Chemistry : Structure of Atom

SECTION - I
SUBJECTIVE TYPE PROBLEMS
Problem 1 : Estimate the wavelength of second line in Balmer series.
Solution : T147he transition responsible for second Balmer line is 4 2.
 1 1 
E = 13.6 Z2  n 2  n 2  = 2.55 eV
 1  2 

hc 6.63 10 19  3 108

Now  = 
E 2.55  1.6  10 19
  = 4.862 × 10–7 m 4862 Å
Problem 2 : A spectral line in the spectrum of H-atom has a wave number of 82200 cm –1 .
What transition is responsible for this radiation? (Rydberg constant
RH=1.096 × 107 m-1).
Solution :  = 1 /  = 1/8220000
 it lies in UV region or in Lyman series
Hence, n1 = 1
Using the relation for wave umber for H-atom:
 1 1 
v = 1/= RH  2
 2
 n1 n 2 
 1 1 
82200 = 1.096 × 105  2  2 
 n1 n 2 
1 3
 1– =
n 22 4
 n2 = 2

Problem 3 : Calculate the wavelength of light radiation that would be emitted, when an electron in
the fourth Bohr’s orbit of He+ ion falls to the second Bohr’s orbit. To what transition
does this light radiation correspond in the H-atom ?
Solution : Let us calculate E first.
 1 1 
E = 21.7 × 10–19 Z2  n 2  n 2 
 1 2 

Substituting n1 = 2 and n2 = 4, Z = 2 we get ; E = 1.632 × 10–8 J

hc
Now  = = 1.218 × 10–7 m = 1218 Å
E
The value of = 1218 Å implies that, in H-atom this transition would lie in Lyman Series.
Hence our aim is now to find the transition : n2 1st orbit)
 1 
 E = 21.7 × 10–18 = 21.7 × 10-19 1  n 2 
 2 
 n2 = 2
Hence the corresponding transition in H-atom is 2 1.
 Chemistry : Structure of Atom

Problem 4 : Find the wavelength of radiation required to excite the electron in ground level of Li++
(Z = 3) to third energy level. Also find the ionisation energy of Li 2+ .
R = 1.097 × 107 m-1
 1 1 
Solution :  = RZ2  2  2 
 n1 n 2 
Putting the values : n1 = 1, n2 = 3, Z = 3
We get  = 8.77 × 107 m–1
1
  = = 113.9 Å

Ionisation energy is the energy required to remove the electron from ground state to infinity
i.e. corresponding transition responsible is 1 
1 1 
i.e. E = 13.6 × 32  2  2 
1  
E = 122.4 eV = 1.95 × 10–7 J = ionisation energy

Problem 5 : Calculate the uncertainty in position assuming uncertainty in momentum within 0.1 %
for :
(a) a tennis ball weighing 0.2 kg and moving with a velocity of 10 m/s.
(b) a electron moving in an atom with a velocity of 2 × 106 m/s.
Solution : Using Uncertainty Principle,
h
x p =
4
(a) p = mv = 0.2 × 10 = 2.0 kgm/s
p = 0.1 % of p = 2 × 10–3
h 6.63  10 34
 x = 
4p 4  3.14  2 10 3
= 2.135 × 10–32 m.
(b) For an electron, p = mv
= 9.1 × 10–31 × 2 10–6
= 1.82 × 10–24 Kgm/s
p = 0.1 % of p = 1.82 × 10–27 Kgm/s
h 6.63 10 34
x = 
4p 2  3.14  1.82 10 21
 x = 2.89 × 10–8 m

Problem 6 : Hydrogen when subjected to photo-dissociation, yields one normal atom and one atom
possessing 1.97 eV more energy than normal atom. The bond dissociation energy of
hydrogen molecule into normal atoms is 103 kcals mol–1 . Compute the wave length of
effective photon for photo dissociation of hydrogen molecule in the given case.
Solution : H2 H + H*
where H is normal H-atom and H* is excited H-atom.
So the energy required to dissociate H2 in this matter will be greater than the usual bond
energy of H2 molecule.
E(absorbed) = dissociation energy of H2 + extra energy of excited atom
energy required to dissociate in normal manner = 103 × 103 cal (given)
Chemistry : Structure of Atom

