STRUCTURE OF ATOM Page No.

[76]
In chapter exercise – 1 (Thomson and Rutherford Model)

1. Heavy atoms have a heavy nucleus carrying a large amount of positive charge. Hence, some -particles are
easily deflected back on hitting the nucleus. Also a number of -particles are deflected through small
angles because of large positive charge on the nucleus. If light atoms are used, their nuclei will be light and
moreover, they will have small positive charge on the nucleus. Hence, the number of particles deflected
back and those deflected through some angle will be negligible

2.(i) Mass of one electron = 9.11 × 10– 31 kg,

i.e., 9.11 × 10– 31 kg = 1 electron
1
 1 g i.e. 103 kg  103 electrons = 1.098 × 10 electrons.
27
31
9.1110
(ii) Mass of one electron = 9.11 × 10– 31 kg
– 31
 Mass of one mole of electrons = (9.11 × 10 ) × (6.022 × 1023) = 5.486 × 10– 7 kg
Charge on one electron = 1.602 × 10– 19 coulomb
– 19
 Charge on one mole of electrons = (1.602 × 10 ) × (6.022 × 1023) = 9.65 × 104 coulombs.
3. (i) 1 molecule of CH4 contains electrons = 6 (in carbon ) + 4 (in 4 hydrogen atom) = 10
 1 mole, i.e., 6.022 × 10 molecules will contain electrons = 6.022 × 10
23 24

(ii) (a) 1 g atom of 14C = 1 mol carbon atom (=14 g) = 6.022 × 1023 atoms = (6.022 × 1023) × 8 neutrons.
(as each 14C atom has 14 – 6 = 8 neutrons)
Thus, 14 g or 14000 mg have 8 × 6.022 × 1023 neutrons
8  6.022 1023
 7 mg will have neutrons   7  2.4088×1021
14000
(b) Mass of 1 neutron = 1.675 ×10– 27 kg
 Mass of 2.4088 × 10– 21 neutrons
= (2.4088 × 1021)(1.675 × 10– 27 kg) = 4.0347 × 10– 6 kg
(iii) (a) 1 mol of NH3 = 17 g NH3
= 6.022 × 1023 molecules of NH3
= (6.022 × 1023) × (7 + 3) protons
= 6.022 × 1024 protons
 34 mg i.e., 0.034 g NH3
6.022 1024
  0.034  1.2044×1022 protons
17
(b) Mass of one proton = 1.6726 × 10– 27 kg
 Mass of 1.2044 × 10 protons
22

= (1.6726 × 10– 27) × (1.2044 × 1022) kg = 2.0145 × 10– 5 kg

(iv) There is no effect of temperature and pressure.
4. Charge carried by one electron = 1.6022 × 10– 19 C
 Electrons present in oil drop carrying

1.282 1018
– 1.282 × 10– 18 charge  8
1.6022 1019 C

Raman Niwas, Near Akashwani, Mahmoorganj, Varanasi, Ph (0542) 2363455. www.catjee.in

STRUCTURE OF ATOM Page No.[77]
Objective:

1.(c) Concept of circular paths of fixed energy was put forward by Bohr and not derived from Rutherford‟s
scattering experiment.

2.(d) Characteristics of cathode rays doesn‟t depend upon the nature of gas present in the cathode ray tube.

3.(b) The mass of electron is very very small as compared to the mass of the neutron.

