes part in chemical reaction to form molecule.
(f) In a given compound, the relative number and kind of atom are same.
(g) Atoms of different elements combine in fixed ratio of small whole numbers to form compound atoms (now
called molecules).
Dalton’s theory explains the law of conservation of mass and some other laws of chemical combination. An atom of
elements take part in chemical reaction is true till today.

Discovery of Electron
The name electron was proposed by Stoney for the
fundamental unit of electricity and these were discovered To Vacuum Pump
by J. J. Thomson. However, cathode rays were
discovered by Julius Plucker. When a high voltage is Gas at Low Pressure
applied to gases at very low pressures, they become
conductors and electricity begins to flow in the form of
rays. These rays are called Cathode rays. Cathode Anode
+

Properties
1. They travel in straight lines.
2. They cause heating effect, when focused on a
thin metal foil.
3. They consist of material particles. High Voltage
4. They get deflected towards positive plate,
when electric field is applied.
5. They get deflected, when magnetic field is applied, perpendicular to the path.
6. They produce faint greenish fluorescence on striking against walls of the discharge tube
7. They ionize the gas through which they pass.
8. They produce X – rays when fall on metals such as tungsten, copper, etc.
9. They can penetrate through thin metal foils.
10. The charge to mass (e/m) ratio for the particles in the cathode is independent of the nature of the gas
taken in the discharge or the nature of the cathode.

Discovery of Proton
As the atom is found electrically neutral to normal T & P so it Perforated cathode
must have some positive charge in it.
The existence of proton in atom was shown by E. Goldstein
(1886). He repeated the discharge tube experiments by Positive
using a perforated cathode and observed that when a high text cathode ray ray
+
potential difference was applied between the electrodes then
besides cathode rays a new type of rays were produced
simultaneously from anode moving towards cathode and
passed through the holes or canal of the cathode. These rays Cathode
are termed as canal ray or anode ray. Proton was named by
Rutherford in 1911. A proton is a sub-atomic particle, which has a mass nearly 1 amu, and a charge of +1 unit.
2 – ATOMIC STRUCTURE – JEE
Characteristics of Anode Rays
(i) They travel in straight lines and cast shadow of the object placed in their path.
(ii) They are deflected by the magnetic and electric fields opposite to the direction of cathode rays, which
mean that these rays are positively charged.
(iii) They have kinetic energy and also produce heating effect.
(iv) There e/m ratio is smaller than that of electrons.
(v) Unlike cathode rays, their e/m value is dependent upon the nature of the gas taken in the tube.
(vi) They produce flashes of light on ZnS screen.
(vii) They can pass through thin metal foils.
(viii) They are capable to produce ionization in gases.
(ix) They can produce physical and chemical changes.

Discovery of Neutron
It was discovered by Chadwick in 1932. He bombarded beryllium with a stream of -particles and observed electrically
and magnetically neutral radiations. There were neutral particles called neutron. Nuclear reaction is as follows:
4 Be  2 He  6 C  0 n
9 4 12 1

A neutron is a subatomic particle which has a mass 1.675  10-24g, approximately 1 amu, or nearly equal to the
mass of proton on hydrogen atom and carrying no electrical charge.

2. Different Types of Atomic Species

Atomic Similarities Differences Examples
species
(i) Atomic No. (Z) (i) Mass No. (A) (i) 11H, 12H, 13H
(ii) No. of protons (ii) No. of neutrons 16
(ii) O, 17 18
8 O, 8 O
(iii) No. of electrons (iii) Physical properties 8
Isotopes (iii) 35 37
Cl, 17 Cl
(iv) Electronic configuration 17
(Soddy)
(v) Chemical properties
(vi) Position in the periodic
table
(i) Mass No. (A) (i) Atomic No. (Z) (i) 40
18
40
Ar, 19 K, 40
20 Ca
(ii) No. of nucleons (ii) No. of protons, electrons and 130
(ii) Te, 130 130
54 Xe, 56 Ba
neutrons 52
Isobars
(iii) Electronic configuration
(iv) Chemical properties
(v) Position in the periodic table.
No. of neutrons (i) Atomic No. (i) 30
14
31
Si, 15 32
P, 16 S
(ii) Mass No., protons and 39 40
(ii) K, 20 Ca
electrons. 19

Isotones (iii) Electronic configuration (iii) 13 H, 24He

(iv) Physical and chemical (iv) 13
C, 14
6 7 N
properties
(v) Position in the periodic table.
Isotopic No. (i) At No., mass No., electrons, (i) 92 U235 , 90 Th231
(N – Z) or (A – 2Z) protons, neutrons.
Isodiaphers (ii) K 39 , 9F19
(ii) Physical and chemical 19

properties. (iii) 29 Cu65 , 24 Cr 55

(i) No. of electrons At. No., mass No. (i) N2O,CO2 , CNO (22e  )
(ii) Electronic configuration
(ii) CO,CN ,N2 (14e  )
Isoelectronic
(iii) H ,He,Li , Be2  (2e  )
species
(iv) P3  ,S2  ,Cl , Ar,
K  ,Ca 2  (18e  )

(i) No. of atoms (i) N2 and CO

(ii) No. of electrons
Isosters (ii) CO2 and N2O
(iii) Same physical and
chemical properties. (iii) HCl and F2
 (iv) CaO and MgS
(v) C6H6 and B3N3H6

3. Electromagnetic Radiations
Light and other forms of radiant energy propagate without any medium Y Direction of
Z propagation
in the space in the form of waves. A charged body moving in a magnetic
field or a magnet in an electric field can produce these waves.
Characteristics of Electromagnetic Radiations
(a) All electromagnetic waves move or travel with the same
velocity equal to that of light.
X
(b) They do not require any medium to propagate.
(c) They consist of electric and magnetic field that oscillate in the
direction perpendicular to each other and to the direction of
propagation of wave.

Some Important Characteristics of Electromagnetic Waves

Wavelength

Amplitude Direction ofwave

propagation

(a) Frequency (): It is defined as the no. of waves which pass through a given point in per sec. Its unit is
expressed by cycle per second (cps) or Hertz (Hz).
c



 A cycle is said to be completed when a wave consisting of crest and trough passes through a
point.

(b) Wavelength (): The distance between two adjacent crest or troughs of the wave as shown in the fig. It is
c
denoted by lambda () and unit is Angstrom (Å) or nanometer (nm).   .

1 Å = 10–10 m or 10–8 cm
–9 –7
1 nm = 10 m or 10 cm
1cm  10 8 Å  10 4   10 7 nm
(c) Wave No. (  ): It is defined as the number of wave per cm and it is equal to the inverse of wavelength. Its
–1
unit is cm .
1 c
 or    c 
 

(d) Amplitude (a): It denotes the height of the crest or depth of the trough of a wave. It determines the
intensity of brightness of radiation. It also represents the maximum displacement from the mean path.
(e) Velocity (v): The distance travelled per sec by a wave is called velocity of a wave. It is expressed as
m/sec. or cm/sec.
C
 C =  or  =

The arrangement of various types of electromagnetic radiations in the order of their increasing or decreasing
wavelengths or frequencies is known as electromagnetic spectrum.

Name Wavelength (Å) Frequency (Hz) Source

Radio wave 3  10  3  10
14 7
1 10  1 10
5 9 Alternating current of high frequency
4 – ATOMIC STRUCTURE – JEE
Microwave 3  107  6  106 1 109  5  1011 Klystron tube

Infrared (IR) 6  106  7600 5  1011  3.95  1016 Incandescent objects

Visible 7600  3800 3.95  1016  7.9  1014 Electric bulbs, sun rays

Ultraviolet (UV) 3800  150 7.9  1014  2  1016 Sun rays, arc lamps with mercury
vapours
X-Rays 150  0.1 2  1016  3  1019 Cathode rays striking metal plate

  Rays 0.1  0.01 3  1019  3  1020 Secondary effect of radioactive decay

Cosmic Rays 0.01- zero 3  1020  infinity Outer space

4. Planck’s Quantum Theory

Max Planck proposed quantum theory of radiation whose postulates are as follows:
(1) Radiant energy is emitted or absorbed not continuously but discontinuously in the form of small packets of
energy called quanta.
Each wave packet or quantum is associated with definite amount of energy. In case of light, the quantum
of energy is often called photon.
(2) The amount of energy associated with a quantum of radiation is proportional to the frequency of radiation.
Ev
or E = hv
–34
Where h is a constant known as Planck’s constant and is equal to 6.625  10 joule-sec.
The energy of a photon of light in terms of wavelength  and velocity of light c, is given as
E = hv
c
E=h ( c = v; v = c/)


(3) A body can emit or absorb energy only in terms of the integral multiple of quantum, i.e.,
E = nhv where n = 1, 2, 3, 4, …….
This means that a body can emit or absorb energy as hv, 2hv, 3hv, 3hv, 4hv….. but it cannot emit or
absorb energy in fractional values of hv such as 1.5hv or 2.5 hv.
14
Illustration 1: Calculate the energy of one mole of photons of radiation whose frequency is 5  10 hz.
Solution: Frequency,
V = 5  1014 s–1
Energy of one photon,
E = hv
–34
H = 6.626  10 Js
–34 14 –1 –19
E = (6.626  10 Js)  (5  10 s ) = 3.313  10 J
Energy of 1 mol of photons
= 3.313  10–19  6.022  1023 = 199.51  103 J mol–1 = 199.51 kJ mol –1
Illustration 2: How many photons of light with a wavelength of 4000 pm are necessary to provide 1 j of
energy?
–12 -9
Solution: Wavelength of light,  = 4000 pm = 4000  10 m = 4  10 m
Energy of 1 photon,
hc
E=

-34 8 -1
h = 6.626  10 Js, c = 3.0  10 m s
6.626  10 -34  3.0  108
 E= -17
= 4.97  10 J
4  10 9
No. of photons providing 1 J of energy
Illustration 3: Electromagnetic radiation of wavelength 242 nm is just sufficient to ionize the sodium
atom. Calculate the ionization energy of sodium in kJ mol-1 (h = 6.626  10-34J s).
h
Solution: E = h =

H = 6.626  10-34 J s, c = 3.0  108 m,  = 242  10-9 m

 E
   
6.626  10 34 Js  3.0  108 ms1 –19
= 8.21  10 J
242  10 
9

Illustration 4: Suppose 10-17J of light energy is needed by the interior of the human eye to see an
object. How many photons of green light ( = 550 nm) are needed to generate this
minimum amount of energy?
Solution: The energy required to see object = 10-17 joule
h.c 6.625  10 34  3.0  108
Energy of photon of  (550  10-9 m) =  9
= 3.61 10-19 joule
 550  10
-19
 3.61  10 J = 1 photon
-17 10 17
 10 J = =27.7 photon
3.61 10 19
 No. of photons for generating minimum amount of energy = 28 (an integer value)
The integer value should be reported in all such cases where minimum no. of photon is asked
because fraction of a photon is never absorbed. Further more the number reported should be
higher one and never lower one because lower integer will not provide minimum value.

Illustration 5: The wave number which corresponds to electro-magnetic radiation of wavelength 500
nm is equal to:
–11 –1 4 –1
(A) 5 10 cm (B) 2  10 cm
–5 –1 –9 –1
(C) 5  10 cm (D) 2  10 sec
1 1 6 -1 4 -1
Solution: (B) Wave number =  9
= 2  10 m = 2  10 cm
 500  10 m
14 –1
Illustration 6: The wave number of a wave of light is 2.0  10 cm . The frequency of this light is:
3 –1 –3 -1
(A) 6.6  10 s (B) 6.6  10 s
24 –1 –14 –1
(C) 6.0  10 s (D) 6.0  10 s
c  10 14
Solution: (C)  =  c   =3.0  10  2.0  10

Illustration 7: 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
–14
of 3.15  10 J is required to trip the signal, what is the minimum number of photons
that must strike the receptor.
(A) 1.347  105 (B) 4.347  10–5
33
(C) 1.347  10 (D) 9.347  105
hc 6.626  1034  3  108
Solution: (A) Energy of one photon E = = = 2.3386  10–19 J
 850  10 9
total energy 3.15  1014
Number of Photons = =
energty of one photon 2.3386  10 19
= 1.347  105
6 – ATOMIC STRUCTURE – JEE

Quiz – 1
1. Cathode rays are produced when the pressure in the discharge tube is of the order of
(A) 76 cm of Hg (B) 106 cm of Hg
(C) 1 cm of Hg (D) 10 2 to 10 3 mm of Hg

2. The electronic configuration of a dipositive metal M2  is 2, 8, 14 and its atomic weight is 56 a.m.u. The
number of neutrons in its nuclei would be
(A) 30 (B) 32 (C) 34 (D) 42

3. (I) orbital angular momentum of the electron having n = 5 and having value of the azimuthal
h
quantum number as lowest for this principle quantum number is .

(II) If n = 3,  = 0, m = 0, for the last valence shell electron, then the possible atomic number
may be 12 or 13.
7
(III) Total spin of electrons for the atom 25Mn is ± .
2
(IV) Magnetic moment of inert gas is 0
Which of the above statement (s) is/are false.
(A) I, II and III (B) II and III Only
(C) I and IV only (D) None of these

4. The increasing order (lowest first) for the values of e/m (charge/mass) for
(A) e, p, n,  (B) n, p, e, 
(C) n, p, , e (D) n, , p, e

5. A 1000 watt radio transmitter operates at a frequency of 880 kc/sec. How many photons per sec does it
emit? [h = 6.626  10–34 Js]
30 28
(A) 2.51  10 (B) 2.27  10
30 27
(C) 1.72  10 (D) 1.77  10

6. A photon of radiation of wavelength 600 nm has an energy E. The wavelength of photon of radiation
having energy 0.25 E is:
(A) 600 nm (B) 2400 nm
(C) 150 nm (D) 300 nm

7. The ratio of energy of photon of 2000 Å wavelength radiation to that of 4000 Å radiation is:
(A) 1/4 (B) 4 (C) 1/2 (D) 2

8. The wavelength of a beam of light is 25.0 m. Its wave number is:
(A) 4.0  102 cm–1 (B) 4.0  106 cm–1
6 –1
(C) 4.0  10 m (D) 25.0  104 cm–1
9. Suppose 10–17 J of light energy is needed by the interior of human eye to see an object. The photons of
green light ( = 550 nm) needed to see the object are:
(A) 27 (B) 28 (C) 29 (D) 30
10. The wavelength of radiation having frequency 1000 Hz is:
13 7
(A) 3  10 cm (B) 3.0  10 cm
(C) 3000 Å (D) 300 nm

5. Various Atomic Models

Thomson’s Model
It was proposed by J.J. Thomson. It explains the arrangement of electrons and protons in an atom. The positive
-8
charge is spread over a sphere of the size of the atom (i.e. 10 cm radius) in which electrons are embedded to
make the atom as whole neutral. However, he could not explain the experimental results of Rutherfords -particle
scattering, therefore it was rejected.
Rutherford’s Experiment (Discovery of Nucleus)
Rutherford carried out experiment on the bombardment of atoms by high speed positively charged -particles
emitted from radium. He observed that:
Radioactive Thin gold few
substance foil

Most

Lead plate few

with hole

(a) Most of the -particles (nearly 99%) continued with their straight path.
(b) Some of the -particles passed very close to the centre of the atom and deflected by small angles.
(c) Very few particles thrown back (180).

Main Features
(a) Most of the -particles was continued their Atom of metal foil
straight path that means most of the space of
the atom is empty.
Few
(b) The centre of an atom has a positively charged Beam of   particles
body (nucleus) which repel positively charged - Majority
 of   rays
particles and thus explains the scattering
phenomenon. Very Nucleus
(c) Whole mass of an atom is concentrated in its Few +
nucleus and very few throw back means the size
-13 Majority
of the nucleus is very small 10 cm. It showed
-5 of   rays
that the nucleus is 10 times small in size as Few
compared to the total size of atom.
(d) The size and volume of the nucleus is very small
as compared to the total size and volume of atom.
(e) As atomic number increases, the angle of deflection () increases.

Drawbacks of Rutherford’s Model

(a) According to classical electromagnetic theory, when an electron moves
around the nucleus under the influence of the attractive force, the electron
loses its energy continuously and move closer and closer to the nucleus
in a spiral path and ultimately fall into the nucleus but it can’t be possible
because an atom is quite stable. +
(b) If an electron loses energy continuously, the observed spectrum -
Nucleus
should be continuous but the actual observed spectrum consist of Electron
discontinuous well-defined lines of definite frequencies.

Bohr developed atomic model for hydrogen and hydrogen like one electron species on the basis of Planck’s
quantum theory. Its postulates are as follows: 4 or N
(a) Electron revolves around the nucleus in a fixed circular orbit of
3 or M
definite energy.
(b) Electron revolves only in those orbits whose angular 2 or L
momentum (mvr) is an integral multiple of the factor h/2. 1 or K
h
mvr = n Nucleus
2
Where, m = mass of the electron, v = velocity of the electron, n =
number of orbit in which electron revolves i.e. n = 1, 2, 3 ......, r =
radius of the orbit and h = Planck’s constant.
(c) As long as the electron occupies a definite energy level, it does
not radiate out energy.
(d) The energy is emitted or absorbed only when the electron jumps from one energy level to another. If
energy supplied to an electron, it may jump from higher energy level to the lower by the emission of
8 – ATOMIC STRUCTURE – JEE
energy. This higher energy level is called excited state. Similarly in the reverse process it may absorb
energy and jump from lower to higher energy level.
(e) The amount of energy emitted or absorbed is given by difference of the energies of the two energy levels
concerned.
n=2 E2 E = E2 – E1 n=2 E2 E = E1 – E2

n=1 E1 Absorbed energy n=1 E1 Emitted energy

Mathematical Term of Bohr’s Postulates

(i) Calculation of the radius of the Bohr’s orbit: Suppose that an electron having mass (m) and charge (e)
revolving around the nucleus of charge - Z.e (Z = atomic number and e = charge) with a tangential/linear
velocity of v. and r is the radius of the orbit in which electron is revolving.
According to Coulomb’s law, the electrostatic force of attraction (F) between the moving electron and nucleus is:
KZe2
F=
r2
1 mv 2
Where, K = constant =  9  109 Nm2 / C2 and the centrifugal force F 
4 0 r
For the stable orbit of an electron both the forces are balanced,
mv 2 KZe2 KZe 2
i.e. at equilibrium  2 then v 2  ... (1)
r r mr
From the postulate of Bohr,
nh nh
mvr  or v 
2 2mr
... (2)
n 2 h2
v 
2

4  2 m 2r 2
From equation (1) and (2);
v
KZe 2 n 2 h2

mr 4  2 m2 r 2 e2 mv 2 /r
Nucleus 2
on solving, we will get, r
n 2h 2 +
r or In C.G.S unit K = 1,
4 mKZe
2 2 r
2 2
nh
 r
4 2mZe2
Where, h = 6.62  10–27 erg. sec., m = 9.1  10–28g, e = 1.6  10–19C
on putting the value of e, h and m, we get,
n2
r = 0.529  A
Z
v
Orbital frequency, f =
2r

(ii) Calculation of velocity of an electron in Bohr’s orbit: Velocity of the revolving electron in nth orbit is
nh
given by: mvr =
2
nh
 v ….(1)
2mr
nh  42mZe2 2Ze2
On putting value of r from equation (1) , we get, v   v 
2mn2h2 nh
On putting the value of , e and h, we get,
Z 1
v  2.188  108  Cm / sec or v  Z and v 
n n
(iii) Calculation of energy of an electron: The total energy of an electron revolving in a particular orbit is:
T.E. = K.E. + P.E.
Where, P.E. = Potential energy, K.E. = Kinetic energy, T.E. = Total energy
 1 KZe2
The K.E. of an electron  mv 2 and the P.E. of an electron  
2 r
2
1 KZe
Hence, T.E. = mv 2 
2 r
mv 2 KZe2 KZe 2
We know that,  2 or mv 2 
r r r
Substituting the value of mv2 in the above equation, we get,
KZe 2 KZe 2 KZe2
T.E. =  
2r r 2r
KZe2 Ze2
So, T.E. =  or In C.G.S unit k = 1  T.E.  
2r 2r
Substituting the value of r in the equation of T.E., we get,
Ze2 4 2 Ze2m 2 2 Z 2 e 4 m
E   
2 n 2 h2 n 2 h2
2 2 Z 2 e 4 m
The total energy of an electron in nth orbit is given by: En  
n 2 h2

 The P.E. at the infinite = 0. The K.E. at the infinite = 0.