103 103   4.18 

=  7.17  10 19 J / atom
6 10 23
extra energy possessed by excited atom is 1.97 eV = 1.97 × 1.6 × 10–19 J
= 3.152 × 10–19
E (abosorbed)= 7.17 × 10–19 + 3.152 × 10–19 = 1.032 × 10–18 J
Now calculate the wavelength of photon corresponding to this energy.
hc 6.63 1034  34  108
 =  = 1.926 × 10–7 m = 1926 Å
E 1.032 10 J

Problem 7 : Find out the number of waves made by a Bohr electron in one complete revolution in
its 3rd orbit.
Solution : For an electron to be in a particular energy level of radius r, with de Bronglie wavelength :
2r = n
(where n = number of waves in one revolution)
h 2r mv
 = n =
mv h
for third orbit ;
r = 0.53 × 10–10 (3)2 m ; v = 2.165 × 106 (1/3)
substituting the value of r, v, m and h, we get,
n =3
Problem 8 : With what velocity should an  particle travel towwards the nucleus of a copper atom
so as to arrive at a distance 10–13 metre from the nucleus of the copper atom?

Solution : To arrive at a distance ‘d’ from the nuceleus, kinetic energy of - particle equals electrostatic
potential energy.
KE = PE
1 K  q   q cu 
m  V2 =
2 d
q = 2 × 1.6 × 10–19 C d = 10–23 m
q = 29 × 1.6 × 10–19 C
m = 4 × 1.67 × 10–27 kg
K = 1/40 = 9 × 109 N-m/C2

2k q q cu
 V = md

Substitute the given values,

V  = 6.325 × 106 m/s.

Problem 9 : Find the energy released (in ergs), when 2.0 gm atom of Hydrogen undergo transition
giving spectral line of lowest energy in visible region of its atomic spectrum.
1 1
Solution : E = 2.178 × 10–18 (Z2)  2  2  J / atom
 n1 n 2 
For visible photon, n1 = 2
 Chemistry : Structure of Atom

For lowest energy transition : n2 = 3

1 1
 E = 2.178 × 10–18 (12)  2  2  J / atom
2 3 
For 2.0 gm atom,
 5 
E = (2 × 6.023 × 1023 ) 2.178 ×10–18  36  Joules. = 3.63 × 105 J
 

= 3.63 × 1012 ergs

Problem 10 : Find the ratio of frequencies of violet light (  = 4.10 × 10–5) to that of red light
( = 6.56 × 10 –5 cm). Also determine the ratio of energies carried by them.
Solution : C =  ;
c : speed of light, : frequency & : wavelength
1 2
2 =  1 : red & 2 : violet
1

1 6.56  10 5
 2 =  1.6
4.10  105
Now the energy associated with electromagnetic radiation is given by E = h.
E1 1 2 
 E2 =     1.6
2 1

Hence the ration of energies is same as that of frequencies.

Chemistry : Structure of Atom

SECTION - II
SINGLE CHOICE PROBLEMS
Problem 1 : A photon of wavelength 300 nm is absorbed by a gas and then reemitted as two photons.
One photon is red with wavelength of 760 nm. The wave number of the second photon will
be
(a) 2.02 × 106 m–1 (b) 3.02 × 106 m–1
(c) 1.02 × 106 m–1 (d) 2.2 × 106 m–1
hc
Solution : E = ...(i)