4.(a) Thomson model of atom could explain only the overall neutrality of the atom.
5.(a) 1 eV = 1.6 × 10– 19 J
mv2 10  (10)2
6.(b) Centripetal force    100 N
r 10
1 1
7.(a)  9 109  0   8.85 1012 C2 / N  m2
40 4 9 109

8.(a) Energy (J) = potential (V) × charge (C)  1 volt = 1 J/C

9.(d) 1 Joule = 107 erg
q1q 2
10.(a) F  K
r2
(2q1 )(2q 2 ) q1q 2
F'  K 2
 K. F
(2r) r2

Hence, force remains the same.

total number of electrons 6.25 1018
11.(a) Time required   seconds
electrons given out in 1 seconds 109

6.25  109
 years  198.18 years
60  60  24  365
12.(b) Total charge on metal sphere = – 6.5 µC
Remove charge = – 5 × 1013 × 1.6 × 10– 19 = – 8 × 10– 6
Net charge = Total – Removed = (– 6.5 × 10– 6) – (– 8 × 10– 6 C) = 1.5 µC
13.(a) Acc. To charge conservation
Average charge on both A and B for equal charge carriage
(3.00 C)  (4.00 C)
  3.50 C
2
So, transfer of charge from B to A = (– 3.50 µC) – (– 4.00 µC) = 0.50 µC
0.50 106
 Electrons required for this charge  19
 3.125 1012
1.6 10

In chapter exercise – 2 (Planck’s quantum theory)

Subjective:
1. Energy emitted by the bulb = 25 watt = 25 J s– 1
hc
Energy of one photon (E) = h f 

Here,   0.57 µ m = 0.57 × 10– 6 m

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STRUCTURE OF ATOM Page No.[78]
8 –1 –34
Putting c = 3 × 10 m s , h = 6.62 × 10 J s,
34 1
(6.62 10 Js)(3 10 ms ) 8
E = 3.48 × 10– 19 J
0.57 106 m
25Js1
 No. of photons emitted per sec   7.18×1019 photons per sec.
3.84 1019 J
1 1
2. (v)f 
Frequency   5×109 s-1
Period 2.0 1010 S
cc 3.0 108 ms 1
Wavelength,   9 1
 6.0×10-2 m
f v 5 10 s
1 1
Wave number, v    16.66 m-1
 6 102 m
hc 6.626 1034  3 108 –19 J = 3.313 10
19
3. E = hf  = = 3.313 × 10 eV = 2.07 eV
 6000 1010 1.6 1019
4.   580 nm = 580 × 10– 9 m
cc 3.0 108 ms 1
Frequency, f    5.17 ×1014 s-1
 580 109 m
1 1
Wave number, v    1.72×106 m-1
 580 109 m
5. (i) f = 3 × 10 Hz, E = hf= (6.626 × 10– 34 Js) (3 × 1015 s– 1) = 1.988 × 10– 18 J
15

(6.626 1034 Js)(3 108 ms 1 )

c
(ii)  = 0.50 × 10 – 10
m, E = h f  h  10
= 3.98×10-15 J.
 0.50 10 m
6.   4000 pm = 4000 × 10– 12 m = 4 × 10– 9 m
hc E (1J)  (4 109 m)
E = n hf = n n  34 1
= 2.012 × 1016 photons.
 hc (6.626 10 Js)(3.0 10 ms )
8

7. (A) = 300 nm
(B) = 300 µm = 300 × 10– 6 m = 3 × 10– 6 × 109 nm=3000 nm
(C) = 3 nm
(D) =30 Å = 3 nm
c 1
E=hf= h . Thus, E  .  Hence, increasing order of energy is B <A < C = D.
 
Objective:
cc 3.0 108 ms1
1.(a)    0.6494 106 m = 649.4 × 10– 9 m = 649.4 nm.
f 4.620 1014 s 1
hc 6.626 1034  3 108 107  495 109
2.(c) E   1017  n   n   24.90 100  25
 495 109 6.626 1034  3 108
1 1
3.(b) Wave number  =  2  104 cm1
 5000  108 cm
E
4.(d) h  [h] = [E × time] = [M1 L2 T– 1]
f
hc 1
5.(d) E  hf   E (hyperbolic curve)
 

In chapter exercise – 3 (Photoelectric effect)

0 1.9 1.602 1019 J
W
1. Work function   h f 0  vf00  =4.59×1014s-1 (1 eV = 1.602 × 10– 19)
h 6.626 1034 Js