Points in Favour of Bohr’s Theory

(i) The frequencies of the spectral lines calculated from Bohr’s equation are in close agreement with the
frequencies observed experimentally in hydrogen spectrum.
(ii) The value of Rydberg constant for hydrogen calculated from Bohr’s equation tallies with experimental
value.
+ 2+ 3+
(iii) The emission and absorption spectra of hydrogen like species such as He , Li and Be can be explained
with the help of Bohr’s theory.

Shortcomings of Bohr’s Model

1. It does not explain the spectra of atoms containing more than one electron and hydrogen spectrum
obtained using high-resolution spectroscope.
2. It does not explain the splitting of spectral lines under the influence of magnetic field (Zeeman effect) and
or electric field (stark effect).
3. Bohr considered only particle nature of electron instead of dual nature (wave and particle).
4. Postulate of Bohr that electrons move in well-defined orbits was not in line with Heisenberg’s uncertainty
principle.
5. It does not explain the geometry and shapes of molecules.

 The energy required to remove an electron from the ground state to form cation, i.e., to take the
electron to infinity, is called ionization energy.
I.E.  E  Eground
I.E.  0  E1(H)
= 13.6 eV atom-1 or = 2.1710-18 J atom-1
Z2 l Z 2 n2
I.E.  2  13.6 eV or 1  21  22
n l2 n1 Z2
(I.E.)H  Z 2
(I.E.)z 
n2
If an electron is already present in the excited state, then the energy required to remove that
electron is called separation energy.
Eseparation  E  Eexcited

Illustration 8: Radius of the fourth orbit in hydrogen atom is 0.85 nm. Calculate the velocity of the
-31
electron in this orbit (mass of electron = 9.1 10 kg).
Solution: From Bohr’s postulate, the angular momentum (mvr) is given as:
10 – ATOMIC STRUCTURE – JEE
nh nh
mvr = or v =
2 2mr
-31 -9 –9
n = 4, m=9.110 kg, r=0.8510 m (0.85 nm = 0.85  10 m)
4  6.626  10-34 26.50 6 –1
 v= =  10 6 = 0.545  10 ms
22 31 9 48.62
2  9.1 10  0.85  10
7
st
Illustration 9: Calculate the longest wavelength, which can remove the electron from I Bohr’s orbit.
Given E1 = 13.6 eV.
Solution: The photon capable of removing electron from Ist Bohr’s orbit must possess energy
-19 -19
= 13.6 eV = 13.6  1.602  10 J = 21.787  10 J
hc
 E

6.625  10 34  3.0  108
21.787  10 19  = 912.24Å

–10
  = 912.24  10 m
This is longest  because a photon having  higher than this will possess energy lesser then
1
required, as E  .


6. Atomic Spectra
An atomic spectrum is line spectra; so atomic spectrum is also called line spectrum. It is of two types.
(1) Emission Spectrum: A substance gets excited on heating at a very high temperature or by giving energy
and radiations are emitted. These radiations when analyzed with the help of spectroscope, spectral lines
are obtained. A substance may be excited as follows:

(i) By heating at a higher temperature.

(ii) By passing electric current at a very low pressure in a discharge tube filled with gas.
(iii) By passing electric current into metallic filament.

Emission spectra are of two types, Continuous spectrum and Line spectrum.

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

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

(2) Absorption Spectrum: When the white light of an incandescent substance is passed through any other
substance, this substance absorbs the radiations of certain wavelength from the white light. On analyzing the
transmitted light we obtain a spectrum in which dark lines of specific wavelengths are observed. These lines
constitute the absorption spectrum. The wavelength of dark line corresponds to the wavelength of light
absorbed.
th
If an electron from n excited state comes to various energy states, the maximum spectral lines obtained
n  n  1
will be:
2
7. Hydrogen Spectrum
When an electric discharge is passed through hydrogen gas its molecules dissociate into hydrogen atoms, the
excited hydrogen atoms, thus produced, emit electromagnetic radiations of discrete frequencies.
The spectrum obtained consists of large number of sharp lines. Each line corresponds to a particular frequency of
light emitted by hydrogen atoms. Lines in the emission spectrum of hydrogen are present in ultraviolet, visible and
infra-red regions.

Lies in Transition n12n22  max n2

Spectral n12
S.No. the max  min   2 2 2
series n2  n1 (n  n12 )R
2
R min n2  n1
region 2

(1) Lyman Ultraviolet n1  1 n1  1 and n2  2 n1  1 andn2  

series region 4
n2  2,3,4.... 4 1
 max  min  3
3R R
(2) Balmer Visible n1  2 n1  2 and n2  3 n1  2 and n2  
series region n2  3,4,5.... 36 4 9
 max  min 
5R R 5

(3) Paschen Infra red n1 = 3 n1  3 and n2  4 n1  3 andn2  

series region n2  4,5,6.... 16
144 9
 max  min  7
7R R
(4) Brackett Infra red n1  4 n1  4 and n2  5 n1  4 andn2  
series region 25
n2  5,6,7.... 16  25 16
 max  min  9
9R R
(5) Pfund Infra red n1  5 n1  5 and n2  6 n1  5 andn2  
series region 36
n2  6,7,8.... 25  36 25
 max   min  11
11R R
(6) Humphrey Far n1  6 n1  6 and n2  7 n1  6 andn2  
series infrared 49
n2  7,8.... 36  49 36
region max   min  13
13R R
The wavelength of each line in the spectrum can be given by:
1  1 1   1 1 
   RH Z 2  2  2  or   RH  2  2 
  n1 n2   n1 n2 
Where, RH is Rydberg constant, having value = 1.097  107 m–1 and n1 and n2 are electronic levels involved in
transition and  = wave number.
Interpretation of Hydrogen Spectrum
Normally, the only electron in the hydrogen atom resides on the first orbit. When energy is supplied, it moves to
higher energy shells depending on the amount of energy absorbed. When this electron returns to any of the lower
energy shells, it emits energy.
12 – ATOMIC STRUCTURE – JEE
Lyman series is formed when the electron returns to the lowest energy state while Balmer series is formed when
the electron returns to second energy shell. Similarly, Paschen, Brackett and Pfund series are formed, when
electron returns to the third, fourth and fifth energy shells from higher energy shells respectively.

n(n  1)
Maximum number of lines produced, when an electron jumps from nth level to ground level is =
2

Example- In the case of n = 4, number of lines produced is 6 (4  3, 4  2, 4  1, 3  2, 3  1, 2  1).

(n2  n1 )(n2  n1  1)
When an electron returns from n2 to n1 state, the number of lines in the spectrum will be = .
2
If the electron comes back from energy level E2 to energy level E1, then the difference may be expressed in terms
E
of energy of photon as E2 - E1 = E = h  and the frequency of the emitted radiation can given by   .
h
Since E can have only definite values depending on the definite energies of E2 and E1,  will have only fixed
c E hc
values in an atom as    or   .
 h E
Since h and c are constants, E corresponds to definite energy. Thus, each transition from one energy level to
another will produce a light of definite wavelength. This is actually observed as a line in the spectrum of hydrogen
atom.
Thus, the different spectral lines in the spectra of atoms correspond to different transitions of electrons from higher
energy levels to lower energy levels

8. Derivation of Rydberg Equation

Let an excited electron come from n2 shell to the n1 shell and release energy. Then wave number  , of the
corresponding spectral line may be calculated as:
22mZ2 e4 22mZ2 e4
E  E2  E1  ( ) 2 2
 ()
n2h n12h2
hc 22mZ 2 e 4  1 1
  2  2
 h 2
 n1 n2 
hc
Where, E  h 

1 2 mZ2 e 4  1
2
1
    2  2
 ch3
 n1 n2 
 1 1
or   RZ 2   2  2 
 n1 n2 
2 me4
2
-1
Where R = Rydberg constant = 109743 cm
ch3
-1
This value of R is in agreement with experimentally determined value 109677.76 cm . Rydberg equation for
hydrogen may be given as:
 1 1 1
  R 2  2 
  n1 n2 

(i) First line of a series: It is the line of longest wavelength or line of shortest energy.
For first line: n2 = (n1+1)
1 1 1 
  first   R 2  
 first  n1 n1  1 
2

Similarly for second, third and fourth lines n2 = n1 + 2; n2 = n1 + 3 and n2 = n1 + 4 respectively.

(ii) Series limit or last line of a series: It is the line of shortest wavelength or line of highest energy.

For last line: n2 = 

1 R
last  
 last n12
En2  En1
Excitation potential for n1  n2 =
Electronic charge
En1
Ionization potential for n1   =
Electronic charg e

Illustration 10: A spectral line obtained when an electron jumps from sixth energy level to first energy level
is spectrum of hydrogen atom fall in:
(A) Visible region (B) Ultra violet region
(C) Infra red region (D) None of these
Solution: (B) It belongs to Lyman series which falls in ultra-violet region.

Illustration 11: The wave number of the shortest wavelength of absorption spectrum of H-atom is
–1
(Rydberg constant = 109700 cm )
–1 –1
(A) 109700 cm (B) 3/4  109700 cm
–1 –1
(C) 1/2  109700 cm (D) 9/10  109700 cm
Solution: (A) The shortest wavelength corresponds to maximum energy,
 n2 = 
 1 1 
 = 109700cm–1  1  2  = 109700 cm–1
1  

Illustration 12: Hydrogen like atom with atomic number Z is in a higher excited state of quantum number n.
This excited state atom can make a transition to the first excited state by successively
emitting two photons of energies 10eV and 17eV, respectively. Alternatively, the atom from
the same excited state can make a transition to the 2nd excited state by emitting two
photons of energies 4.25 eV and 5.95 eV, respectively. Determine n and Z
(A) 6 and 2 (B) 6 and 3
(C) 2 and 6 (D) 4 and 6
Solution: (B) Energy difference between n = 2 and n = 3 n
= 10 + 17 – 4.25 – 5.95 = 16.8 Ev 10eV
4.25eV
 1 1
16.8 = 13.6   2   Z2 17eV 5.95eV
2 3 
2

n=3
Z = 2.98  3 n=2
Energy difference between n = n and n = 2 n=1
= 10 + 17 = 27 eV
 1 1
27 = 13.6   2   32
2 n 
2

n = 5.83  6
14 – ATOMIC STRUCTURE – JEE
n = 6; Z = 3
Illustration 13: The energy of the second Bohr orbit of H atom is –3.41eV. The energy of the second Bohr
orbit of He+ ion is:
(A) –0.85 eV (B) –1.70 eV
(C) –6.82 eV (D) –13.64 eV
+ 2
Solution: (D) Energy of second orbit of He = –3.41 eV  2 = –13.64eV
Illustration 14: Calculate the wavelength of the spectral line when the electron in the hydrogen atom
undergoes a transition from fourth energy level to second energy level. What is the colour
of the radiation?
1  1 1
Solution: According to Rydberg equation, = R  2 - 2 
  n1 n2 
Here n1 = 2, n2 = 4 and R = 109677 cm-1

1  1 1 1 1  12
=109677  2 - 2  cm-1 =109677  -  cm-1 =109677  cm-1
λ  2 4   4 16  64
64
or  = cm = 4.86  10 cm or = 486  10 -9 m = 486 nm
-5

109677  12

This line corresponds to bluish green colour.

Illustration 15: In the Rydberg equation for an hydrogen atom, a spectral line corresponds to n1 = 3 and n2 = 5.
(i) Calculate the wavelength and frequency of this spectral line?
(ii) To which spectral series does this line belong?
(iii) In what region of the electromagnetic spectrum will this line fall?
1  1 1 -1
Solution: (i) According to Rydberg equation, = R  2 - 2  Where R = 109677 cm , n1 = 3 and n2 = 5
 n n
 1 2
1  1 1  -1  1 1  -1
Substituting the values, =109677  2 - 2  cm =109677  -  cm
  3 5   9 25 
16
Or =109677  cm-1
225
225
 = cm =12.82  10 -5 cm=1282  10 -9 m
109677  16
Or  = 1282 nm
c
Now   v = c or v = Where c = 3.0  10 8 ms-1, λ = 1282 nm = 1282  10-9 m
λ
3.0  108 ms-1 3 14 -1
v=   1017 s-1 =2.34  10 s
1282  10-9 m 1282
(ii) Since this line corresponds to n = 3, it belongs to Paschen series.
(iii) The spectral line will fall in infrared region.
Illustration 16: Calculate the wavelength of radiations emitted producing a line in Layman series, when an
7 –1
electron falls from fourth stationary state in hydrogen atom (RH = 1.1  10 m ).
1  1 1 
Solution: = RH  2 - 2 
  n1 n2 
7
Given - RH = 1.1  10 ; for Layman series and n1 = 1 and n2 = 4
1 1 1 -7
  1.1  107  2  2    = 0. 9696  10 meter
 1 4 
 QUIZ – 2
1. The wave number of the series limiting line for the Lyman series for hydrogen atom is (R = 109678 cm–1)
(A) 82259 cm–1 (B) 109678 cm–1
–5
(C) 1.2157  10 cm (D) 9.1176  10–6 cm
2. 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) 32 (B) 52 (C) 41 (D) 25
3. In H-atom electron jumps from 3 to 2 energy level the energy released is:
(A) 3.03  10–19 J/atom (B) 1.03  10–19 J/atom
–12
(C) 3.03  10 J/atom (D) 6.06  10–19 J/atom
4. The wavelength of the first line of Balmer series of H-atoms is 6561 Å. The wavelength of the second line
of the series is:
(A) 13122 Å (B) 3280 Å (C) 4860 Å (D) 2180 Å
5. If the shortest wavelength of H atom in Lyman series is x, then the longest wavelength in Balmer series of
He+ is:
36x 5x 9x x
(A) (B) (C) (D)
5 9 5 5
6. The wave number of the shortest wavelength transition in the Balmer series of H atom is:
–1 –1 –1 –1
(A) 27419.5 cm (B) 219356 cm (C) 12186.2 cm (D) 24372 cm

7. Ratio of radii of the first three Bohr orbit is:

(A) 1 : 0.5 : 0.33 (B) 1:2:3 (C) 1:4:9 (D) 1 : 8 : 27

8. If the radius of first Bohr orbit be a0 , then the radius of third orbit would be:
1
(A) 3  a0 (B) 6  a0 (C) 9  a0 (D) a0
9

9. The frequency of one of the lines in Paschen series of hydrogen atom is 2.340  1014 Hz . The quantum
number n2 which produces this transition is:
(A) 6 (B) 5 (C) 4 (D) 3

10. The energy of an electron in the second Bohr orbit of H-atom is –E. The energy of the electron in the
Bohr’s first orbit is:
(A) – E/4 (B) – 4E (C) 4E (D) – 2E
+
11. The electronic transition in the He spectrum from n = 4 to n = 2 corresponds to which transition in the H-
spectrum?
(A) n = 2 to n = 1 (B) n = 3 to n = 1
(C) n = 4 to n = 2 (D) n = 3 to n = 2
+
12. What is the kinetic energy of an electron in second excited state of He ?
{Energy of electron in first shell of H = – 13.6 eV}
(A) –1.51 eV (B) –6.04 eV (C) –13.08 eV (D) –13.6 eV
13. The ratio of difference in energy between the first and second Bohr orbit to that between the second and
third Bohr orbit is:
(A) 1/2 (B) 1/3 (C) 4/9 (D) 27/5

14. The series limit for Balmer series of H-spectra is:

(A) 3800Å (B) 4200Å (C) 3664Å (D) 4000Å
15. The ionization energy of hydrogen atom is – 13.6 eV. The energy required to excite the electron in a
hydrogen atom from the ground state to the first excited state is: (Avogadro’s constant  6.022  1023 )
(A) 1.69  10 20 J (B) 1.69  10 18 J (C) 1.69  1023 J (D) 1.69  1025 J
16 – ATOMIC STRUCTURE – JEE

9. Wave Particle Duality

Luis De broglie suggested that like light, matter also behave as a wave and particle.
If wavelength () of the wave associated with a particle of mass (m) moving with a velocity ():
h h
  or  
m p
where, h = plank’s constant = 6.626 × 10-34 Js, m = mass of object (kg), v = velocity (ms-1) and P = momentum (kg ms-1).
It states that all the moving material objects have wave like characteristics.
Wave character is significant only in case of small particles like electrons, protons, atoms etc. However, it has no
significance in case of large objects like cricket ball, car, train, etc.
The energy of a photon (E) = hv …..(i)
Where,  is the frequency of photon
Also according to Einstein’s equation, E = mc2 ……(ii)
Where, m is mass and c is velocity of photon on equating both equations, we get:
E=E
mc2 = h
2 c  c
mc = h  ν =  
  
By rearranging the equation, we get:
h
 = (for radiation light)
mc
h
or  = (for matter particle) ….(iii)
mν
Above equation is called as De – Broglie equation and also can be expressed as:
h
 = ….(iv)
p
Where, p is the momentum of the particle.