hc
E1 = λ ...(ii)
1
hc
E2 = λ ...(iii)
2
 1 1 
E = E1 + E2 = hc  + 
λ
 1 λ 2
1 1 1
= λ +λ
λ 1 2
1 1 1
= +
-9 -9 λ2
(300 ×10 ) (760×10 )
1  1 1  9
= -  ×10
λ2  300 760 
= (0.00333 – 0.00131) × 109 = 2.02 × 106 m–1
(a)
Problem 2 : A certain laser transition emits 6.37 × 1015 quanta per second per square meter. The power
output in joules per square meter per second would be (l = 632.8 nm).
(a) 5 × 10–5 J m–2 sec–1 (b) 2 × 10–3 J m–2 sec–1
(c) 9.2 × 10–3 J m–2 sec–1 (d) none of the above

Solution : Energy falling per square meter per sec.

No. of quanta falling per square meter per second 6.37 ×1015 × 6.626 ×10-34 × 3×108
= =
Energy of one qunta 632.8×10-19
= 2 × 10–3 J m–2 sec–1
(b)
Problem 3 : The uncertainity in the location of circulating electron is equal to its de Broglie wavelength.
The minimum percent error in its measurement of velocity under this circumstance will be
approximately
(a) 4 (b) 8
(c) 18 (d) 22
Solution : Let the electron be moving with momentum, p, its wavelength will be equal to h/p.
 Chemistry : Structure of Atom

h
x 
p
From Heisenberg’s uncertainity principle,
h
x  p 
4π
h×p
p 
4π × h
Δp 1
p
=
4π
Minimum percent error in measuring its velocity would be
Δv Δp 100 100
100 × = p ×100 = = = 7.96 » 8
v 4π 4 × 3.14
(b)
Problem 4 : A mono electronic species in energy level with energy X was provided with excess of energy
so that it jumps to higher energy level with energy Y. If it can emit 6 wavelenths originated
from all possible transition between these group levels, then which of the following relation is
correct?
X 3 X n
(a) = 1+ (b) =
Y n Y 6

X X 3
(c) = (n - 1) 2 (d) = 1+
Y Y n
(where n is the principal quantum number of energy level X).
Solution : If n is the principal quantum number of energy level corresponding to energy X, the principal
quantum number of energy level Y is (n + 3) as it emit 6 wavelengths.
X (n + 3) 2

Y n2

X 3
= 1+
Y n
(a)
Problem 5 : If we plot a graph of stopping potential of photoelectrons against the frequency of radiation
that has emitted it, then its sope would be equal to
(a) 6.625 × 10–34 (b) 3.656 × 1012
(c) 2.414 × 1014 (d) 5.796 × 1018
Solution : From Fintein’s equation for photoelectric effect, we have
hv = hv0 + 1/2 mv2max;
where v0 is threshold frequency
If Vstop be the stopping potential of photoelectrons then its maximum possible kinetic energy
must be equal to the opposing work i.e. eVstop.
hv = hv0+ eVstop
Chemistry : Structure of Atom

e
v = v0 +   Vstop
h
So the given graph will be a straight line with slope equal to
e 1.6 ×1019
=
h 6.626 ×1034
= 2.414×1014
(c)

Problem 6 : The radius of hydrogen atom in its ground state is 5.3 × 10–11 m. After collision with an
electron it is found to have a radius of 21.2 × 10–11m. The principal quantum number of the
final state of the atom is
(a) 2 (b) 3
(c) 4 (d) 5
Solution : Radius of H– atoms in its ground state,
r1 = 5.3 × 10–11 meters
Radius of Bohr atom in its nth orbit,

n2
rn = 5.3 × 10–11 meters
z
For H-atom, z = 1 and rn = 2.2 × 10–11 meters
1/2
 21.2 ×1011 
n =  11 
 =2
 5.3×10 
(a)

Problem 7 : Suppose 10–17 J of energy is needed by theinterior of human eye to see an object. How many
photons of green light (l = 550 nm) are needed to generate this minimum amount of energy?
(a) 14 (b) 28
(c) 39 (d) 42
Solution : Let the number of photons required be n.
nhc
= 10–17