Illustration 17: A beam of helium atoms moves with a velocity of 2.0  103 ms-1. Find the wavelength of
particles constituting the beam (h = 6.626  10–34 Js).
4
Solution: Mass of helium atom =  6.64  10 24 g = 6.64  10-27 kg
6.023  1023
According to De-broglie equation,
h
=
m.v
–34 –27 3 -1
h = 6.626  10 Js, m = 6.64  10 kg, v = 2.0  10 ms
2 1
6.626  10 kg m s
-34

 =  4.99  10 11 m = 49.9 pm

(6.64  10-27kg) (2.0  103m s-1 )

Illustration 18: Calculating the momentum of a moving particle that has de-Broglie wavelength of 2 Å.
-34 -34 2 -1
Solution: h = 6.63  10 Js = 6.63  10 kg m s
-10
 = 2 Ǻ = 2  10 m
h h
 or mv=
mv 
6.63  10 34 kg m2 s -1
Momentum, mv = = 3.31  10-24 kg ms-1.
2  10 10 m
Illustration 19: Calculate the number of waves made by an electron revolving in fourth orbit of hydrogen
atom in one complete revolution.
2r
Solution: Number of waves made =

2r 2    2 nh
mvr
= = = . =n=4
 h / mv  h h 2
Illustration 20: An electron in H-atom in ground state absorbs 1.5 times as much energy as the minimum
required for its escape (i.e., 13.6 eV) from the atom. Calculate the wavelength of emitted electron.
Solution: Energy of I orbit of H-atom = –13.6 eV
Energy absorbed by H-atom = (3/2)  13.6 eV
 Energy used in imparting velocity to electron = (13.6/2) eV
 1 2 –19
Or  2  mu = (13.6/2)  1.602  10 J
 
13.6  1.602  10 19
 u= = 1.547  106 m sec–1
9.108  10 31
h 6.626  10 34
Now     = 4.70  10–10 m
mu 9.108  10 31  1.547  106

10. Heisenberg’s Uncertainty Principle

It is impossible to determine momentum and position of a subatomic particle like electron exactly and
simultaneously. Mathematically, it can be represented as -
h
p.x 
4
h
m..x 
4
h
.x 
4m
Where, p = uncertainty in momentum, x = uncertainty in position, and  = uncertainty in velocity.
It must be kept in mind that the uncertainty principle applies to position and momentum of the particle along the
same axis. Thus, if x is the uncertainty in position along the x-axis then p must be the uncertainty in momentum
along x-axis.
Now let us understand the physical picture of uncertainty principle. In order to observe the position of an object,
light of some suitable wavelength is made to fall on the object which scatters light. Now when the scattered light
enters our eye we can see the object. For scattering to take place, the wavelength of the light used should be of
the same order as the size of the object. If the object is of reasonable size its position and velocity will not change
by the impact of the light radiations. Thus, it is possible to know both the position and velocity of the object exactly.
In case of microscopic particles like electron, the impact of striking photon causes large displacement from the
normal path. As a result, both the velocity and momentum of the particle change and send the electron in the
unpredictable direction.
It can be shown that if  is the wavelength of the radiation used to observe the particle then the position of the
particle cannot be determined with accuracy greater than . Therefore, in order to observe the position of the
particle accurately, wavelength of the light, should be as small as possible. However, we known that photons of
radiations of smaller wavelength are associated with large amount of energy and therefore when such photons
strike the particle these disturb the momentum of the particle to a greater extent i.e., uncertainty in momentum
increases. In order to determine momentum with less uncertainty we will use radiations of longer wavelengths, but
in that case uncertainty in position would become large. It may, thus, be concluded that it is not possible to
determine simultaneously both the position and momentum of a small moving particle such as electron with
absolute accuracy.
th
pa
al
iti
In

Significance of Uncertainty Principle

Heisenberg’s principle rules out the concept of definite paths or trajectories of electrons in an atom as proposed by
Bohr. In order to define the trajectory of an object one must know the location and velocity of the object at various
18 – ATOMIC STRUCTURE – JEE
moments. Since for a subatomic particle such as an electron, it is not possible to simultaneously determine the
position and velocity with absolute accuracy, it is not possible to talk of the trajectory of an electron.
Instead it is only possible to predict the probable region in a given space where we can find electron. Thus,
Heisenberg replaced the concept of definite orbits by the concept of probability.

Illustration 21: Calculate the uncertainty in velocity of a cricket ball (mass = 0.15 kg) if its uncertainty in
position is of the order of 1 Å.
h
Solution: u. x =
4m
h 6.625 ×10-34
u = = = 3.51×10-24 m sec -1
4 m.x 22 -10
4× × 0.15 ×10
7

Illustration 22: Calculate the uncertainty in the velocity of cricket ball of mass 150 g, if the uncertainty in its
position is of the order of 1 Ǻ.
Solution: m = 150 g = 0.150 kg
x = 1 Ǻ = 10–10 m
h
x .mv=
4
h 6.63  10 34 kg m 2 s 1 -28 -1
v   = 1.31 10 ms .
4   m  x 4  3.14  20  10 3 kg  2  10 -5 m

Illustration 23: Calculate the uncertainly in momentum of a particle if the uncertainty in its position is 6.6 
10-32 m.
Solution: x  6.6  10 32 m; p=?
h
x  p 
4
h 6.63  10 34 kg m2 s-1
p   = 7.99  10–4 kg ms-1.
4   x 4  3.14  6.6  10-32 m

QUIZ – 3
1. Two particles A and B are in motion. If the wavelength associated with the particle A is 5.0  10–8 m, the
wavelength of particle B having momentum half of A is:
–8 –8 –7 –8
(A) 2.5  10 m (B) 1.25  10 m (C) 1.0  10 m (D) 1.0  10 m

2. The mass of electron is 9.11  10–31 kg, h is 6.626  10–34 J-sec, the uncertainty involved in the
measurement of velocity within a distance of 0.1 Å is:
5 –1 6 –1
(A) 5.79  10 m sec (B) 5.79  10 m sec
7 –1 9 –1
(C) 5.79  10 m sec (D) 5.79  10 m sec

3. A 200 g golf ball is moving with a speed of 5 m per hour. The associated wavelength is:
( h  6.625  10 34 J  sec)
(A) 2.38  10 10 m (B) 2.38  10 20 m (C) 2.38  10 30 m (D) 2.38  10 40 m

–34
4. If the Planck’s constant, h = 6.6  10 J s, the de Broglie wavelength of a particle having momentum of
–24 –1
3.3  10 kg m s will be:
(A) 0.02 Å (B) 0.5 Å (C) 2Å (D) 500 Å

5. An electron of a velocity ‘x’ is found to have a certain wavelength. The velocity to be possessed by the
neutron to have half the de Broglie wavelength possessed by electron is:
(A) x/1840 (B) x/920 (C) 3680 x (D) x/3680
6. The position of both an electron and a helium atom is known within 1.0 nm and the momentum of the
electron is known within 50  10 26 kgms1 . The minimum uncertainty in the measurement of the
momentum of the helium atom is
(A) 50 kg ms1 (B) 60 kgms 1
(C) 80  10 26 kg ms1 (D) 50  10 26 kg ms1

7. de-Broglie wavelength of electron in second orbit of Li2+ ion will be equal to de-Broglie of wavelength of
electron in
(A) n = 3 of H-atom (B) n = 4 of C5+ ion
(C) n = 6 of Be3+ ion (D) n = 3 of He+ ion

8. An electron in a hydrogen like atom makes transition from a state in which its de-Broglie wavelength is 1
to a state where its de-Broglie wavelength is 2 then wavelength of photon () generated will be
4mc  12  22 
(A)  =  1 – 2 (B) =  
h  12   22 
12  22 2mc  12  22 
(C) = (D) =  
12   22 h  12   22 
where m is mass of the electron, c is speed of light in vaccum.

9. If (KE)e, (KE) and (KE)p represents the kinetic energies of an electron, -particle and proton respectively,
each moves with same de-Broglie wavelength than:
(A) (KE)e = (KE)  = (KE)p (B) (KE) > (KE)p > (KE)e
(C) (KE)e > (KE)p > (KE)  (D) (KE)p > (KE)  > (KE)e

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

11. An electron has kinetic energy 2.8  10 23 J . de–Broglie wavelength will be nearly (me  9.1 10 31 kg)
(A) 9.28  10 4 m (B) 9.28  10 7 m (C) 9.28  10 8 m (D) 9.28  10 10 m

12. Identify the correct statement

(A) Wavelength associated with the 1 kg ball moving with the velocity 100 m/s can’t be calculated.
(B) Wave nature of the running train is difficult to observe because wavelength is extremely small.
hc
(C) Wavelength associated with the electron can be calculated using the formulae E =

(D) If an electron is accelerated through 17 V potential difference if it has already 5eV kinetic energy
then wavelength of the electron is approximately 6 Å.

13. When uncertainty in position and momentum are equal, then uncertainty in velocity is:
h 1 h 1 h h
(A) (B) (C) (D) 2m
 2  2m  
5
14. At 200C the velocity of hydrogen molecule is 2.4  10 cm/sec. In this case the de Broglie wavelength is
about:
(A) 1Å (B) 1000 Å
(C) 100 Å (D) 10 Å

15. The wave number of electromagnetic radiation emitted during the transition of electron in between two
levels of Li2+ ion whose principal quantum numbers sum is 4 and difference is 2 is :
(A) 3.5 RH (B) 4 RH
8
(C) 8 RH (D) R
9 H
20 – ATOMIC STRUCTURE – JEE

11. Photoelectric Effect

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

The phenomenon is called Photoelectric effect. The results observed in this experiment were :
(i) The electrons are ejected from the metal surface as soon as the beam of light strikes the surface, i.e.,
there is no time lag between the striking of light beam and the ejection of electrons from the metal surface.
(ii) The number of electrons ejected is proportional to the intensity or brightness of light.
(iii) For each metal, there is a characteristic minimum frequency,  0 (also known as threshold frequency)
below which photoelectric effect is not observed. At a frequency  >  0, the ejected electrons come out with
certain kinetic energy. The kinetic energies of these electrons increase with the increase of frequency of
the light used.
When a photon of sufficient energy strikes an electron in the atom of the metal, it transfers its energy
instantaneously to the electron during the collision and the electron is ejected without any time lag or
delay. Greater the energy possessed by the photon, greater will be transfer of energy to the electron and
greater the kinetic energy of the ejected electron. In other words, kinetic energy of the ejected electron is
proportional to the frequency of the electromagnetic radiation. Since the striking photon has energy equal
to h and the minimum energy required to eject the electron is h0 (is also called work function, W 0) then
the difference in energy (h – h0) is transferred as the kinetic energy of the photoelectron. Following the
conservation of energy principle, the kinetic energy of the ejected electron is given by the equation
1
h = h0 + me2
2
where me is the mass of the electron and v is the velocity associated with the ejected electron.

QUIZ – 4
1. The threshold frequency  0 for a metal is 6 × 1014 s–1. Calculate the kinetic energy of an electron emitted
when radiation of frequency  = 1.1 × 1015 s–1 hits the metal.
–19 –19
(A) 3.313 × 10 J (B) 3.967 × 10 J
–19
(C) 2.345 × 10 J (D) 5.857 × 10–19 J

2. A photon of wavelength 3000 Å 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.
5 –1
(A) I. E4.125 eV, II. = 2.20 eV, III. velocity (v) = = 8.22 × 10 ms
5 –1
(B) I. E3.125 eV, II. = 3.20 eV, III. velocity (v) = = 6.02 × 10 ms
(C) I. E5.569 eV, II. = 2.96 eV, III. velocity (v) = = 5.09 × 10 ms–1
5

(D) I. E6.125 eV, II. = 2.20 eV, III. velocity (v) = = 9.96 × 105 ms–1
3. Photoelectrons are liberated by ultra violet light of wavelength 2000 Å from a metallic surface for which the
photoelectric threshold is 4000 Å. Calculate the de Broglie wavelength of electrons emitted with maximum
kinetic energy.
(A)  = 0.421 × 10–9 m (B)  = 0.696 × 10–9 m
–9 –9
(C)  = 0.587 × 10 m (D)  = 0.321 × 10 m
4. Iodine molecule dissociates into atoms after absorbing light of 3000 Å. If one quantum of radiation is absorbed
by each molecule, calculate the kinetic energy of iodine atoms. (Bond energy of I2 = 240 kJ (mol).
 (A) 3.313 × 10–19 J (B) 1.318 × 10–19 J
–19 –19
(C) 12.345 × 10 J (D) 6.359 × 10 J
5. Find the energy in kJ per mole of electronic charge accelerated by a potential of 2 volt.
–19 4
(A) 3.313 × 10 J (B) 22.264 × 10 J
–19 4
(C) 12.345 × 10 J (D) 19.264 × 10 J
6. The threshold wavelength for the ejection of electro from metal X is 330 nm. The work function for
–34
photoelectric emission from metal X is {h = 6.6  10 s}
–18
(A) 1.2  10 J (B) 1.2  10–20 J
–19
(C) 6  10 J (D) 6  10–12 J
7. According to Einstein's photoelectric equation, the graph between the kinetic energy of photoelectrons
ejected and the frequency of the incident radiation is:

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

8. Photoelectrons are liberated by ultra violet light of wavelength 2000 Å from a metallic surface for which the
photoelectric threshold is 4000 Å. Calculate the de Broglie wavelength of electrons emitted with maximum
kinetic energy.
–9 –9
(A) 0.696  10 m (B) 0.529  10 m
–6 –7
(C) 0.696  10 m (D) 0.696  10 m
9. The work function of potassium is 2.25 eV. Predict whether photoelectrons will come out from potassium
surface or not when electromagnetic radiations of wavelength 4000Å fall on it.
(A) Yes (B) No
(C) may or may not be
14 –1
10. The threshold frequency for a metal is 7.0  10 s . Calculate the maximum kinetic energy of an electron
15 –1
emitted when radiation of frequency 1.0  10 s falls on the metal.
–19 –19
(A) 1.99  10 J (B) 1.99  10 eV
–17 –12
(C) 1.99  10 J (D) 1.99  10 J

12. Quantum Numbers

The discoveries of wave particle duality (p = h/) by De–broglie and the uncertainty principal (p . x  h/4) by
Heisenberg have completely changed the picture about behavior of electrons in an atom. Each electron in an atom
is characterized by a mathematical expression (wave function) – whose square value at a given point gives the
probability of finding the electron at that point. The different wave functions can be obtained by solving the
appropriate Schrödinger equation. The four quantum numbers (n, l, m, and s) are results of Schrödinger wave
equation.
Principal Quantum No.: It is denoted by ‘n’ and represents size and energy level of major energy shell. Values of
n ranges from 1 to n. e.g.
n = 1 K – Shell
n = 2 L – Shell
n = 3 M – Shell
n = 4 N – Shell
Azimuthal or angular Quantum No.: It is denoted by ‘l’ and represents shape and energy level of subshells.
Values of ‘  ’ ranges from 0 to n – 1 e.g.
 = 0 s – subshell
 = 1 p – subshell
 = 2 d – subshell
 = 3 f – subshell
The angular momentum of an electron in an orbital is given by:
 h 
 2      1 
 
22 – ATOMIC STRUCTURE – JEE

Magnetic Quantum No.: It is denoted by ‘m’ and represents possible no. of orientations of subshells
e.g. Suppose
 =1 m = –1 0 +1
px or py pz py or px

 =2 m=–2 –1 0 +1 +2
2 2 2 2 2
dxy or dx –y dxz or dyz dz dyz or dxz dx –y or dxy

The angular magnetic movement of electron will be

h
=m
2

Spin Quantum No.: It is denoted by ‘s’ and represents the direction of spin of electron in a sub–shell or orbital.
Values of ‘s’ are + 1/2 and –1/2.
1
The total spin (s) of an atom is given by s =  n, where n is number of unpaired electrons.
2
The spin magnetic moment of electron (excluding orbital magnetic moment) is given by:
 effective   4s  s  1 
1
Putting, s= n
2
 effective  n  n  2   BM
The magnetic moment is expressed in Bohr Magneton (BM), where 1 BM = 9.27  10–24 J/T.

Principal
Number of
quantum Name of Possible values of Possible value of ml No. of electrons in
electrons in
number shell l (sub level) (orbitals) shell
sub shell
(n)
n=1 K 0 0 2 2
(1s- subshell) (1 orbital)
n=2 L 0 0 2
(2s-subshell) (1 orbital) 8
1 -1, 0, +1 6
2p-subshell (3 orbitals)
n=3 M 0 0 2
(3s-subshell) (1 orbital)
1 -1, 0, +1 6
(3p-subshell) (3 orbitals) 18
2 -2, -1, 0, +1, +2 10
(3d-subshell) (5 orbitals)
n=4 N 0 0 2
(4s-subshell) (1 orbital)
1 -1, 0, +1 6
(4p-subshell) (3 orbitals) 32
2 -2, -1, 0, +1, +2 10
(4d-subshell) (5 orbitals)
3 -3, -2, -1, 0, +1, +2, +3 14
(4f-subshell) (7 orbitals)

 (i) Maximum number of orbitals in each shell is n .

2

(ii) Maximum number of electrons is 2n2.

Illustration 24: Which of the following sets of quantum numbers are not allowable and why?
(i) n = 2,  = 1, ml = 0, ms = + 1/2
(ii) n = 2,  = 2, ml = -1, ms = – 1/2
(iii) n = 3,  = 2, ml = 0, ms = – 1/2
(iv) n = 3,  =1, ml = + 1, ms = 0
 (v) n = 2,  = 1, ml = + 2, ms = – 1/2
(vi) n = 3,  = 0, ml = 0, ms = + 1/2
Solution: Out of these (ii), (iv) and (v) are not allowable. The main reasons are:
(ii) n = 2,  = 2, ml = – 1, ms = – 1/2 is not allowable because  cannot have value equal to 2
for n = 2.
(iv) n = 3,  = 1, ml = + 1, ms = 0 is not allowable because s cannot be equal to 0.
(v) n = 2,  = 1, ml = + 2, ms = – 1/2 is not allowable because ml cannot be equal to +2 for  = 1
+ 2+
Illustration 25: Cu is diamagnetic whereas Cu is paramagnetic, why?
Solution: The electronic configuration of Cu+ is 3d10 and of Cu2+ is 3d9 (one unpaired electron) and thus,
2+ +
Cu is paramagnetic whereas Cu having no unpaired electron is diamagnetic.
Illustration 26: Which quantum numbers must be same in order that orbitals be degenerate in (a) H-atom
(b) Poly electronic atom?
Solution: Degenerate orbitals means orbitals having same energy. In H-atom if n is same for two orbitals,
their energy is same, (e.g., 2s = 2p). In poly electronic atom if (n +  ) is same, their energy is
same (e.g., 2px = 2py = 2pz), and not 3d and 4p, although n +  is same.

13. Rules for filling of electrons

Aufbau Principle
Electrons can be filled in a poly electronic atom one by one in the order of increasing energy level. Increasing order
of energies of various orbitals is - 1s, 2s, 2p, 3s, 3p, 4s, 3d, 4p, 5s, 4d, 5p, 6s, 4f, 5d, 6p, 7s ……………………..
(n +  ) rule: It states that:
(a) Sub shell having lower values of (n +  ) possess lower energy
level and should be filled first e.g.

19K - 1s2, 2s2 2p6, 3s2 3p6 3d1 (Wrong)

2 2 6 2 6 1
- 1s , 2s 2p , 3s 3p 4s (Correct)

Because - (n +  ) value of 4s = 4 + 0 = 4

and - (n +  ) value of 3d = 3 + 2 = 5

Thus, 4s should be filled first.

(b) If (n + l) value for two sub shell is same than the one with lower
values of n possess lower energy and should be filled first e.g.
2 2 6 2 6 2 1
21Sc - 1s , 2s 2p , 3s 3p , 4s 4p (Wrong)
2 2 6 2 6 1 2
- 1s , 2s 2p , 3s 3p 3d , 4s (Correct)
Because - (n +  ) value of 4p = 4 + 1 = 5
and - (n +  ) value of 3d = 3 + 2 = 5
Thus, 3d should be filled first  n of 3d < n of 4s.
A sub shell having nearly full filled or nearly half filled configuration tends to acquire exactly full filled or exactly half
filled nature in order to attain stability
The completely filled and completely half filled sub-shells are stable due to the following reasons:
1. Symmetrical distribution of electrons: It is well known that symmetry leads to stability. The completely
filled or half filled sub shells have symmetrical distribution of electrons in them and are therefore more
stable. Electrons in the same sub shell (here 3d) have equal energy but different spatial distribution.
Consequently, their shielding of one another is relatively small and the electrons are more strongly
attracted by the nucleus.
2. Exchange Energy: The stabilizing effect arises whenever two or more electrons with the same spin are
present in the degenerate orbitals of a sub shell. 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 sub shell is either half filled or completely filled. As a result the exchange
energy involved is maximum and so is the stability.
2 2 6 2 6 4 2
24Cr - 1s , 2s 2p , 3s 3p 3d , 4s (Wrong)
24 – ATOMIC STRUCTURE – JEE
2 2 6 2 6 5 1
- 1s , 2s 2p , 3s 3p 3d , 4s (Correct)

2 2 6 2 6 9 2
29Cu - 1s , 2s 2p , 3s 3p 3d , 4s (Wrong)
2 2 6 2 6 10 1
- 1s , 2s 2p , 3s 3p 3d , 4s (Correct)

Pauli’s Exclusion Principle

It is impossible for two electrons of an atom to have all their four quantum
2 2
Numbers same e.g. is correct for 1s and is wrong for 1s .
2
It leads to following conclusions – (a) Maximum no. of electrons in a shell can be 2n . (b) Maximum no. of electrons
in a subshell can be 2, 6, 10, 14 in s, p, d, f respectively. (c) Maximum no. of electrons in a sub-shell is 2 only.

Hund’s Rule
It states that:
(a) When a group of orbitals of equal energy (or subshells) is filled then it is preferred to assign electrons to
empty orbitals rather than pair them in a particular subshell, because the former arrangement leads to
lower energy level and hence stability.
(b) Same spin of unpaired electrons in subshell also gives rise to lower energy level e.g. 7N - 1s2, 2s2 2px1 2py1 2pz1
3
For 2p
is correct

px py pz
is wrong (statement a)

px py pz
is wrong (statement b)

px py pz

Illustration 27: The maximum number of 3d-electrons having spin quantum number, s =+1/2 is:
(A) 10 (B) 5
(C) 2 (D) 1
Solution: (B)
Illustration 28: The maximum number of electrons theoretically possible for a seventh principal shell is:
(A) 49 (B) 196
(C) 86 (D) 98
2 2
Solution: (D) No. of electrons in a shell = 2n = 2  7 = 98

Concept of Orbitals
The probability of finding the electron at a particular location is given by the square of wave function (2)
corresponding to that location. There are certain regions around the nucleus where probability of finding the
electron is high and there are certain regions where probability of finding the electron is low. The probability of
finding the electron does not become zero even at large distances from the nucleus, although it may become
negligible. Therefore, it is not possible to draw a boundary that will enclose the region of 100% probability.
However, for the sake of simplicity we draw arbitrary boundaries which enclose the regions where probability of
finding the electron is maximum (about 90-95%). An orbital may be defined as the region of space around the
nucleus where the probability of finding an electron is maximum (90–958%).
Shapes of Orbitals
 Y
Z

(i) 1s-orbital: It is spherically symmetrical

about the nucleus. So that the electronic X
charge is not concentrated in any particular
direction.

Charge cloud picture of 1s orbital

Y
Z

(ii) 2s-orbital: It is also spherically symmetrical

X
but it is larger than (i.e. away from) the 1s-
orbital.

Nodal
surface
Charge cloud picture of 2s orbital
(iii) p-orbitals –There are three p-orbitals viz. px, py and pz and they are dumb-bell shaped.
z z z

x x x
y y y
2p x 2p y 2p z
2p orbitals
(iv) d-orbitals: There are five d-orbitals. The shape of four d-orbitals is like double dumb-bell, and resemble
with four-leaf clovers. However, the fifth d-orbital looks like that of a p-orbital.

dxy dxz dx2  y2 dyz dz2

14. Nodal Plane and Nodal Surface

Node: The region of orbital where the probability of finding electron is zero.
Number of radial nodes = (n –  – 1)

In any orbital total number of nodes = (n – 1)

Number of Angular nodes or nodal plane =  (angular momentum quantum number)
26 – ATOMIC STRUCTURE – JEE
QUIZ – 5
2+
1. The "spin-only" magnetic moment [in units of Bohr magneton, (B)] of Ni in aqueous solution would be:
(At. No. Ni = 28)
(A) 1.73 (B) 2.84 (C) 4.90 (D) 0

2. If the value of n +  is more than 3 and less than 6, what will be the possible number of orbitals?
(A) 10 (B) 11 (C) 13 (D) 6

3. Which of the following has maximum magnetic moment?

2+ 2+ 3+
(A) Mn (Z = 25) (B) Fe (Z = 26) (C) Fe (Z = 26) (D) Ce (Z = 24)

4. Which of the following sets of quantum numbers represents the highest energy of an atom?
(A) n = 3,  = 1, m = 1, s = +1/2 (B) n = 3,  = 2, m = 1, s = +1/2
(C) n = 4,  = 0, m = 0, s = +1/2 (D) n = 3,  = 0, m = 0, s = +1/2
5. Orbital angular momentum for a d-electron is
6h 6h 12h 12h
(A) (B) (C) (D)
2 2 2 2

6. The total no. of d-electron in Fe2+ (at. no. = 26) is not equal to:
(A) p-electron in 10Ne (B) s-electron in 12Mg
–
(C) d-electron in Fe (D) p-electron in Cl

7. Which of the following set of quantum number is correct for an electron present in 4f-orbital?
(A) n = 3,  = 2, m = – 2, s = + 1/2 (B) n = 4,  = 4, m = – 4, s = – 1/2
(C) n = 4,  = 3, m = + 1, s = + 1/2 (D) n = 4,  = 3, m = + 4, s = + 1/2

8. The maximum number of electrons in an atom with l = 2 and n = 3 is:

(A) 2 (B) 6 (C) 12 (D) 10

9. For 4py orbital: There are: nodal plane = ................ and azimuthal quantum number  = ............
(A) 1, 0 (B) 0, 1 (C) 1, 1 (D) 2, 1
10. What are the values of the orbital angular momentum of an electron in the orbitals 1s, 3s, 3d and 2p?
(A) 0, 0, 6, 2 (B) 1,1, 4, 2
(C) 0,1, 6, 3 (D) 0,0, 20 , 6

11. Five valence electrons of 15 P are labelled as

If the spin quantum of B and Z is + 1 /2, the group of electrons with three of the quantum number same are
(A) AB, XYZ, BY (B) AB (C) XYZ, AZ (D) AB, XYZ
12. Select the correct relation between azimuthal quantum number (  ) and magnetic quantum number (m):
m 1
(A)  (B) m2 (C) m  22  1 (D)   2m  1
2
13. Following electronic configuration violates:
2s 2p
   
(A) Only Pauli's rule (B) Only Hund's rule
(C) Only (n +  ) rule (D) All of these
rd
14. What is the order of energy of sub-shells of 3 orbit of H-atom?
(A) 3s < 3p < 3d (B) 3s > 3p > 3d (C) 3s = 3p = 3d (D) 3p > 3s > 3d
15. The number of radial nodes in 3s and 2p orbitals respectively are:
(A) 2 and 0 (B) 1 and 2 (C) 0 and 2 (D) 2 and 1
15. Electronic Configurations of Elements
At. Name of Electron At. Name of Electron
No. Element Symbol Configuration No. Element Symbol Configuration
1 Hydrogen H 1s1 57 Lanthanum La [Xe] 6s2 5d1
2 Helium He 1s2 58 Cerium Ce [Xe] 6s2 4f2
3 Lithium Li 1s2 2s1 59 Praseodymium Pr [Xe] 6s2 4f3
4 Beryllium Be 1s2 2s2 60 Neodymium Nd [Xe] 6s2 4f4
5 Boron B 1s2 2s2 2p1 61 Promethium Pm [Xe] 6s2 4f5
2 2 2 2 6
6 Carbon C 1s 2s 2p 62 Samarium Sm [Xe] 6s 4f
2 2 3 2 7
7 Nitrogen N 1s 2s 2p 63 Europium Eu [Xe] 6s 4f
2 2 4 2 7 1
8 Oxygen O 1s 2s 2p 64 Gadolinium Gd [Xe] 6s 4f 5d
2 2 5 2 9
9 Fluorine F 1s 2s 2p 65 Terbium Tb [Xe] 6s 4f
2 2 6 2 10
10 Neon Ne 1s 2s 2p 66 Dysprosium Dy [Xe] 6s 4f
2 2 6 1 2 11
11 Sodium Na 1s 2s 2p 3s 67 Holmium Ho [Xe] 6s 4f
2 2 6 2 2 12
12 Magnesium Mg 1s 2s 2p 3s 68 Erbium Er [Xe] 6s 4f
2 2 6 2 1 2 13
13 Aluminium Al 1s 2s 2p 3s 3p 69 Thullium Tm [Xe] 6s 4f
14 Silicon Si 1s2 2s2 2p63s23p2 70 Ytterbium Yb [Xe] 6s2 4f14
15 Phosphorus P 1s2 2s2 2p63s2 3p3 71 Lutetium Lu [Xe] 6s2 4f14 5d1
16 Sulphur S 1s2 2s2 2p6 3s2 3p4 72 Hafnium Hf [Xe] 6s2 4f145d2
17 Chlorine Cl 1s2 2s2 2p6 3s2 3p5 73 Tantalum Ta [Xe] 6s2 4f145d3
18 Argon Ar 1s2 2s2 2p6 3s2 3p6 74 Tungsten W [Xe] 6s2 4f145d4
1 2 14 5
19 Potassium K [Ar] 4s 75 Rhenium Re [Xe] 6s 4f 5d
2 2 14 6
20 Calcium Ca [Ar] 4s 76 Osmium Os [Xe] 6s 4f 5d
2 1 2 14 7
21 Scandium Sc [Ar] 4s 3d 77 Iridium Ir [Xe] 6s 4f 5d
2 2 1 14 9
22 Titanium Ti [Ar] 4s 3d 78 Platinum Pt [Xe] 6s 14f 5d
2 3 1 14 10
23 Vanadium V [Ar] 4s 3d 79 Gold Au [Xe] 6s 4f 5d
1 5 2 14 10
24 Chromium Cr [Ar] 4s 3d 80 Mercury Hg [Xe] 6s 4f 5d
2 5 2 14 10 1
25 Manganese Mn [Ar] 4s 3d 81 Thalium Tl [Xe] 6s 4f 5d 6p
2 6 2 14 10
26 Iron Fe [Ar] 4s 3d 82 Lead Pb [Xe] 6s 4f 5d 6p2
27 Cobalt Co [Ar] 4s23d7 83 Bismuth Bi [Xe] 6s2 4f145d10 6p3
28 Nickel Ni [Ar] 4s23d8 84 Polonium Po [Xe] 6s2 4f145d10 6p4
29 Copper Cu [Ar] 4s13d10 85 Astatine At [Xe] 6s2 4f145d10 6p5
30 Zinc Zn [Ar] 4s23d10 86 Radon Rn [Xe] 6s2 4f145d10 6p6
31 Gallium Ga [Ar] 4s23d10 4p1 87 Francium Fr [Rn] 7s1
2 10 2 2
32 Germanium Ge [Ar] 4s 3d 4p 88 Radium Ra [Rn] 7s
2 10 3 2 1
33 Arsenic As [Ar] 4s 3d 4p 89 Actinium Ac [Rn] 7s 6d
2 10 4 2 2
34 Selenium Se [Ar] 4s 3d 4p 90 Thorium Th [Rn] 7s 6d
2 10 5 2 2 1
35 Bromine Br [Ar] 4s 3d 4p 91 Protactinium Pa [Rn] 7s 5f 6d
2 10 6 2 3 1
36 Krypton Kr [Ar] 4s 3d 4p 92 Uranium U [Rn] 7s 5f 6d
1 2 4 1
37 Rubidium Rb [Kr] 5s 93 Neptunium Np [Rn] 7s 5f 6d
2 2 6
38 Strontium Sr [Kr] 5s 94 Plutonium Pu [Rn] 7s 5f
2 1 2 7
39 Yttrium Y [Kr] 5s 4d 95 Americium Am [Rn] 7s 5f
2 2 2 7 1
40 Zirconium Zr [Kr] 5s 4d 96 Curium Cm [Rn] 7s 5f 6d
28 – ATOMIC STRUCTURE – JEE
1 4 2 8 1
41 Niobium Nb [Kr] 5s 4d 97 Berkelium Bk [Rn] 7s 5f 6d
1 5
42 Molybdenum Mo [Kr] 5s 4d 98 Californium Cf [Rn] 7s2 5f10
43 Technetium Tc [Kr] 5s1 4d6 99 Einsteinum Es [Rn] 7s2 5f11
1 7 2 12
44 Ruthenium Ru [Kr] 5s 4d 100 Fermium Fm [Rn] 7s 5f
1 8 2 13
45 Rhodium Rh [Kr] 5s 4d 101 Mendelevium Md [Rn] 7s 5f
10 2 14
46 Palladium Pd [Kr] 4d 102 Nobelium No [Rn] 7s 5f
1 10 2 14 1
47 Silver Ag [Kr] 5s 4d 103 Lawrencium Lr [Rn] 7s 5f 6d
2 10 2 14 2
48 Cadmium Cd [Kr] 5s 4d 104 Rutherfordium Rf [Rn] 7s 5f 6d
2 10 1 2 14 3
49 Indium In [Kr] 5s 4d 5p 105 Dubnium Db [Rn] 7s 5f 6d
2 10 2 2 14 4
50 Tin Sn [Kr] 5s 4d 5p 106 Seaborgium Sg [Rn] 7s 5f 6d
2 10 3 2 14 5
51 Antimony Sb [Kr] 5s 4d 5p 107 Bohrium Bh [Rn] 7s 5f 6d
2 10 4 2 14
52 Tellurium Te [Kr] 5s 4d 5p 108 Hassium Hs [Rn] 7s 5f 6d6
53 Iodine I [Kr] 5s2 4d10 5p5 109 Meitnerium Mt [Rn] 7s2 5f14 6d7
54 Xeon Xe [Kr] 5s2 4d10 5p6 110 Ununnilium Uun [Rn] 7s2 5f14 6d8
55 Cesium Cs [Xe] 6s1 111 Unununium Uuu [Rn] 7s2 5f14 6d9
2 2 14 10
56 Barium Ba [Xe] 6s 112 Ununbium Uub [Rn] 7s 5f 6d
16. Level – 1 (Main)
1. What is the radius ratio He+ ion, when the electron is in the second excited level to Li2+ ion when the
st
electron is in the 1 excited level?
(A) 3/2 (B) 4/3 (C) 27/8 (D) 8/23
st + nd
2. What is ratio of frequency of revolution of an electron in 1 excited level of He ion to and electron in 2
excited level of Li2+ ion?
(A) 3/2 (B) 1/2 (C) 3:1 (D) 1:3

3. The potential energy of an electron in hydrogen atom is – 3.02 eV, its kinetic energy will be:
(A) 1.51 eV (B) 15.10 eV (C) 13.6 eV (D) 1.36 eV

1
4. Select the incorrect graph for velocity of e– in an orbit VS. Z, and n:
n

v v v v

n 1/n z n
(A) (B) (C) (D)

5. According to Bohr’s atomic theory, which of the following is correct?

Z2
(A) Potential energy of electron  3
n
(B) The product of velocity of electron and principle quantum number (n)  Z2
Z2
(C) Frequency of revolution of electron in an orbit  3
n
Z2
(D) Coulombic force of attraction on the electron  3
n

th 13.6 2
6. The energy of an electron moving in n Bohr’s orbit of an element is given by En  Z eV/atom (Z =
n2
2
atomic number). The graph of E Vs Z (keeping “n” constant) will be:

Z2
(A) (B) (C) (D)

7. The ratio of the radius difference between 4th and 3rd orbit of H-atom and that of Li2+ ion is:
(A) 1:1 (B) 3:1 (C) 3:4 (D) 9:1
– 6
8. The velocity of an e in excited state of H-atom is 1.093  10 m/s. What is the circumference of this orbit?
–10 –10
(A) 3.32  10 m (B) 6.64  10 m
–10 –8
(C) 13.30  10 m (D) 13.28  10 m
9. The number of photons emitted in 10 hours by a 60 W sodium lamp ( of photon = 6000 Å)
[Take hc = 12400 eVÅ, h = Plank’s constant, c = speed of light]
24 23 23 23
(A) 6.5  10 (B) 6.40  10 (C) 8.40  10 (D) 3.40  10
10. If the shortest wavelength of H atom in Lyman series is x, then longest wave length in Balmer series of He+
ion is:
(A) 9x/5 (B) 36x/5 (C) x/4 (D) 5x/9
th th
11. What is difference in wavelengths of the 4 and 5 lines of Balmer series in spectrum of hydrogen atom?
(A) 131 Å (B) 520 Å (C) 390 Å (D) 262 Å
30 – ATOMIC STRUCTURE – JEE

12. A dye absorbs a photon of wavelength  and re-emits the same energy into two photons of wavelengths 1
and 2 respectively. The wavelength  is related with 1 and 2 as:
1   2 1 2 12  22 1 2
(A)  (B)  (C)  (D) 
1 2 1   2 1   2  1   2 
2

13. A hydrogen atom in the ground state in excited by monochromatic radiation of wavelength  Ǻ. The
resulting spectrum consists of maximum 15 different lines. What is the wavelength ? (RH = 109737 cm–1)
(A) 937.3 Ǻ (B) 1025 Ǻ (C) 1236 Ǻ (D) None of these

14. A photon of 300 nm is absorbed by a gas and then remits two photons one are emitted photon has
wavelength 496 nm; the wavelength of second re remitted photon is:
(A) 757 (B) 857 (C) 957 (D) 657
–19
15. In a photoelectric effect, the energy of the photon striking a metallic surface is 5.6  10 J. The kinetic
–20
energy of the ejected electrons is 12.0  10 J. The work function is:
–19 –19 –19 –20
(A) 6.4  10 J (B) 6.8  10 J (C) 4.4  10 J (D) 6.4  10 J
2+ th
16. If the I.P. of Li is 122.4 eV. Find out 6 I.P. of carbon.
(A) 122.4  4 eV (B) 122.4  2 eV (C) 122.4  3 eV (D) 122.4  5 eV

17. If the electron of a hydrogen atom is present in the first orbit, the total energy of the electron is:
2 2 2 2 2 2
(A) – e / 2r (B) –e /r (C) –e /r (D) – e / 2r

18. What is the difference in the wavelengths of 4th and 5th lines of Balmer series in the spectrum of hydrogen
atom?
(A) 131 Å (B) 520 Å (C) 390 Å (D) 262 Å

19. An energy of 24.6 eV is required to remove one of the electrons from a helium atom. The energy required
to remove both electrons from helium atom is:
(A) 38.2 eV (B) 49.2 eV (C) 51.8 eV (D) 79 eV

20. The angular momentum of electron in hydrogen atom is proportional to:

1 1
(A) r (B) (C) r2 (D)
r r

21. If the electron in hydrogen atom jumps from the third orbit to second orbit, the wavelength of the emitted
radiation is given by:
36 5R 5 R
(A)  (B)  (C)  (D) 
5R 36 R 6
22. The de Broglie wavelength of neutron at 27C is . The wavelength at 927C will be:
   
(A) (B) (C) (D)
9 4 2 3
23. The ratio of time periods (T1/T2) in second orbit of hydrogen to third orbit of He+ ion is:
(A) 8/27 (B) 32/27 (C) 27/32 (D) 24/36
3+ 2+
24. The ratio of spin only magnetic moments of Fe and Co is:
(A) 24 : 15 (B) 7:3 (C) 35 : 15 (D) 5: 7

25. The frequency of radiation emitted, when the transition of electron takes place from (n + 1) level to nth
level will be: (n >>>1)
2CRz 2 CRz 2 CRz 2 2CRz 2
(A)  2
(B)  2
(C)  4
(D) 
n n n n3
26. Which of the following curves represent the speed of the electron of
hydrogen atom as a function of principal quantum number 'n'?
(A) 1
(B) 2
(C) 3
(D) 4

27. The ratio of frequency of electrons moving in second excited state of He+ to that of in second excited state
of H is:
4 27 1 27
(A) (B) (C) (D)
1 32 54 2

28. The uncertainty in momentum of an electron is 1 10 5 kg  m / s . The uncertainty in its position will be
( h  6.62  10 34 kg  m 2 / s)
(A) 1.05  10 28 m (B) 1.05  10 26 m (C) 5.27  10 30 m (D) 5.25  10 28 m

29. What is the de Broglie wavelength of photon having 5% velocity to the velocity of light?
–5 –5 –5 –5
(A) 0.26  10 nm (B) 0.62  10 nm (C) 6.2  10 nm (D) 2.6  10 nm

30. The wavelength associated with a ball of mass 100 g moving with a speed 103 cm sec–1 (h = 6.6  10–34 J s–1) is:
(A) 6.6  1032 cm (B) 6.6  10–27 cm (C) 6.6  1027 cm (D) 6.6  10–32 cm

17. Level – 2 (Main)

1. The ratio of the difference between 2nd and 3rd Bohr’s orbit energy to that between 3rd and 4th orbit energy is:
(A) 7/20 (B) 5/27 (C) 20/7 (D) 27/5

2. What is the ratio of time periods (T1/T2) in second orbit of hydrogen atom to third orbit of He+ ion?
(A) 8/27 (B) 32/27 (C) 27/32 (D) None of these

3. 
Find the value of wave number  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.
8R 32R 3R
(A) (B) (C) (D) None of these
9 9 4

4. If the total energy of an electron in a hydrogen like atom in excited state is –3.4 eV, then the de Broglie
wavelength of the electron is:
–10 –10 9 –12
(A) 6.6  10 (B) 3  10 (C) 5  10 (D) 9.3  10

5. Which of the following best describes the emission spectrum of atomic hydrogen?
(A) a discrete series of lines of equal intensity and equally spaced w.r.t. wavelength
(B) a series of only four lines.
(C) a continuous emission of radiation of all frequencies.
(D) several discrete series of lines with both intensity and spacing between lines decreasing as the
wave number increases with each series.