10 17   1017  550 109

n= = = 27.6 » 28 photons
hc 6.626 1034  3 108
(b)

Problem 8 : Which element has a hydrogen like spectrum whose lines have wavelength one fourth of
atomic hydrogen?
(a) He+ (b) Li2+
(c) Be3+ (d) B4+
 Chemistry : Structure of Atom

1 2
 1 1 
Solution : = R  1    ...(i)
H 2
 n1 n 22 

1  1 1 
= RZ2    ...(ii)
X  n2 n2 
 1 2

x 1
Dividing equation (i) by equation (ii), we get  = 2
H Z
1 1
= 2
4 Z
Z = 2 (He+)
(a)

Problem 9 : Ionisation potential of hydrogen is 13.6 eV. Hydrogen atom in the ground state are excited
by monochromatic light of energy 12.1 eV. The spectral lines emitted by hydrogen according
to Bohr’s theory
(a) One (b) Two
(c) Three (d) Four
Solution : The electron in H atom is excited to III shell after absorbing 12.1 eV. The possible transition
state = (3-1) = 3.
(c)

Problems 10 : Which of the following statements is not correct?

(a) Special stability of half-filled and fully-filled atomic configurations 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
Solution : Aufbau order is obeyed in cases where energy difference between ns and (n–1)d subshell
is large.
Chemistry : Structure of Atom

SECTION - III
MULTIPLE CHOICE PROBLEMS
Problem 1: In hydrogen like sample two different types of photons A and B are produced by electronic
transition. Photon B has it’s wavelength in the infrared region if photon A has more energy
than B, then the photon A may belong to the region
(a) ultraviolet (b) visible
(c) infrared (d) none
Solution : (a, b, c)
Since B is in infrared region and A has more energy than B hence it will have lesser wave
length i.e. ultra violet, visible or infrared region.
Problem 2 : A hydrogen like atom in ground state absorbs ‘n’ photons having the same energy and it
emits exactly ‘n’ photons when electronic transition takes place. Then the energy of the
absorbed photon may be
(a) 91.8 eV (b) 40.8 eV
(c) 48.4 eV (d) 54.4 eV
Solution : (a, b)
Since it absorbs ‘n’ photons and it also emits exactly n-photons therefore transition must
have taken place from 1 to 2.
 Energy of photon = 10.2 Z2
where Z = 1, 2, 3, 4
Problem 3: Identify the correct statement(s)
(a) || is the probability of finding the electron in an orbital
(b) p-orbital is directional in nature
(c) d x 2  y 2 has dumb bell shape along x-and y-axis

(d) d z 2 has dumb bell shape along x-axis and y-axis.

Solution : (b, c)
It is obvious from the fact.
Problem 4 : If uncertainty in momentum is twice the uncertainty in position of an electron then uncertainty
 h 
in velocity is :   
 2 
1 
(a)  (b)
2m 4m
1 1
(c)  (d) 
4m m
Solution : (d)
h
P.x 
4
 2x = – P (given)
 Chemistry : Structure of Atom

P 2 h
 
2 4

h
m 2 ( V) 2  { P  mV}
2
P 2 h

2 4

h
 V 
2m 2 

1 h 1
 V  or V  
m 2 m
Problem 5 : In a hydrogen like sample electron is in 2nd excited state, the binding energy of 4th state of
this sample is 13.6 eV, then
(a) A 25 eV photon can set free the electron from the second excited state of this sample
(b) 3 different types of photon will be observed if electrons make transition up to ground
state from the second excited state
(c) If 23 eV photon is used then K.E. of the ejected electron is 1eV
(d) 2nd line of Balmer series of this sample has same energy value as 1st excitation energy
of H-atoms
Solution : (a, b)