6. The wavelength of certain line in Balmer series is observed to be 4341 Å. To what volume of ‘n’ does this
correspond?
(A) 5 (B) 3 (C) 4 (D) 6

7. The angular momentum of an electron in a Bohr’s orbit of He+ is 3.1652  10–34 kg-m2 / sec. What is the
wave number is terms of Rydberg constant (R) of the spectral line emitted when an electron falls from this
–34
level to the first excited state. [Use h = 6.626  10 Js]
5R 3R 8R
(A) 3R (B) (C) (D)
9 4 9
32 – ATOMIC STRUCTURE – JEE
2+
8. If radiation corresponding to second line of “Balmer series” of Li ion, knocked out electron from first
excited state of H-atom, then kinetic energy of ejected electron would be:
(A) 2.55 eV (B) 4.25 eV (C) 11.25 eV (D) 19.55 eV

9. The emission spectra is observed by the consequence of transition of electron from higher energy state to
+
ground state of He ion. Six different photons are observed during the emission spectra, then what will be
the minimum wavelength during the transition?
4 4 15 16
(A) (B) (C) (D)
27RH 15RH 16RH 15RH

10. Wavelength of high energy transition of H atom is 91.2 nm. The corresponding wavelength of He+ ion will be:
(A) 22.8 nm (B) 24.2 nm (C) 45.6 nm (D) 11.4 nm

11. Calculate the number of quanta of radiations of frequency 4.67  1013 s–1 that must be absorbed in order to
melt 5 g of ice (The energy required to melt 1g of ice is 333 J)
18 22 –21
(A) 3.36  10 (B) 17 (C) 5.38  10 (D) 30.91  10

12. A particle X moving with a certain velocity has a de Broglie wave length of 1Ǻ. If particle Y has a mass of
25% that of X and velocity 75% that of X, de Broglie wave length of Y will be:
(A) 3Ǻ (B) 5.33 Ǻ (C) 6.88 Ǻ (D) 48 Ǻ

13. An electron is allowed to move freely in a closed cubic box of length of side 10 cm. The minimum
uncertainty in its velocity will be:
–4 –1 –4 –1
(A) 3.35  10 m sec (B) 5.8  10 m sec
–5 –1 –6 –1
(C) 4  10 m sec (D) 4  10 m sec

14. Two particles of mass m and 2m have equal kinetic energy. Their de Broglie wave lengths are in the ratio:
(A) 1:1 (B) 1:2 (C) 1: 2 (D) 2 :1

15. Wave function of an orbital is given below in the variation or w.r.t. distance from 
nucleus. It may be graphical representation of:
(A) 1s
(B) 2s
(C) 2p
(D) 3s

16. If 0 is threshold wavelength for photoelectric emission,  the wavelength of light falling on the surface of a
metal and m the mass of the electron then velocity of ejected electron is given by:
1/ 2 1/ 2
 2h   2hc 
(A)  m (  0   ) (B)  m (  0   )
   
 2hc     1/ 2   2hc   0    
1/ 2

(C)  
0
  (D)   
 m   0     m   0   

16 –1
17. When a certain metal was irradiated by light of frequency 3.0  10 sec photoelectron emitted had twice
the kinetic energy as did photoelectrons emitted when the same metal was irradiated with light of
16 –1
frequency 2.0  10 sec . The threshold frequency is:
16 –1
(A) 1.0  10 sec (B) 8.0  1013 sec–1
16 –1
(C) 6.4  10 sec (D) 3.2  1015 sec–1

18. A photosensitive metallic surface has work function h0. If photons of 2h0 fall on the surface, the electrons
6
come out with a maximum velocity of 4  10 m/s. If photon energy is increased to 5h 0, the maximum
velocity of photo electrons will be:
(A) 2  107 m/s (B) 8  106 m/s
6
(C) 2  10 m/s (D) 8  105 m/s
19. The emission spectrum of hydrogen is found to satisfy the expression for the energy change. E (in joules)
 1 1
such that E  2.18  10  2  2  J where n1  1,2,3.... and n2  2,3,4.... The spectral lines correspond to
n
 1 n 2 

Paschen series to
(A) n1  1 and n2  2,3,4 (B) n1  3 and n2  4,5,6
(C) n1  1 and n2  3,4,5 (D) n1  1 and n2  infinity

20. The wavelength of the radiations emitted, when in a hydrogen atom electron falls from infinity to stationary
7 –1
state is (RH = 1.097  10 m ):
–8
(A) 9.1  10 nm (B) 192 nm (C) 406 nm (D) 91 nm
+
21. If the shortest wavelength of H-atom in Lyman series is , then longest wavelength in Balmer series of He ion is:
9 36   5
(A) (B) (C) (D)
5 5 4 9

22. Which of the following is correctly matched?

Ion / atom Ionization Potential
(A) H 54.16 eV
+
(B) He 13.6 eV
2+
(C) Li 121.8 eV
(D) Be3+ 216.6 eV

23. An excited hydrogen atom returns to the ground state. The wavelength of emitted photon is . The
principal quantum number of the excited state will be:
1/ 2 1/ 2
 R   R  1
(A)  R  1 (B)  R 
   
1/2
 1 
R  R  1 
1/2
(C) (D)  
 R  R  1 

24. Two electrons are revolving around a nucleus at distances 'r' and '4r'. The ratio of their periods is:
(A) 1:4 (B) 4:1 (C) 8:1 (D) 1:8

25. Select the correct matching:

(I) Momentum of photon — Independent of wavelength of light
(II) Radius of nucleus — (Mass number)1/3  10–15 m
Charge
(III) ratio of anode rays — Independent of the gas filled in the discharge tube
Mass
4
(IV) Wavelength of radiation when electron —
3R
of H-atom returns from n = 2 to n = 1
(A) I, II (B) II, IV (C) I, III (D) I, II, III, IV

26. If 0 is the threshold wavelength of a metal for photoelectron emission. If the metal is exposed to the light
2h
of wavelength , then the velocity of ejected electron will be  0    K. The value of K is:
m
C 1
(A) speed of light (B) 1 (C) (D)
0   0

y
27. In the transition of electron in an atom, its kinetic energy changes from y to . The change in potential
4
energy will be:
3 3 3 3
(A)  y (B)  y (C)  y (D)  y
4 4 8 2
34 – ATOMIC STRUCTURE – JEE
28. The given diagram indicates the energy levels of a certain atom. 2E
When the system moves from 2E level to E level, a photon of 4
E
wavelength  is emitted. The wavelength of photon produced 3
E
4E
during the transition from to E level is:
3 0

 3
(A) (B)
3 4
4
(C) (D) 3
3

29. An -particle approaches the target nucleus of copper (Z = 29) in such a way that the value of impact
parameter is zero. The distance of closest approach will be:
20 (K.E.) 29 e 2
(A) (B)
29 e 2
20 (K.E.)
40 (K.E.)
(C) (D) (K.E.)
29 e2

30. The value of Planck’s constant is 6.63  10 34 Js . The velocity of light is 3.0  108 ms1 . Which value is
closest to the wavelength in nanometres of a quantum of light with frequency of 8  1015 s1 ?
(A) 3  10 7 (B) 2  10 25
(C) 5  10 18 (D) 4  101

18. Level – 3 (Advanced)

Single Choice
1. A hydrogen atom in its ground state absorbed a photon and the electron was promoted to the fifth orbit. When
the excited atom returned to its ground state, visible and other quanta were emitted. Other quanta are:
(A) 21 (B) 52 (C) 31 (D) 41

2. Which of the following orbitals has/have zero probability of finding the electron in xy plane:
(A) pz (B) dyz (C) dzx (D) px

3. The electrons, identified by quantum number n and l, (i) n = 4,  = 1 (ii) n = 4,  = 0 (iii) n = 3,  = 1 can
be placed in order of increasing energy, from the lowest to highest, as:
(A) (iii) < (ii) < (i) (B) (ii) < (i) < (iii)
(C) (i) < (iii) < (ii) (D) (iii) < (i) < (ii)
+ 2+
4. The ionisation energy of H atom is 13.6 eV. What will be ionisation energy of He and Li ions?
(A) 54.4 eV, 122.4 eV (B) 54.4 eV, 112.4 eV
(C) 544 eV, 122.4 eV (D) 122.4 eV, 122.2 eV

5. A single electron in an ion has ionization energy equal to 217.6 eV. What is the total number of protons
present in one ion of it?
(A) 2 (B) 4
(C) 5 (D) 9

6. Which of the following is wrong?

(A) according to quantum mechanics wave function  has by itself no physical meaning
(B) for s orbital  = f(r).f(x).f(y).f(z)
+

(C) the diagram of 2 for 'p' orbital should be but not

(D) all
7. The Schrödinger wave equation for hydrogen atom is
3/2
1  1  r  r / a
 2s    2  e 0
4 2  a 0   a0 
Where a0 is Bohr’s radius. If the radial node in 2s be at r 0 would be equal to:
a0 a0
(A) (B) 2a0 (C) 2a0 (D)
2 2

8. The Schrödinger wave equation for hydrogen atom is

3/2
1  Z
(radial)   
16 4  a0     
   1 2  8  12  e  / 2

2Zr
Where a0 and Z are the constant in which answer can be expressed and   minimum and maximum
a0
position of radial nodes from nucleus are….. respectively:
a0 3a0 a0 a0 a0 3a0 a0 4a0
(A) , (B) , (C) , (D) ,
Z Z 2Z Z 2Z Z 2Z Z

9. The angle made by angular momentum vector of an electron with z-axis is given as:
(A) cos    / m (B) cos    / m
(C) cos       1 m (D) cos   m     1

10. Which of the following statements is not correct?

(A) The shape of an atomic orbital depends on the azimuthal quantum number.
(B) The orientation of an atomic orbital depends on the magnetic quantum number.
(C) The energy of an electron in an atomic orbital of multielectron atom depends on principal quantum
number.
(D) The number of degenerate atomic orbitals of one type depends on the values of azimuthal and
magnetic quantum number.

11. Which of the following statements is not correct?

(A) Special stability of half-filled and fully-filled atomic configuration amongst s- and p-block elements
is reflected in ionization potential trends along a period.
(B) Special stability of half-filled and fully-filled atomic configurations amongst s- and p-block elements
is reflected in electron affinity trends along a period.
(C) Aufbau order is not obeyed in cases where energy difference between ns and (n – 1)d subshell is large.
(D) Special stability of half-filled subshell is attributed to higher exchange energy of stabilization.

1 2
12. A small particle of mass m moves in such a way that P.E. =  mkr , where k is a constant and r is the
2
distance of the particle from origin. Assuming Bohr’s model of quantization of angular momentum and
circular orbit, r is directly proportional to:
2
(A) n (B) n (C) n (D) None of these

13. An element undergoes a reaction as shown:

X + 2e–   X2–, energy released = 30.87 eV/atom. If the energy released, is used to dissociate 4 gms
of H2 molecules, equally into H+ and H*, where H* is excited state of H atoms where the electron travels in
orbit whose circumference equal to four times its de Broglie’s wavelength. Determine the least moles of X
that would be required: (Given: I.E. of H = 13.6 eV/atom, bond energy of H2 = 4.526 eV/molecule)
(A) 1 (B) 2 (C) 3 (D) 4
14. A hydrogen like species (atomic number Z) is present in a higher excited state of quantum number n. This
excited atom can make a transition to the first excited state by successive emission of two photons of
energies 10.20 eV and 17.0 eV respectively. Alternatively, the atom from the same excited state can make
a transition to the second excited state by successive emission of two photons of energy 4.25 eV and 5.95
eV respectively. Determine the value of Z.
(A) 1 (B) 2 (C) 3 (D) 4
36 – ATOMIC STRUCTURE – JEE
15. The electron of H-atom in ground state is excited to higher energy level by the monochromatic light of
energy 13.22 eV, then how many number of different photons emitted when it will return to ground state?
(A) 4 (B) 10 (C) 6 (D) 15

16. If the radius of the first Bohr's orbit is 'r' then the de-Broglie wavelength of the electron in the 3rd orbit will be:
2r 3 r
(A) 2r (B) (C) (D) 6r
3 3

17. Li(g)   Li3+ + 3e–, H = 19612 kJ/mole

If the first I.E. of Li is 520 kJ/mole, then what would be the it's IInd I.E.
(A) 19092 kJ/mole (B) 7275 kJ/mole
(C) 779 kJ/mole (D) 8720 kJ/mole

18. If the lowest energy X-rays have  = 3.055  10–8 m, estimate the minimum difference in energy between
two Bohr's orbits such that an electronic transition would correspond to the emission of an X-ray. Assuming
that the electrons in other shells exert no influence, at what Z (minimum) would a transition from the
second energy level to the first result in the emission of an X-ray?
(A) 1 (B) 2 (C) 3 (D) 4

19. Threshold frequency of a metal is f0. When light of frequency v = 2f0 is incident on the metal plate,
maximum velocity of e– emitted is v1. When frequency of incident radiation is 5f0, maximum velocity of
– v
emitted e is v2. Find ratio of 1 :
v2
(A) 1:4 (B) 1:2 (C) 2:1 (D) none of these

20. A light source of wavelength  illuminates a metal and ejects photo-electrons with (K.E.)max = 1 eV

Another light source of wavelength , ejects photo-electrons from same metal with (K.E.)max = 4 eV.
3
Find the value of work function?
(A) 1 eV (B) 2 eV (C) 0.5 eV (D) None of these
2+
21. de-Broglie wavelength of electron in second orbit of Li ion will be equal to de-Broglie of wavelength of
electron in:
5+
(A) n = 3 of H-atom (B) n = 4 of C ion
3+ +
(C) n = 6 of Be ion (D) n = 3 of He ion

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
–5
volume around x = a, y = z = 0 is 1  10 . what is the probability of finding the same s-orbital electron in
the same sized volume around x = z = 0, y = a.
(A) 1  10–5 (B) 1  10–5  a
–5 2
(C) 1  10  a (D) 1  10–5  a–1

23. For an electron, with n = 3 has only one radial node. The orbital angular momentum of the electron will be
h h  h 
(A) 0 (B) 6 (C) 2 (D) 3 
2 2  2 

24. In a certain electronic transition in the hydrogen atom from an initial state i to a final state f, the difference
in the orbit radius (ri  rf) is seven times the Bohr radius. Identify the transition.
(A) 41 (B) 42 (C) 43 (D) 31

25. The kinetic energy of an electron in a particular orbit in H atom is 3.4 eV. The angular momentum of
electron in this orbit is :
(A) h/2 (B) h/
(C) 3h/2 (D) 2h/
 Multiple Choice
1. The angular momentum of electron can have the value(s):
h h h h
(A) 0.5 (B) (C) (D) 2.5
  0.5 2

2. Select the correct statement(s):

(A) An electron near the nucleus is attracted by the nucleus and has a low potential energy
(B) According to Bohr's theory, an electron continuously radiate energy if it stayed in one orbit
(C) Bohr's model could not explain the spectra of multielectron atoms
(D) Bohr's model was the first atomic model based on quantization of energy

3. For radial probability curves, which of the following is/are correct?

(A) The number of maxima in 2s orbital are two
(B) The number of spherical or radial nodes is equal to n –  – 1
(C) The number of angular nodes are '  '
(D) 3d2z has 3 angular nodes

4. Select the correct statement(s):

(A) Heisenberg's principle is applicable to stationary e–
(B) Pauli's exclusion principle is not applicable to photons
–
(C) For an e , the product of velocity and principal quantum number will be independent of principal
quantum number
(D) Quantum number  and m determine the value of angular wave function

5. Select the correct statement(s) regarding 3Py orbital:

(A) Total no. of nodes are 2
2 2
(B) Number of maxima in the curve 4r R vs r is one
(C) Quantum no. n,  and m for orbital may be 3, 1, –1 respectively
(D) The magnetic quantum number may have a positive value

6. Select the correct statement(s):

–
(A) In wave mechanical modal the energy of e in the orbital remains the same
(B) dxy orbital is lies in Y-Z plane
(C) Nodal planes are yz and xy in dx 2  y2 orbital
(D) Rest mass of photon is zero and increases with it's velocity

7. Select incorrect statement(s):

(A) If the value of  = 0, the electrons distribution is spherical
(B) the shape of the orbital is given by magnetic quantum number
(C) Angular momentum of 1s, 2s, 3s electrons are equal
(D) In an atom, all the electrons travel with the same velocity

8. Select the correct statement(s):

(A) An orbital with  = 1 is symmetrical about the nucleus
(B) An orbital with  = 1 is spherically symmetrical about the nucleus
(C) 3dz2 is spherically symmetrical about the z-axis
(D) All are correct

9. Which of the following statements are correct?

(A) The probability of finding a 4d electron right at the nucleus is zero
(B) For all values of m, the p-orbital have the same shape, for a given atom
(C) A 2px atomic orbital consists of two lobes of electron density
(D) There is no probability of finding a p-electron right at the nucleus

10. Which of quantum number are consistent with the theory?

(A) n = 2,  = 1, m = 0, s = +1/2 (B) n = 4,  = 3, m = –2, s = –1/2
(C) n = 3,  = 2, m = –3, s = +1/2 (D) n = 4,  = 3, m = –3, s = +1/2
38 – ATOMIC STRUCTURE – JEE
11. Select the correct curve(s):
If v = Velocity of electron in Bohr's orbit
r = Radius of electron in Bohr's orbit
P.E. = Potential energy of electron in Bohr's orbit
K.E. = Kinetic energy of electron in Bohr's orbit

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

12. The charge cloud of single electron in a 2px atomic orbital has two lobes of electron density. It means:
(A) there is high probability of locating the electron in a 2p x atomic orbital at values of x > 0
(B) there is a high probability of locating it for values of x < 0 but no probability at all of locating if
anywhere in the yz-plane along which x = 0
(C) there is great probability of finding a p-electron right at the nucleus
(D) all are correct

13. Which of the following statements are correct?

(A) For all values of n, the p-orbital have the same shape, but the overall size increases at it increases
for a given atom.
(B) The fact that there is a particular direction along with each p-orbital has maximum electron density,
play an important role in determining molecular geometries.
(C) The charge cloud of a single electrons in 2px atomic orbital consists of two lobes of electron
density
(D) none are correct

14. The radial distribution functions [P(r)] is used to determine the most probable radius, which is used to find
dP  r 
the electron in a given orbital for 1s-orbital hydrogen like atom having atomic number Z, is
dr
dP 4Z3  2Zr 2  2Zr /a0
 3  2r  e :
dr a0  a0 
Then which of the following statements is/are correct?
dP(r)
(A) At the point of maximum value of radial distribution function  0 ; one antinode is present
dr
a
(B) Most probable radius of Li2+ is 0 pm
3
+ a
(C) Most probable radius of He is 0 pm
2
(D) Most probable radius of hydrogen atom is a0 pm

15. Select the correct statement(s):

(A) Radial function [R(r)] a part of wave function is dependent on quantum number n only
(B) Angular function depends only on the direction, and is independent to the distance from the
nucleus
(C) 2 (r, , ) is the probability density of finding the electron at a particular point in space
(D) Radial distribution function (4r2R2) gives the probability of the electron being present at a distance
r from the nucleus
19. Level – 4 (Comprehension & Match the Column)
CMP: On exchanging the position in space of two electrons with parallel spins there is no change in the
electronic arrangement. It would lead to decrease in energy. The pair of electrons is called
exchange pair. The energy decrease per exchange pair of electrons is termed as exchange energy
(E). The energy required for placing two electrons together in the same orbital is called pairing
energy (P) configuration with even or uniform or symmetrical distribution of charge in all direction
would be associated with lower energy and hence higher stability than the configuration with
unsymmetrical distribution of electronic charge. The energy required to promote an electron from a
lower energy orbital to a higher energy orbital is promotional energy (E).

1. Which of these arrangement are not possible according Aufbau principle:

(A) (B)
4s 3d 4s 3d

(C) (D)
4s 3d 4s 3d

2. Which of these arrangement is most stable:

(A) (B)

(C) (D)

1 10 2 9
3. 4s 3d outer electronic configuration of Cu arrangement is more stable than 4s 3d because of:
(A) exchange energy (B) pairing energy
(C) symmetrical charge distribution (D) all
+
4. The spin only magnetic moment of Cr is:
(A) 5.93 BM (B) 4.61 BM (C) 3.92 BM (D) 2.68 BM

CMP: The letters n,  , m proposed by Bohr, Sommerfeld and Zeeman respectively for quantization of
angular momentum in classical physics were later on obtained as the results of solution of
Schrödinger wave equation on quantum mechanics. The term n,  , m were named as principal
quantum number, azimuthal quantum number and magnetic quantum number respectively. The
fourth quantum number s was given by uhlenback the name spin quantum number on the basis of
two spins of electrons. The first two quantum numbers value  4, 3, 0 denotes:
5. The numerical value 4, 3, 0 denotes:
(A) 3d-orbital (B) 4f-orbital (C) 2s-orbital (D) 4d-orbital

 h 
6. The angular momentum of 3p-orbitals in terms of     is:
 2 
 
(A) 2 (B) 2 (C) (D)
2 2
7. Number of radial and angular nodes in 3p-orbitals respectively are:
(A) 1, 1 (B) 2, 1 (C) 1, 2 (D) 2, 2

8. Which statement about energy level in H-atom is correct?

(A) Only n and  decides energy level (B) Only ‘  ’ decides energy level
(C) Only n decides energy level (D) n,  and m decides energy level
9. The quantum numbers of +1/2 and –1/2 for the electron spin represents:
(A) rotation of electron in clockwise and anticlockwise direction respectively
(B) rotation of electron in anticlockwise and clockwise direction respectively
(C) two quantum mechanical states having classical analogue
(D) Two quantum mechanical states having no classical analogue
40 – ATOMIC STRUCTURE – JEE
CMP: The concept of atomic orbitals, i.e., wave function () of electrons in atom was chosen to suggest
something less definite than an orbit of an electron around a nucleus to take an account of the
wave function of the electron. The square of a wave function tells us the probability density of
electron at each point. The atomic orbitals are described by the location of each point around a
nucleus in terms of spherical polar co-ordinates.
(a) r, the distance from the centre of atom,
(b) , the angle from the positive Z-axis, (the north pole); which can be thought of as playing
the role of lattitude; and
(c) , the angle about the Z-axis, the longitude.
The wave function of an orbital is thus a product R (r) the radial wave function and Y (, ) the
angular wave function.
Thus,  (r, , ) = R(r). Y (, )
The radial wave function and angular wave function for H-atom for different values of n,  , m are
given below:
n  Rn (r)  m  m ( , )
2 r / a0 1
1 0 e 0 0
a0 3 / 2 4
1  r  r /2a0 3
2 0 2  e 1 X .sin .cos 
8 a0 3/ 2
 a0  4
1  r  r / 2a0 3
1  e 1 Y .sin .sin 
 a0 
3/2
24 a0 4
3
.cos 
1 Z
4
In all cases except m = 0, the orbitals are sums and difference of orbitals with specific values of m .
10. The probability of finding the electron in a small region at a distance r = 2a0 from the nucleus relative to the
probability of finding it in the same small region located right at the nucleus is:
(A) 1.8% (B) 98.2% (C) 14% (D) 86%

11. The radial wave function R(r) and angular wave function for ground state of H-atom respectively are:
2e r0 /a0  2e r0 / a0 1 2e r0 /a0 1 2e r0 /a0
(A) , (B) , (C) 0, (D) ,
3 a
0
2 3 a
0 2  3 a
0 2  3 a
0

-13.6z 2
CMP: Electronic energy of hydrogen like atom in to ground state is given as ev, by Bohr’s theory.
n2
However this theory is not directly applicable to multielectron atoms like He, Li, Be, O etc, due to
inter electronic repulsion. These atom are studied by help of quantum mechanics. Quantum
mechanics deals with probabilistic interpretation of electron by a wave function  and its square
2
modules  , a mathematical expression of probability of finding a electron at all points in space.
Quantum mechanics tells us the exact probability of finding an electron at any two unrelated
points, however it does not tell us how electron moves from one place to another therefore concept
of Bohr orbit is lost. It is replaced by description of where electron is most likely to be found. A
collection of point where there is probability of finding an electron is called orbital. Each orbital is
classified as their values of ‘n’, ‘l’ and ‘m’. Wave function () of orbitals are divided into two parts
radial and angular like (1s) for hydrogen atom
1/2 3 /2
 1   2  -2zr
(s) =   R(1s) = 2   e
 4π  a
 0 na0
Here (s) = angular part of 1s orbital, R(1s) = radial part of 1s orbital
If we multiply radial and angular part of  with each other we get the
1/2 3/2 -2zr
 1   2 
(1s) =   2  e na0 ; a0 = 0.529 Å (Bohr’s radius), z = atomic no.
 4π   a0 
12. In an electron moving along x–axis only has wave function (x) = A sin2x for 0  x  1, what is the
probability distribution graph of electron along x–axis is:

Probability
Probability
Probability 1 Probability 1 O
O O 0.25 0.5 0.75 1
O 0.5 0.5
x -axis 1 x -axis
x -axis x -axis

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

13. The nature of radial probability D(r) = 4r2 R2(r) for three hydrogenic atomic orbital as follows:

Identify the corresponding atomic orbitals (choose your answer from (1s, 2s, 3s, 3p, 3d, 4s)
(A) I  1s, 2s (B) I  1s
II  3s, 3p II  2s, 3p
III  4s III  3s, 3d
(C) I  1s (D) I  1s
II  3s II  3s
III  2s, 3p, 4s III  2s, 3p

CMP: It is not possible to determine precisely both the position and the momentum (or velocity) of a
small moving particle (e.g., electron, proton etc.)

14. If uncertainties in the measurement of position and momentum of an electron are equal, then uncertainty in
the measurement of its velocity is approximately:
(A) 8.0  1012 ms–1 (B) 6.0  1012 ms–1
12 –1
(C) 4.0  10 ms (D) 2.0  1012 ms–1
–1 –1
15. If a 1.00 g body is travelling along the x-axis at 100 cms within 1 cm s , then uncertainty in its position is:
–30 –30
(A) 5.28  10 m (B) 2.64  10 m
–30 –30
(C) 1.32  10 m (D) 0.66  10 m

CMP: In the quantum mechanics there is operator ( A  ) for every physically observable property like
momentum (linear or angular), position, K.F., total energy etc., and whenever the function () is
operated upon by the operator of any property, we get back  multiplied by a constant (a) which is
the value of the property under consideration. The function  obeying the condition is called
 and the constant "a" is called eigen-value. Mathematically
eigenfunction of the operator A
  = a.
A
This equation is called eigen-value equation.
The Schrodinger wave equation is the energy eigen value equation. The operator for total energy is
called Hamiltonion operator (H) defined as
h2   2 2 2 
H  2  2  2  2 V
8  m  x y z 
Where V = PE, m = mass of microparticle.
Solving Schrodinger wave equation for H-atom after putting proper value of V, we get wave functions
2
() and corresponding energy values. Each wave function denotes an orbital.  measures the
2
probability of finding the electron and  dx gives the probability of finding the electron in the region
2 2
x and x + dx. 4r  (r)dr gives the probability of finding the electron in spherical shell of thickness
2 2
dr at a distance r from the nucleus. A plot of radial distribution function [4r  (r)] vs distance from
the nucleus (r) gives the radial probability distribution curve of electron. For 1s and 2s orbitals each
containing only one electron, these curves are as given below
42 – ATOMIC STRUCTURE – JEE

4r 2  2 r  4r 2  2  r 

The wave functions of 1s and 2s orbitals of hydrogenic atom or ion are given below:
1/ 2
 Z
1s  2   e Zr / a0
 a0 
1/2
 Z   Zr   Zr /a0
 2s    2  e
2a
 0  a0 

In 2s-orbital there occurs a point at the radius at which curve touches X-axis. Here the probability
of finding the electron is zero. This is called radial node.
16. An electron is moving along X-axis in absence of any external field. The energy eigen-value of electron
–5ix
with  = e , is:
25 h2 3 h2 h2 h2
(A) (B) (C) (D)
8 2m 8 2 m 8 2 m 4 2 m

17. The de-Broglie's wavelength of the electron as described in the previous question mentioned above is:
2 5 2h 5h
(A) (B) (C) (D)
5 2 5 2

2+
CMP: The hydrogen-like species Li 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.
18. Equation(s) related to above statement is/are:
h h
(A) x.p  (B) x.v 
2 2m
h
(C) E.t  (D) All of these
2

19. 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
20. The orbital angular momentum quantum number of the state S2 is:
(A) 0 (B) 1 (C) 2 (D) 3

Match The Column

21. Match the Column
Column I Column II
(A) K.E. (P) 2
P.E.
(B) P. E. + 2 K.E. (Q) 1

2
(C) P.E. (R) –1
T.E.
(D) K.E. (S) 0
T.E.
22. Match the columns A and B
Column I Column II
4s 3d
(A) (P) 2s

2
4r 2 
(B) (Q) 1s

(C) Number of waves in Bohr’s second orbit (R) Violation of Aufbau principle
(D) Potential energy of electron in first excited state (S) Violation of Pauli’s exclusion principle
2+
of Li
(T) –12.6ev
(U) –25.2 ev
(V) 2

23. If in Bohr's model, for unielectronic atom following symbols are used
th
rn, z  Radius of n orbit with atomic number Z;
– –
Un, z  Potential energy of e ; Kn, 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, 3 : V3, 1 (R) 1:1
(D) T1, 2 : T2, 2 (S) 8:1

24. Match the Column

Column I Column II


(A) R3s (P)


(B) R2s (Q)


(C) R2p (R)


(D) R3p (S)
r
44 – ATOMIC STRUCTURE – JEE
25. Match the Column
Column I Column II

(A) (P) 4s

4r 2R2
(B) (Q) 5py

(C) Angular probability is dependent of  and  (R) 3s

(D) Atleast one angular node is present (S) 6dxy

20. Level – 5 (Single Integer Subjective Type)

h
1. The magnitude of an orbital angular momentum vector of an electron is 6 . Into how many
2
components will be vector split if an external field is applied to it?

2. A certain transition in H spectrum from an excited state to ground state in one or more steps gives rise to
total 10 lines. How many of these belong to UV spectrum?
3. How many of the following ions have the same magnetic moments?
2+ 2+ 2+ 2+
Fe , Mn , Cr , Ni
4. The uncertainty in the position of an electron is equal to its de Broglie wavelength. The minimum percent
error in its measurement of velocity under this circumstance will be approximately.
5. If each hydrogen atom in the ground state, 1.0 mol of H atoms are excited by absorbing photons of energy
8.4 eV, 12.09 eV, and 15.0 eV of energy, then the number of spectral lines emitted is equal to.
6. The number of total radial nodes in 3p orbital are:
7. The number of spectral lines obtained in Bohr spectrum of hydrogen atom when an electron is excited from
ground level to 4th orbit is:
35 37
8. By what times should 17C be abundant in nature to 17Cl so that the average atomic mass of Cl is 35.5?
9. The ratio of potential energy and total energy of an electron in a Bohr orbit of a hydrogen-like species is:
16
10. A certain metal when irradiated to light (v = 3.2  10 Hz) emits photoelectrons with twice kinetic energy
16
as did photoelectrons when the same metal is irradiated by light (v = 2.0  10 Hz). If threshold frequency
15
of the metal is expressed as x  10 then value of x is:

11. At 200C, hydrogen molecules have velocity 2.4  105 cm s–1. The de Broglie wavelength in this case is
approximately (in Å):

12. Determine the de-Broglie wavelength (in Å) associated with an electron in the 3rd Bohr's orbit of He + ion.

13. Which line of Paschen series of Li2+ ion would have same wavelength as 3rd transition in Lyman series of
H-atom?
1 r

 

14. The normalized wave function of the hydrogen atom for the 1s orbital is 1s  a03 2
e a0
. If in such a
state the most probable distance from nucleus to electron is a 0, then the ratio of r/a0 is:

15. The radial wave equation for hydrogen atom is:

 3/2
1  1

16 4  a0  

   x  1 x  8x  12  e
2

 x/ 2

2r
Where x = ; a0 = Radius of first Bohr’s orbit.
a0
Then number of radial nodes will be:

21. Level – 6 (Previous Years Main & Advanced)

JEE-Main
1. The number of nodal planes in a p x orbital is: [IIT 2000]
(A) One (B) Two (C) Three (D) Zero

2. The electronic configuration of an element is 1s2 2s2 2p6 3s2 3p6 3d5 4s1 . This represents its [IIT 2000]
(A) Excited state (B) Ground state (C) Cationic form (D) Anionic form
nd
3. In a hydrogen atom, if energy of an electron in ground state is 13.6 eV, then that in the 2 excited state is:
[AIEEE 2002]
(A) – 1.51 eV (B) – 3.4 eV (C) – 6.04 eV (D) – 13.6 eV

4. Uncertainty in position of a 0.25 g particle is 10 5 m . Uncertainty of velocity is ( h  6.6  10 34 J  s)

[AIEEE 2002]
(A) 1.2  1034 (B) 2.1 10 26
(C) 1.6  10 20 (D) 1.7  109

5. Which has the maximum magnetic moment? [AIEEE 2002]

2+ 2+ 2+ 2+
(A) Mn (B) Fe (C) Ti (D) Cr

6. The orbital angular momentum of an electron in 2s orbital is: [AIEEE 2003]

1 h h h
(A)  . (B) (C) 2. (D) None
2 2 2 2

7. Which one of the following grouping represents a collection of iso-electronic species? [AIEEE 2003]
(A) Na ,Ca2  ,Mg2 (B) N3  ,F  ,Na 
(C) Be,Al3  ,Cl (D) Ca 2  ,Cs  ,Br

9. The number of d-electrons retained in Fe2+ ion is: [AIEEE 2003]

(A) 5 (B) 6 (C) 3 (D) 4

10. Which set is correct for an electron in 4f-orbital? [AIEEE 2004]

(A) n=3  = 2 m = –2 ms = +1/2
(B) n=4  = 4 m = –4 ms = –1/2
(C) n=4  =3 m = +1 ms = +1/2
(D) n=4  =3 m = +4 ms = +1/2

11. The number of electrons with the azimuthal quantum number  = 1 and  = 2 in ground state of 24Cr is
respectively: [AIEEE 2004]
(A) 16 and 5 (B) 12 and 5
(C) 16 and 4 (D) 12 and 4

12. Of the following outer electronic configurations of atoms, the highest oxidation state is achieved by which
one of them: [AIEEE 2004]
(A) (n – 1) d5ns2 (B) (n – 1) d5ns1
3 2 8 2
(C) (n – 1) d ns (D) (n – 1) d ns
46 – ATOMIC STRUCTURE – JEE
13. In a multi-electron atom, which of the following orbital described by the three quantum numbers will have
the same energy in the absence of magnetic field? [AIEEE 2005]
(i) n = 1,  = 0, m = 0 (ii) n = 2,  = 0, m = 0
(iii) n = 2,  = 1, m = 1 (iv) n = 3,  = 2, m = 1
(v) n = 3,  = 2, m = 0
(A) (i) and (ii) (B) (ii) and (iii) (C) (iii) and (v) (D) (iv) and (v)

14. Which of the following statement is correct in relation to the hydrogen atom? [AIEEE 2005]
(A) 3s-orbital is lower in energy than 3p-orbital
(B) 3p-orbital is lower in energy than 3d-orbital
(C) 3s and 3p-orbitals are of lower energy than 3d-oritals
(D) 3s, 3p and 3d-orbitals all have the same energy

15. Which one of the following sets of ions represents a collection of isoelectronic species?
[AIEEE 2006]
+ + 2+ 2+ + – 2+ 3+
(A) Li , Na , Mg , Ca (B) K , Cl , Ca , Sc
2+ 2+ + 2+ 3– 2– – 2–
(C) Ba , Sr , K , Ca (D) N ,O ,F ,S

16. The ionization enthalpy of hydrogen atom is 1.312  106 J mol–1. The energy required to excite the electron
in the atom from n = 1 to n = 2 is: [AIEEE 2008]
5 –1 5 –1
(A) 8.51  10 J mol (B) 6.56  10 J mol
5 –1 5 –1
(C) 7.56  10 J mol (D) 9.84  10 J mol

17. Calculate the wavelength (in nanometer) 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): [AIEEE 2009]
(A) 0.032 nm (B) 0.40 nm
(C) 2.5 nm (D) 14.0 nm