z2 z2
B.E. of 4th state = 13.6  13.6  13.6  z4
n2 42
sample is Be3+  energy of elecron in 3rd state
state = 1.5 × 42 = 24 eV
therefore 25 eV photon will cause ionisation.
Problem 6 : The orbitals which have same number of nodes are
(a) 2s, 2p (b) 3p, 3d
(c) 2s, 3p (d) 3s, 4d
Solution : (a, b)
2s has one spherical node and 2p has one planar node, 3p has one planar and one spherical
node whereas 3d has two planar nodes but no spherical node.
Problem 7 : The probability of finding the electron in the px orbital is
(a) Zero at the nucleus
(b) Maximum on two opposite sides of the nucleus along X-axis
(c) Zero on Z-axis
(d) Same on all sides around the nucleus.
Solution : (a, b, c) Fact.
Chemistry : Structure of Atom

Problem 8 : The possible correct sets of quantum numbers for the unpaired electron of oxygen atom in
the orbitals of p-subshel are
(a) n = 2, l = 1, m = 0 (b) n = 2, l = 1, m = –1
(c) n = 2, l = 1, m = + 1 (d) n = 2, l = 1, m = – 2
Solution : (a, b, c)
Option (d) is not possible because if l = 1, m has three values i.e. –1, 0, + 1.
Problem 9 : The diagram illustrates a possible electronic configuration of which of the following species

        
(a) Cl+ ion (b) S atom
(c) Ar+2 ion (d) P–2 ion
Solution : (a, b)
Total number of electrons = 16
Cl+ ion and S atom have 16 electrons.
Problem 10 : Which of the following statements are wrong?
(a) Heisenberg’s uncertainity principle is applicable only to microscopic particles
(b) de Broglie concept of dual nature is applicable to all material particles
(c) The electronic configuration of palladium (Z = 46) is [Kr] 4d85s2
(d) dxy, dyz and dxz orbitals have identical shapes.
Solution : (a, c)
Heisenberg’s uncertainity principle is applicable to microscopic as well as macroscopic
particles but has significance only for microscopic particles. Hence, (a) is wrong. Electronic
configuration of Pd is [Kr] 4d105s0. Hence, (c) is wrong.
 Chemistry : Structure of Atom

MISCELLANEOUS PROBLEMS
SECTION - IV
COMPREHENSION TYPE PROBLEMS

Write up – I
In the Rutherford’s experiment, -particles were bombarded towards the copper atoms so as to arrive
at a distance of 10–13 metre from the nucleus of copper and then getting either deflected or traversing
back. The -particles did not move further closer.

Problem 1 : The velocity of the -particles must be

(a) 8.32 × 108 cm/sec (b) 6.32 × 108 cm/sec
(c) 6.32 × 108 m/sec (d) 6.32 × 108 km/sec
Solution : (b)

2 2Ze 2e 1
At the distance of closest approach v  
40  r0 m
Hence, substituting the value of m = 4, z = 29, e = 1.66 × 10–19, r0 = 10–13 mts.
v = 6.32 × 108 cm/sec
Hence, choice (b) is correct while (a), (c), (d) are incorrect as from above calculation.
Problem 2 : Which of the following metals can be used instead of gold in -scattering experiment
(a) Pt (b) Na
(c) K (d) Cs
Solution : (a)
It is because ‘Pt’ is highly malleable and ductile and least ractive.
(b), (c) and (d) are soft metals and highly reactive, therefore, cannot be used.
Problem 3 : From the Rutherford’s -particle scattering, it can be concluded that

 1
(a) N  sin 4 (b) N 
2 sin  

1 
(c) N  (d) N  sin
sin  / 2 2
Where N = Number of -particles scattered by an angle .