18. In an atom, en electron is moving with a speed of 600 m/s with an accuracy of 0.005%. Certainity with
–34 2 –1
which the position of the electron can be located is (h = 6.6  10 kg m s ,
–31
mass of electron, em = 9.1  10 kg): [AIEEE 2009]
(A) 1.52  10–4 m (B) 5.10  10–3 m (C) 1.92  10–3 m (D) 3.84  10–3 m
+ –18 –1 2+
19. Ionization energy of He is 19.6  10 J atom . The energy of the first stationary state (n = 1) of Li is:
[AIEEE 2010]
15 –1 –17 –1
(A) – 2.2  10– J atom (B) 8.82  10 J atom
(C) 4.41  10–16 J atom–1 (D) – 4.41  10–17 J atom–1
–1
20. The energy required to break one mole of Cl – Cl bonds in Cl2 is 242 kJ mol . The longest wavelength of
light capable of breaking a single Cl – Cl bond is: [AIEEE 2010]
(c = 3  108 ms–1 and NA = 6.02  1023 mol–1)
(A) 700 nm (B) 494 nm
(C) 594 nm (D) 640 nm

21. A gas absorbs a photon of 355 nm and emits at two wavelengths. If one of the emissions is at 680 nm, the
other is at: [AIEEE 2011]
(A) 325 nm (B) 743 nm
(C) 518 nm (D) 1035 nm

22. The electrons identified by quantum numbers n and I: [AIEEE 2012]

(a) n = 4,  = 1 (b) n = 4,  = 0 (c) n = 3,  = 2 (d) n = 3,  = 1
Arrange them in increasing sequence of energy
(A) (b) < (d) < (a) < (c) (B) (a) < (c) < (b) < (d)
(C) (c) < (d) < (b) < (a) (D) (d) < (b) < (c) < (a)

23. The increasing order of the ionic radii of the given isoelectronic species is: [AIEEE 2012]
(A) Ca2  , K  , Cl , S2  (B) K  , S2  , Ca2  , Cl
(C) Cl , Ca2  , K  , S2  (D) S2  , Cl , Ca2  , K 
24. Energy of an electron is given by
–18  Z2 
E = –2.178  10 J  2 
n 
Wavelength of light required to excite an electron in an hydrogen atom from level n = 1 to n = 2 will be
–34 8 –1
(h = 6.62  10 J s and c = 3.0  10 m s ) [JEE-Main 2013]
–7 –7
(A) 8.500  10 m (B) 1.214  10 m
–7 –7
(C) 2.816  10 m (D) 6.500  10 m

25. The correct set of four quantum numbers for the valence electrons of rubidium atom (Z = 37) is:[JEE-Main 2014]
1 1
(A) 5, 0, 1, + (B) 5, 0, 0, +
2 2
1 1
(C) 5, 1, 0, + (D) 5, 1, 1, +
2 2

26. Which of the following is the energy of a possible excited sate of hydrogen? [JEE-Main_Offline 2015]
(A) –3.4 eV (B) +6.8 eV
(C) +13.6 eV (D) –6.8 V

27. If the principal quantum number n = 6, the correct sequence of filling of electrons will be
(A) ns  np  (n – 1)d  (n – 2)f (B) ns  (n – 2)f  (n–1)d  np
(C) ns  (n – 1)d  (n – 2)f  np (D) ns  np  (n – 1)d [JEE-Main_Online 2015]

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

29. The total number of orbitals associated with the principal quantum number 5 is:
(A) 20 (B) 25 [JEE-Main_Online 2016]
(C) 10 (D) 5
–34
30. The radius of the second Bohr orbit for hydrogen atom is (Planck's constant (h) = 6.6262  10 J s:
–31
mass of electron = 9.1091  10 kg;
charge of electron = 1.60210  10–19 C;
permittivity of vacuum (0 = 8.854185  10–12 kg–1 m–3 A2) [JEE-Main_Offline 2017]
(A) 0.529 Å (B) 2.12 Å
(C) 1.65 Å (D) 4.76 Å

31. If the shortest wavelength in Lyman series of hydrogen atom is A, then the longest wavelength in Paschen
series of He+ is: [JEE-Main_Offline 2017]
5A 36A
(A) (B)
9 5
36A 9A
(C) (D)
7 5

32. The electron in the hydrogen atom undergoes transition from higher orbitals to orbital of radius 211.6 pm.
This transition is associated with [JEE-Main_Online 2017]
(A) Paschen series (B) Brackett series
(C) Lyman series (D) Balmer series
48 – ATOMIC STRUCTURE – JEE
JEE Advance
Single Choice
33. The kinetic energy of an electron in the second Bohr orbit of a hydrogen atom [a0 is Bohr radius]
[JEE-Advance_ 2012]
2 2 2
h h h h2
(A) (B) (C) (D)
42ma20 162ma02 322ma20 642ma02

34. P is the probability of finding the 1s electron of hydrogen atom in a spherical shell of infinitesimal thickness,
2
dr, at a distance r from the nucleus. The volume of this shell is 4 dr. The qualitative sketch of the
dependence of P on r is: [JEE-Advance_ 2016]

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

Single Integer
35. The maximum number of electrons that can have principal quantum number, n = 3, and spin quantum
1
number, ms =  , is: [JEE-Advance_ 2011]
2

36. The work function () of some metals is listed below. The number of metals which will show photoelectric
effect when light of 300 nm wavelength falls on the metal is: [JEE-Advance_ 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

37. The atomic masses of He and Ne are 4 and 20 amu, respectively. The value of the de-Broglie wavelength of He
gas at –73C is M times that of the de Broglie wavelength of Ne at 727C. M is: [JEE-Advance_ 2013]

38. In an atom, the total number of electrons having quantum numbers, n = 4, m  1 and ms = –1/2 is
[JEE-Advance_ 2014]

39. Not considering the electronic spin, the degeneracy of the second excited state (n = 3) of H atom is 9,
–
while the degeneracy of the second excited state of H is: [JEE-Advance_ 2015]

Match The Column

Answer Q.40, Q.41 and Q.42 by appropriately matching the information given in the three columns of the following
table.
The wave function, n,,m is a mathematical function whose value depends upon spherical polar coordinates (r, , ) of
the electron and characterized by the quantum numbers n,  and m . Here r is distance from nucleus,  is colatitude
and  is azimuth. In the mathematical functions given in the table, Z is atomic number and ao si Bohr radius.
Column 1 Column 2 Column 3
(I) 1s orbital 3
 Zr 
 Z  2   
(i) n,,m    e  ao 
 ao 
 n,,m (r)

(P)

0 r/a0

(II) 2s orbital (ii) One radial node 1

(Q) Probability density at nucleus 
a3o
(III) 2pz orbital 5
 Zr  (R) Probability density is maximum at
 Z  2    nucleus
(iii) n,,m    re  2ao  cos 
 ao 
(IV) 3d2z orbital (iv) xy-plane is a nodal plane (S) Energy needed to excite electron from
27
n = 2 state to n = 4 state is times the
32
energy needed to excite electron from n =
2 state to n = 6 state
[JEE-Advance_ 2017]
+
40. For He ion, the only INCORRECT combination is:
(A) (I) (iii) (R) (B) (II) (ii) (Q)
(C) (I) (i) (R) (D) (I) (i) (S)

41. For hydrogen atom, the only CORRECT combination is:

(A) (II) (i) (Q) (B) (I) (i) (P)
(C) (I) (iv) (R) (D) (I) (i) (S)

42. For the given orbital in Column 1, the only CORRECT combination for any hydrogen-like species is:
(A) (I) (ii) (S) (B) (IV) (iv) (R)
(C) (II) (ii) (P) (D) (III) (iii) (P)

22. Level – 7 (NCERT Corner)

1. Calculate the total number of electrons present in one mole of methane.

2. How many neutrons and protons are there in the following nuclei?
13 16 24 56 88
6 C, 8 O, 12 Mg, 26Fe, 38 Sr

–10
3. Calculate the wavelength, frequency and wave number of a light wave whose period is 2.0  10 s.

4. A photon of wavelength 4  10–7 m strikes on metal surface, the work function of the metal being 2.13 eV.
Calculate
(i) the energy of the photon (eV),
(ii) the kinetic energy of the emission, and
–19
(iii) the velocity of the photoelectron (1 eV= 1.6020  10 J).

5. A 25 watt bulb emits monochromatic yellow light of wavelength of 0.57m. Calculate the rate of emission
of quanta per second.

6. Electrons are emitted with zero velocity from a metal surface when it is exposed to radiation of wavelength
6800 Å. Calculate threshold frequency (v0) and work function (W 0) of the metal.

7. How much energy is required to ionise a H atom if the electron occupies n = 5 orbit? Compare your answer
with the ionization enthalpy of H atom (energy required to remove the electron from n =1 orbit).

8. What is the maximum number of emission lines when the excited electron of an H atom in n = 6 drops to
the ground state?
–18 –1
9. (i) The energy associated with the first orbit in the hydrogen atom is –2.18  10 J atom . What is
the energy associated with the fifth orbit?
(ii) Calculate the radius of Bohr’s fifth orbit for hydrogen atom.

10. Calculate the wave number for the longest wavelength transition in the Balmer series of atomic hydrogen.
–18 2
11. The electron energy in hydrogen atom is given by En = (–2.18  10 )/n J. Calculate the energy required
to remove an electron completely from the n = 2 orbit. What is the longest wavelength of light in cm that
can be used to cause this transition?
–31 –25
12. The mass of an electron is 9.1  10 kg. If its K.E. is 3.0  10 J, calculate its wavelength.
13. What is the lowest value of n that allows g orbitals to exist?
50 – ATOMIC STRUCTURE – JEE
14. An atom of an element contains 29 electrons and 35 neutrons. Deduce
(i) the number of protons and
(ii) the electronic configuration of the element.

15. How many electrons in an atom may have the following quantum numbers?
1
(a) n = 4, ms   (b) n = 3,  = 0
2

16. Show that the circumference of the Bohr orbit for the hydrogen atom is an integral multiple of the de
Broglie wavelength associated with the electron revolving around the orbit.

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

18. Calculate the energy required for the process

He   g  He2   g  e
–18 –1
The ionization energy for the H atom in the ground state is 2.18 ×10 J atom

19. If the diameter of a carbon atom is 0.15 nm, calculate the number of carbon atoms which can be placed
side by side in a straight line across length of scale of length 20 cm long.

20. In Milikan’s experiment, static electric charge on the oil drops has been obtained by shining X-rays. If the
–18
static electric charge on the oil drop is –1.282  10 C, calculate the number of electrons present on it.

21. In Rutherford’s experiment, generally the thin foil of heavy atoms, like gold, platinum etc. have been used
to be bombarded by the -particles. If the thin foil of light atoms like Aluminium etc. is used, what
difference would be observed from the above results?

22. An element with mass number 81 contains 31.7% more neutrons as compared to protons. Assign the
atomic symbol.

23. An ion with mass number 37 possesses one unit of negative charge. If the ion contains 11.1% more
neutrons than the electrons, find the symbol of the ion.

24. Nitrogen laser produces a radiation at a wavelength of 337.1 nm. If the number of photons emitted is 5.6 
1024, calculate the power of this laser.

25. In astronomical observations, signals observed from the distant stars are generally weak. If the photon
detector receives a total of 3.15  10–18 J from the radiations of 600 nm, calculate the number of photons
received by the detector.

26. Lifetimes of the molecules in the excited states are often measured by using pulsed radiation source of
duration nearly in the nano second range. If the radiation source has the duration of 2 ns and the number
15
of photons emitted during the pulse source is 2.5  10 , calculate the energy of the source.
27. The work function for caesium atom is 1.9 eV. Calculate (a) the threshold wavelength and (b) the threshold
frequency of the radiation. If the caesium element is irradiated with a wavelength 500 nm, calculate the
kinetic energy and the velocity of the ejected photoelectron.
28. Following results are observed when sodium metal is irradiated with different wavelengths.
Calculate (a) threshold wavelength and, (b) Plank's constant.
 (nm) 500 450 400
–5 –1
v  10 (cm s ) 2.55 4.35 5.35

29. The ejection of the photoelectron from the silver metal in the photoelectric effect experiment can be
stopped by applying the voltage of 0.35 V when the radiation 256.7 nm is used. Calculate the work function
for silver metal.
30. If the photon of the wavelength 150 pm strikes an atom and one of its inner bound electrons is ejected out
7 –1
with a velocity of 1.5  10 ms , calculate the energy with which it is bound to the nucleus.
31. Calculate the wavelength for the emission transition if it starts from the orbit having radius 1.3225 nm and
ends at 211.6 pm. Name the series to which this transition belongs and the region of the spectrum.

32. Similar to electron diffraction, neutron diffraction microscope is also used for the determination of the
structure of molecules. If the wavelength used here is 800 pm, calculate the characteristic velocity
associated with the neutron.
6 –1
33. If the velocity of the electron in Bohr’s first orbit is 2.19  10 ms , calculate the de Broglie wavelength
associated with it.

34. If the position of the electron is measured within an accuracy of + 0.002 nm, calculate the uncertainty in the
momentum of the electron. Suppose the momentum of the electron is h/4 m  0.05 nm, is there any
problem in defining this value.

35. The quantum numbers of six electrons are given below. Arrange them in order of increasing energies. If
any of these combination(s) has/have the same energy lists:
1. n = 4,  = 2, m = –2 , ms = –1/2
2. n = 3,  = 2, m = 1 , ms = +1/2
3. n = 4,  = 1, m = 0 , ms = +1/2
4. n = 3,  = 2, m = –2 , ms = –1/2
5. n = 3,  = 1, m = –1 , ms= +1/2
6. n = 4,  = 1, m = 0 , ms = +1/2

36. Among the following pairs of orbitals which orbital will experience the larger effective nuclear charge?
(i) 2s and 3s, (ii) 4d and 4f, (iii) 3d and 3p

37. Indicate the number of unpaired electrons in:

(a) P, (b) Si, (c) Cr, (d) Fe and (e) Kr.
52 – ATOMIC STRUCTURE – JEE

23. Answer Sheet

Quiz - 1
1 2 3 4 5 6 7 8 9 10

D A A D C B D A B B

Quiz - 2
1 2 3 4 5 6 7 8 9 10

B B A C C A C C B B

11 12 13 14 15

A B D C B

Quiz - 3
1 2 3 4 5 6 7 8 9 10

C B C C B D B D C A

11 12 13 14 15

C B C A C

Quiz - 4
1 2 3 4 5 6 7 8 9 10

A A B B D C C A A A

Quiz - 5
1 2 3 4 5 6 7 8 9 10

B C A B B D C D C A

11 12 13 14 15

A A D C A

Level – 1 (Main)
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15

C A A D C B B C A A A B A A C

16 17 18 19 20 21 22 23 24 25 26 27 28 29 30

A A A D A A C B C D A A C D D

Level – 2 (Main)
 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15

C B D A D A B D B A C B A D D

16 17 18 19 20 21 22 23 24 25 26 27 28 29 30

C A B B D A D A D B C D D B D

Level – 3 (Advanced)
1 2 3 4 5 6 7 8 9 10

A A A A B B B C D C

11 12 13 14 15 16 17 18 19 20

C C B C D A B B B C

21 22 23 24 25 26 27 28 29 30

B A C C B ABC ACD ABC BCD ABCD

31 32 33 34 35 36 37 38 39 40

ABCD BCD AC ABCD ABD ABCD AB ABC ABCD BCD

Level – 4 (Comprehension & Match the Column)

1 2 3 4 5 6 7 8 9 10

C D C A B A A C D A

11 12 13 14 15 16 17 18 19 20

B C D A B A A D C B

21. A–Q, B–S, C–P, D–R 22. A–R, B–Q, C–V, D–U
23. A–Q, B–S, C–R, D–P 24. A–P, B–S, C–Q, D–R 25. A–P, B–PQS, C–QS, D–QS

Level – 5 (Single Integer Subjective Type)

1 2 3 4 5 6 7 8 9 10

5 4 2 8 3 1 6 3 2 8

11 12 13 14 15

1 5 9 1 3
54 – ATOMIC STRUCTURE – JEE

Level – 6 (Previous Years Main & Advanced)

1 2 3 4 5 6 7 8 9 10

A B A B A D B B B B

11 12 13 14 15 16 17 18 19 20

A D D B D B D B B B

21 22 23 24 25 26 27 28 29 30

D A B B A B D B B C

31 32 33 34 35 36 37 38 39 40

D C D 9 4 5 6 3 A D

41

Level – 7 (NCERT Corner)

1. Number of electrons present in 1 molecule of methane (CH4)
{1(6) + 4(1)} = 10
Number of electrons present in 1 mole i.e., 6.023  1023 molecules of methane
= 6.022  1023  10 = 6.022  1024

13
2. 6 C
Atomic mass = 13
Atomic number = Number of protons = 6
Number of neutrons = (Atomic mass) – (Atomic number)
= 13 – 6 = 7
16
8 O
Atomic mass = 16
Atomic number = 8
Number of protons = 8
Number of neutrons = (Atomic mass) – (Atomic number)
= 16 – 8 = 8
24
12Mg
Atomic mass = 24
Atomic number = Number of protons = 12
Number of neutrons = (Atomic mass) – (Atomic number)
= 24 – 12 = 12
56
26Fe
Atomic mass = 56
Atomic number = Number of protons = 26
Number of neutrons = (Atomic mass) – (Atomic number)
= 56 – 26 = 30
88
38Sr
Atomic mass = 88
Atomic number = Number of protons = 38
Number of neutrons = (Atomic mass) – (Atomic number)
= 88 – 38 = 50
1
3. Frequency (ν) of light =
Period
 1
=  5.0  109 s1
2.0  1010 s
c
Wavelength () of light =
v
Where,
8
c = velocity of light in vacuum = 3  10 m/s
Substituting the value in the given expression of  :
3  108
  6.0  102 m
5.0  109
1 1
Wave number ( v ) of light =   1.66  101m1  16.66 m
 6.0  10 2
hc
4. (i) Energy (E) of a photon = hν =

Where, h = Planck’s constant = 6.626  10–34 Js
c = velocity of light in vacuum = 3  108 m/s
 = wavelength of photon = 4  10–7 m
Substituting the values in the given expression of E:

E
 
6.626  10 34 3  108 
 4.9695  10 19 J
4  10 7
Hence, the energy of the photon is 4.97  10–19 J.

(ii) The kinetic energy of emission Ek is given by

= hv = hv0
= (E – W)eV
 4.9695  10 19 
=  19 
eV  2.13 eV
 1.6020  10 
= (3.1020 – 2.13) eV
= 0.9720 eV
Hence, the kinetic energy of emission is 0.97 eV.
(iii) The velocity of a photoelectron (ν) can be calculated by the expression,
1
mv 2  hv  hv 0
2
2 hv  hv 0 
 v
m
Where  hv  hv 0  is the kinetic energy of emission in Joules and 'm' is the mass of the
photoelectron. Substituting the values in the given expression of v:

v

2  0.9720  1.6020  10 19 J 
31
9.10939  10 kg
2 2
=  0.3418  10 m s 12

v = 5.84  105 ms–1

Hence, the velocity of the photoelectron is 5.84  105 ms–1.