1
Solution : It is observed that N = no. of particles of scattering  4
sin ( / 2)
Hence, choice (c) is correct while choice (a), (b) and (d) are incorrect.
Chemistry : Structure of Atom

Write up – II
The branch of science which deals with dual behaviour of mater is said to be quantum mechanics. The
fundamental equation of quantum mechanics is Schrodinger wave equation. The important features of
quantum mechanics are
(i) The energy of electron is quantized as a result of wave like properties of electrons.
(ii) The position and momentum of an electron cannot be determined simultaneously. The path of
electron cannot be determined. We can only talk of probability of finding electron.
(iii) An atomic orbitals is represented by wave function ‘’ for an electron. ‘R’ is radial wave function
whose value varies with distance from the nucleus  2 determines total probability (angular and
radial) whereas R2 is called raidal probability. All information about electron in an atom is stored in
orbital wave function . ‘R’ is radial wave function.
(iv) R can be +ve or –ve but R2 is always +ve. Similarly, can be +ve or – ve but 2 is always +ve 2
can be equal to zero.

Problem 4 : The regions or space where 2 = 0 are called

(a) nodes (b) antinodes
(c) orbitals (d) energy levels
Solution : (a).
Nodes are region where there is no probability of finding elctron, i.e.,  2 = 0.
Problem 5 : Number of nodal planes in f-orbitals are
(a) 0 (b) 1
(c) 2 (d) 3
Solution : (d)
There are three nodal planes in f-orbitals
No. of nodal planes = l = 3
Problem 6 : Which of the following probability distribution curves represents 2s orbital for H-atom

(a) R
2 (b) R2

r r

(c) R
2 (d) R2

r r
Solution : (b)
It is because 2s orbital has one node where R2 = 0.
 Chemistry : Structure of Atom

MATCHING TYPE PROBLEM

7. Column (I) Column (II)

+
(a) Binding energy of He atom in an excited state (p) infrared region
(b) 7  3 transition in hydrogen atom (q) 3.4 eV
(c) 5 transition in hydrogen atom (r) 13.6 eV
(d) Series limit of Balmer series in hydrogen atom (s) 10 spectral lines observed

+
13.6  22
Sol. (a) B.E. of He atom =
n2
n = 1, 2, 3 .....
Hence it can be 13.6 eV, 3.4 eV both
(b) In 7  3 transition n = 7 – 3 = 4

4(4  1)
 Maximum no. of spectral line observed =  10
2
It is line of Paschen series Hence infrared region
(c) 5  1 : 10 lines
(d) Series limit of Balmer series is the last line i.e. 3.4 eV energy.
(a) — (q, r) (b) — (p, s)
(c) — (s) (d) — (q)

ASSERTION-REASON TYPE PROBLEMS

The question given below consist of an ASSERTION and the REASON. Use the following key for the
appropriate answers
(a) If both Assertion and Reason are correct and Reason is the correct explanation for Assertion
(b) If both Assertion and Reason are correct and Reason is not the correct explanation for
Assertion
(c) If Assertion is correct but Reason is not correct.
(d) If Assertion is incorrect but Reason is correct.
8. Assertion : In third energy level there is no f-subshell.
Reason : For n = 3, the possible values of l are 0,1 and 2.
Solution : Both assertion and reason are true and reason is a correct explanation for assertion Hence
Ans. (a)
9. Assertion : Heisenberg’s uncertainty principle holds good for all objects but it is of significance only for
microscopic particles.
Reason : Heisenberg’s uncertainity principle is due to the limitation of the measuring instruments to
measure accurately the position and velocity of microscopic particles.
Solution : Heisenberg uncertainity principle is not due to limitation of the measuring instrument.
Ans. (c)
Chemistry : Structure of Atom

10.Assertion : Electronic configurations of Fe3+ (containing 23 electrons) is not same as that of Vanadium
(Z = 23), i.e. isoelectronic species do not have the same electronic configuration.
Reason : Here, Fe3+ follows Aufbau principle where as Vanadium does not.
Solution : Assertion is correct but reason is false.
Electronic configuration of Fe3+ : [Ar]3d5
Electronic configuration of V : [Ar]3d34s2
Ans. (c)