5. Power of bulb, P = 25 Watt = 25 Js–1

hc
Energy of one photon, E = hν =

Substituting the values in the given expression of E:

E
 
6.626  10 34 3  108 
 34.87  10 20 J

0.57  10 6 
–20
E = 34.87  10 J
Rate of emission of quanta per second
25
  7.169  1019 s1
34.87  10 20
56 – ATOMIC STRUCTURE – JEE
–10
6. Threshold wavelength of radiation (0) = 6800Å = 6800  10 m
Threshold frequency (v0) of the metal
c 3  108 ms 1 14 –1
=  = 4.41  10 s
0 6.8  10 7 m
Thus, the threshold frequency (v0) of the metal is 4.41  1014 s–1.
Hence, work function (W 0) of the metal = hν0
–34 14 –1 –19
= (6.626  10 Js) (4.41  10 s ) = 2.922  10 J
7. The expression of energy is given by,

En 
 
 2.18  10 18 Z 2
n2
Where, Z = atomic number of the atom n = principal quantum number
For ionization from n1 = 5 to n2 = ,
E = E – E5
   
   2.18  10 18 J 12    2.18  10 18 J 12  
 
   
 
  5  
2 2

  

 1   1 
 
= 2.18  10 18 J  
  5 2   Since   0 
 
 
–18
= 0.0872  10 J
–20
E = 8.72  10 J
Hence, the energy required for ionization from n = 5 to n = 
–20
Energy required for n1 = 1 to n = , is 8.72  10 J.
E '  E  Ei

   
   2.18  10 18 J 12    2.18  10 18 J 12 
= 
   
 
    
2 2
   1

–18
= (2.18  10 ) [1 – 0]
–18
= 2.18  10 J
Hence, less energy is required to ionize an electron in the 5th orbital of hydrogen atom as compared to that
in the ground state.
8. When the excited electron of an H atom in n = 6 drops to the ground state, the following transitions are
possible:
n
Energy

Hence, a total number of (5 + 4 + 3 + 2 + 1) 15 lines will be obtained in the emission spectrum.

The number of spectral lines produced when an electron in the nth level drops down to the ground state is
n  n  1
given by .
2
Given, n = 6
 6  6  1
Number of spectral lines = = 15
2

9. (i) Energy associated with the fifth orbit of hydrogen atom is calculated as:

E5 

 2.18  10 18


2.18  10 18
5
2
25
–20
E5 = –8.72  10 J
(ii) Radius of Bohr’s nth orbit for hydrogen atom is given by, rn = (0.0529 nm) n2
For, n = 5
2
r5 = (0.0529 nm) (5)
r5 = 1.3225 nm

10. For the

Balmer series, ni = 2. Thus, the expression of wavenumber (v) is given by,
 1 1

v   2  2  1.097  107 m1
  2  nf 


Wave number ( v ) is inversely proportional to wavelength of transition. Hence, for the longest wavelength
transition, ( v ) has to be the smallest.
For ( v ) to be minimum, nf should be minimum.
For the Balmer series, a transition from ni = 2 to nf = 3 is allowed.
Hence, taking nf = 3, we get:
1 1

v  1.097  107  2  2 
 2 3 

7 1 1

v  1.097  10   
4 9

94 7  5 

= 1.097  107  
 36 

 = 1.097  10  36 
 

v  1.5236  106 m1

11. Given,
2.18  10 18
En   J
n2
Energy required for ionization from n = 2 is given by,
E = E – E2
 2.18  10 18   2.18  10 18  
=    J
   
2
 
   2 
2



 2.18  10 18  –18
=   0  J = 0.545  10 J
 4 
E = 5.45  10–19 J
hc

E
Here,  is the longest wavelength causing the transition.



6.626  10 34 3  108   –10
 3.647  10 7 m = 3647  10 m = 3647 Å
5.45  10 19

12. From de Broglie’s equation,

h

mv
Given, Kinetic energy (K.E.) of the electron = 3.0  10–25 J
1
Since K.E. = mv 2
2
58 – ATOMIC STRUCTURE – JEE
2K.E.
 Velocity (v) =
m

=

2 3.0  10 25 J 
31
9.10939  10 kg
= 6.5866  10 4

v = 811.579 ms–1
Substituting the value in the expression of :
6.626  10 34 Js –7
 or  = 8.9625  10 m
 
9.10939  10 31kg 811.579 ms 1 
–7
Hence, the wavelength of the electron is 8.9625  10 m.

13. For g-orbitals  = 4.

As for any value ‘n’ of principal quantum number, the Azimuthal quantum number (l) can have a value from
zero to (n – 1).
 For  = 4, minimum value of n = 5
14. (i) For an atom to be neutral, the number of protons is equal to the number of electrons.
 Number of protons in the atom of the given element = 29
(ii) The electronic configuration of the atom is
2 2 6 2 6 2 10
1s 2s 2p 3s 3p 4s 3d .
2
15. (a) Total number of electrons in an atom for a value of n = 2n
For n = 4,
2
Total number of electrons = 2 (4) = 32
The given element has a fully filled orbital as
1s2 2s2 2p6 3s2 3p6 4s2 3d10.
Hence, all the electrons are paired.
1
Number of electrons (having n = 4 and ms   ) = 16
2
(b) n = 3,  = 0 indicates that the electrons are present in the 3s orbital. Therefore, the number of
electrons having n = 3 and  = 0 is 2.
16. Since a hydrogen atom has only one electron, according to Bohr’s postulate, the angular momentum of
that electron is given by:
h
mvr  n …..(i)
2
Where, n = 1, 2, 3, …
According to de Broglie’s equation:
h

mv
h
or mv = …..(ii)

Substituting the value of ‘mv’ from expression (ii) in expression (i):
hr h
n
 2
or 2r = n ……(iii)
Since ‘2r’ represents the circumference of the Bohr orbit (r), it is proved by equation (iii) that the
circumference of the Bohr orbit of the hydrogen atom is an integral multiple of de Broglie’s wavelength
associated with the electron revolving around the orbit.
+
17. For He ion, the wave number ( v ) associated with the Balmer transition, n = 4 to n = 2 is given by:
1  1 1
v   RZ2  2  2 
 n
 1 n 2 

Where, n1 = 2, n2 = 4
Z = atomic number of helium
1 2 1 1
v   R  2   
  4 16 
  4  1
= 4R  
 16 
1 3R
v 
 4
4
 
3R
According to the question, the desired transition for hydrogen will have the same wavelength as that of
He+.
2  1 1  3R
 R 1  2  2  
 n1 n2  4
1 1 3
 2  2 …..(i)
 n1 n2  4
By hit and trail method, the equality given by equation (i) is true only when n1 = 1 and n2 = 2.
 The transition for n2 = 2 to n = 1 in hydrogen spectrum would have the same wavelength as Balmer
transition n = 4 to n = 2 of He+ spectrum.

18. Energy associated with hydrogen-like species is given by,

 Z2 
En  2.18  10 18  2  J
n 
For ground state of hydrogen atom,
E = E – E1
  12  
= 0   2.18  10 18  2   J

  1  
E = 2.18  10–18 J
For the given process,
He   g  He2   g  e
An electron is removed from n = 1 to n = ∞.
E = E – E1
   2  
2

= 0   2.18  10 18  2 

  1 
–18
E = 8.72  10 J
 The energy required for the process is 8.72  10–18 J

19. 1 m = 100 cm
1 cm = 10–2 m
Length of the scale = 20 cm
–2
= 20  10 m
Diameter of a carbon atom = 0.15 nm
= 0.15  10–9 m
One carbon atom occupies 0.15  10–9 m.
 Number of carbon atoms that can be placed in a straight line
20  102 m 7 9
= = 133.33  10 = 1.33  10
0.15  10 9 m
20. Charge on the oil drop = 1.282  10–18C
Charge on one electron = 1.6022  10–19C
 Number of electrons present on the oil drop
1.282  10 18 C 1
 = 0.8001  10 = 8.0
1.6022  10 19 C

21. A thin foil of lighter atoms will not give the same results as given with the foil of heavier atoms.
Lighter atoms would be able to carry very little positive charge. Hence, they will not cause enough
deflection of -particles (positively charged).
60 – ATOMIC STRUCTURE – JEE
22. Let the number of protons in the element be x.
 Number of neutrons in the element
= x + 31.7% of x
= x + 0.317 x
= 1.317 x
According to the question,
Mass number of the element = 81
 (Number of protons + number of neutrons) = 81
 x + 1.317x = 81
2.317x = 81
81
x = 34.95
2.317
 x  35
Hence, the number of protons in the element i.e., x is 35.
Since the atomic number of an atom is defined as the number of protons present in its nucleus, the atomic
number of the given element is 35.
 The atomic symbol of the element is 81
35 Br .

23. Let the number of electrons in the ion carrying a negative charge be x.
Then, Number of neutrons present
= x + 11.1% of x
= x + 0.111 x
= 1.111 x
Number of electrons in the neutral atom = (x – 1)
(When an ion carries a negative charge, it carries an extra electron)
 Number of protons in the neutral atom = x – 1
Given, Mass number of the ion = 37
 (x – 1) + 1.111x = 37
2.111x = 38 x = 18
 The symbol of the ion is 17
37
Cl .

24. Power of laser = Energy with which it emits photons

Nhc
Power = E =

Where,
N = number of photons emitted
h = Planck’s constant
c = velocity of radiation
 = wavelength of radiation
Substituting the values in the given expression of Energy (E):

E=
  
5.6  10 24 6.626  10 34 Js 3  108 ms1 

337.1 10 9 m 
7 6
= 0.3302  10 J = 3.33  10 J
6
Hence, the power of the laser is 3.33  10 J.

25. From the expression of energy of one photon (E),

hc
E

Where,  = wavelength of radiation h = Planck’s constant c = velocity of radiation
Substituting the values in the given expression of E:

E=
 
6.626  10 34 Js 3  108 ms1 
–19
= 3.313  10 J
 600  10 9 m 
Energy of one photon = 3.313 × 10–19 J
Number of photons received with 3.15  10–18 J energy
 3.15  10 18 J
= = 9.5 ≈ 10
3.313  10 19 J

26. Frequency of radiation (ν),

1
v
2.0  10 9 s
8 –1
ν = 5.0  10 s
Energy (E) of source = Nhν
Where, N = number of photons emitted, h = Planck’s constant ν = frequency of radiation
Substituting the values in the given expression of (E):
E = (2.5  1015) (6.626  10–34 Js) (5.0  108 s–1)
E = 8.282  10–10 J
Hence, the energy of the source (E) is 8.282  10–10 J.

27. It is given that the work function (W0) for caesium atom is 1.9 eV.
hc
(a) From the W0  expression, we get:
0
hc
0 
W0
Where, 0 = threshold
wavelength h = Planck’s
constant c = velocity of radiation
Substituting the values in the given expression of (0):

0 
 6.626  10 34

Js 3.0  108 ms1 
19
1.9  1.602  10 J
0 = 6.53  10–7 m
Hence, the threshold wavelength 0 is 653 nm.
(b) From the expression, W 0 = hv0, we get:
W
v0  0
h
Where, ν0 = threshold frequency, h = Planck’s constant
Substituting the values in the given expression of ν0:
1.9  1.602  10 19 J
v0 
6.626  10 34 Js
(1 eV = 1.602  10–19 J) ν0
= 4.593  1014 s–1
Hence, the threshold frequency of radiation (ν0) is 4.593  1014 s–1.
(c) According to the question:
Wavelength used in irradiation () = 500 nm
Kinetic energy = h (ν – ν0)
1 1 
= hc   
  0 
–34 8 –1     
= (6.626  10 Js) (3.0  10 ms )  0 
  0 
  653  500 10 9 m 

= 1.9878  10 26 Jm   2 
  653  500  10 m 
18

=
1.9878  10 153  10  J = 9.3149 × 10–20 J
26 9

 653  500 
Kinetic energy of the ejected photoelectron = 9.3149  10–20J
1 2 –20
Since K.E = mv = 9.3149  10 J
2
62 – ATOMIC STRUCTURE – JEE

v=

2 9.3149  10 20 J  = 2.0451 1011m2 s2
31
9.10939  10 kg
5 –1
v = 4.52  10 ms
5 –1
Hence, the velocity of the ejected photoelectron (v) is 4.52  10 ms .

28. (a) Assuming the threshold wavelength to be 0 nm (=0  10–9), the kinetic energy of the radiation is given
as:
1
h  v  v 0   mv 2
2
Three different equalities can be formed by the given value as:
1 1  1
hc     mv
2

  0  2
 1 1  1
hc 
500  10 9

  10 9
m 2
5
 2
  m 2.55  10  10 ms
1

 0 
hc  1 1 1
 
2
9     m 2.55  103 ms1 …..(i)
10 m  500  0  2
Similarly,
hc  1 1 1
 
2
9     m 3.45  103 ms1 …..(ii)
10 m  450  0  2
hc  1 1 1
 
2
    m 5.35  103 ms1 ….(iii)
10 9 m  400  0  2
Dividing equation (iii) by equation (i):
  0  400 
 
 
2
3 1
 400 0   5.35  10 ms
 0  500   
2
2.55  10 3 ms1
 
 500 0 
2
50  2000  5.35  28.6225
  
4 0  2000  2.55  6.5025
50  2000
 4.40177
4 0  2000
17.60700 – 50 = 8803.537 – 2000
6805.537
0  = 539.8 nm  540 nm
12.607
So, threshold wavelength (0) = 540 nm
Note: part (b) of the question is not done due to the incorrect values of velocity given in the question.
2
50  2000  5.35  28.6225
  
4 0  2000  2.55  6.5025
50  2000
 4.40177
4 0  2000
17.60700 – 50 = 8803.537 – 2000
6805.537
0   539.8 nm  540 nm
12.607

29. From the principle of conservation of energy, the energy of an incident photon (E) is equal to the sum of
the work function (W 0) of radiation and its kinetic energy (K.E) i.e.,
E = W 0 + K.E
 W 0 = E – K.E
hc
Energy of incident photon (E) =

Where, c = velocity of radiation, h = Planck’s constant,  = wavelength of radiation
 Substituting the values in the given expression of E:

E
 
6.626  10 34 Js 3.0  108 ms 1
=
7.744  10
–19
J =
7.744  10 19
eV
256.7  10 9 m 1.602  10 19
E = 4.83 eV
The potential applied to silver metal changes to kinetic energy (K.E) of the photoelectron.
Hence,
K.E = 0.35 V
K.E = 0.35 eV
 Work function, W 0 = E – K.E
= 4.83 eV – 0.35 eV = 4.48 eV

30. Energy of incident photon (E) is given by,

E
hc

 
6.626  10 34 Js 3.0  10 8 ms 1 1.3252  10 15 J  13.252  10 16 J
 
150  1012 m 
Energy of the electron ejected (K.E)
1 1
  
2
= me v 2  9.10939  10 31kg 1.5  107 ms1
2 2
= 10.2480  10–17 J
= 1.025  10–16 J
Hence, the energy with which the electron is bound to the nucleus can be obtained as:
= E – K.E
= 13.252 × 10–16 J – 1.025  10–16 J
= 12.227  10–16 J
12.227  10 16 –3
= eV = 7.6  10 eV
1.602  10 19

31. The radius of the nth orbit of hydrogen-like particles is given by,
0.529n2 
r A
Z
52.9n2
r pm
Z
For radius (r1) = 1.3225 nm
= 1.32225  10–9 m
= 1322.25  10–12 m
= 1322.25 pm
rZ
n12  1
52.9
1322.25Z
n12 
52.9
Similarly,
211.6Z
n22 
52.9
2
n1 1322.5

n22 211.6
n12
 6.25
n22
n1
 2.5
n2
n1 25 5
 
n2 10 2
 n1 = 5 and n2 = 2
th nd
Thus, the transition is from the 5 orbit to the 2 orbit. It belongs to the Balmer series.
wave number ( v ) for the transition is given by,
64 – ATOMIC STRUCTURE – JEE
7  1 1  -1
1.097  10  2  2  m
 2 5 
7 –1  21 
= 1.097  10 m  
 100 
6 –1
= 2.303  10 m
Wavelength () associated with the emission transition is given by,
1 1 –6
 = = 0.434 ×10 m  = 434 nm
v 2.303  10 6 m1

32. From de Broglie’s equation,

h

mv
h
v
m
Where, v = velocity of particle (neutron), h = Planck’s constant, m = mass of particle (neutron),  =
wavelength
Substituting the values in the expression of velocity (v),
6.626  10 34 Js
v
 
1.67493  10 27 kg 800  10 12 m 
2 –1
= 4.94  10 ms v
= 494 ms–1
 Velocity associated with the neutron = 494 ms–1

h
33. According to de Broglie’s equation,  
mv
Where,  = wavelength associated with the electron, h = Planck’s constant, m = mass of electron
v = velocity of electron
Substituting the values in the expression of :
6.626  10 34 Js

 
9.10939  10 31kg 2.19  106 ms 1 
100
= 3.32  10–10 m = 3.32  10–10 m 
100
= 332  10–12 m
 = 332 pm
 Wavelength associated with the electron = 332 pm

34. From Heisenberg’s uncertainty principle,

h 1 h
x  p   p  .
4 x 4 
Where,
x = uncertainty in position of the electron
p = uncertainty in momentum of the electron
Substituting the values in the expression of p:
1 6.626  10 34 Js
p  
0.002nm 4   3.14 
1 6.626  10 34 Js
=  = 2.637  10–23 Jsm–1
2  10 12 m 4  3.14
p = 2.637  10–23 kgms–1 (1 J = 1 kgms2s–1)
 Uncertainty in the momentum of the electron = 2.637  10–23 kgms–1.
h 6.626  10 34 Js
Actual momentum = = = 1.055  10–24 kgms–1
4m  0.05 nm 4  3.14  5.0  10 11m
 Since the magnitude of the actual momentum is smaller than the uncertainty, the value cannot be defined.

35. For n = 4 and  = 2, the orbital occupied is 4d.

For n = 3 and  = 2, the orbital occupied is 3d.
For n = 4 and  = 1, the orbital occupied is 4p.
Hence, the six electrons i.e., 1, 2, 3, 4, 5, and 6 are present in the 4d, 3d, 4p, 3d, 3p, and 4p orbitals
respectively.
Therefore, the increasing order of energies is 5(3p) < 2(3d) = 4(3d) < 3(4p) = 6(4p) < 1(4d).

36. Nuclear charge is defined as the net positive charge experienced by an electron in the orbital of a multi-
electron atom. The closer the orbital, the greater is the nuclear charge experienced by the electron (s) in it.
(i) The electron(s) present in the 2s orbital will experience greater nuclear charge (being closer to the
nucleus) than the electron(s) in the 3s orbital.
(ii) 4d will experience greater nuclear charge than 4f since 4d is closer to the nucleus.
(iii) 3p will experience greater nuclear charge since it is closer to the nucleus than 3f.

37. (a) Phosphorus (P):

Atomic number = 15
The electronic configuration of P is:
1s2 2s2 2p6 3s2 3p3
The orbital picture of P can be represented as:

From the orbital picture, phosphorus has three unpaired electrons.

(b) Silicon (Si):

Atomic number = 14
The electronic configuration of Si is:
2 2 6 2 2
1s 2s 2p 3s 3p
The orbital picture of Si can be represented as:

From the orbital picture, silicon has two unpaired electrons.

(c) Chromium (Cr):

Atomic number = 24
The electronic configuration of Cr is:
2 2 6 2 6 1 5
1s 2s 2p 3s 3p 4s 3d

The orbital picture of chromium is:

From the orbital picture, chromium has six unpaired electrons.

(d) Iron (Fe):

Atomic number = 26
The electronic configuration is:
1s2 2s2 2p6 3s2 3p6 4s2 3d6
The orbital picture of chromium is:

From the orbital picture, iron has four unpaired electrons.

(e) Krypton (Kr):

Atomic number = 36
66 – ATOMIC STRUCTURE – JEE
The electronic configuration is:
2 2 6 2 6 2 10 6
1s 2s 2p 3s 3p 4s 3d 4p
The orbital picture of krypton is:

Since all orbitals are fully occupied, there are no unpaired electrons in krypton.