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STRUCTURE OF ATOM Page No.[79]
cc 3.0 108 ms1
(a) 00    6.54 107 m  654 109 m  654 nm
fv00 4.59 1014 s 1

1 1  1 1 
(b) K max  h(f  f 0 )  h c (  )  (6.626 1034 Js)(3.0 108 ms1 )  9
 9 
 0  500 10 m 654 10 m 

6.626  3.0 1026  154  – 20

 9  500  654  J = 9.36 × 10 J
10  

1
mu 2  9.36 1020 J =9.3610 kg m s
2 –2
max 
-20
(c) K
K.E.
2
1
 (9.111031 kg) u 2  9.36 1020 kg m2s 2  u = 2.055 × 10 m s
2 11 2 –2
2
 u = 4.53 × 105 m s– 1.
2. Energy of the incident radiation (E) = Work function (  )+ Kinetic energy of photoelectron(K)

c (6.626 1034 Js)(3.0  108 ms1 )

Energy of incident radiation = h f = h  9
= 7.74 × 10– 19 J = 4.83 eV The
 (256.7  10 m)
potential applied gives the kinetic energy to the electron. Hence, kinetic energy of the electron = 0.35 eV
 Work function = 4.83 eV – 0.35 eV = 4.48 eV

hc (6.626 1034 Js)(3.0 108 ms 1 )

3. Energy of the incident photon (E)    13.25 1016 J
 (150 1012 m)

1 1
Energy of the electron ejected (K)  mu 2  (9.111031 kg)(1.5 107 ms 1 ) 2  1.025 1016 J
2 2
Energy with which the electron was bound to the nucleus (  ) = 13.24 × 10– 16 J – 1.025 × 10– 16 J

12.225 1016
 12.225 1016 J 
3
19
eV = 7.63 × 10 eV
1.602 10
4. Photoelectric effect :
When radiations with frequency greater than a certain minimum frequency (v0) strike the surface of a metal,
the electrons are ejected from the surface of the metal. This phenomenon is called photoelectric effect. The
electrons emitted are called photoelectrons.

The apparatus used for studying the photoelectric effect is shown in figure. It consists of an evacuated tube
fitted with metal surface to be exposed as cathode and a suitable detector as the anode and then connected to
the external circuit. When light of sufficient energy is allowed to strike the surface of the metal, electrons
are ejected which move towards the detector. By observing the amount of current flowing, the kinetic
energy of the electrons can be determined.
5. hv = h f 0 + K.E. or h f 0 = h f – K.E.

K.E. 1.988 1019 J

 f0 = f   1.0 1015 s 1  = (1.0 × 1015 – 0.30 × 1015) s– 1 = 9.7 × 1014 s– 1
h 6.626 1034 Js
When  = 600 nm = 600 × 10– 19 m = 6.0 × 10– 7 m

Raman Niwas, Near Akashwani, Mahmoorganj, Varanasi, Ph (0542) 2363455. www.catjee.in

STRUCTURE OF ATOM Page No.[80]
cc 3.0 108 ms 1
 0.5 1015 s 1 = 5 × 10 s
14 – 1
f  
 7
6.0 10 m
Thus, f < f0. Hence, no electron will be emitted.
Objective:
1.[c] Energy of the incident photon = hc / 
19.878 1019
Energy of the incident photon = eV = 3.105 eV
4 1.6 1019
Kinetic energy of the emitted electron K = h f –  = 3.105 eV - 2.00 eV= 1.105 eV
hc 6.626 1034  3 108 Jm
2.[d] Threshold wavelength =  o = = =3779 1010 m = 3779 Å
 5.26 10 J19

3.[b]
hc 1242 eV.nm
4.[b] The maximum kinetic energy is Kmax= –  = – 2.5 eV
 280 nm
= 4.4 eV – 2.5 eV = 1.9 eV
Stopping potential V is given by eV = Kmax
V = Kmax/e = (1.9 / e) eV = 1.9 V
hc
5.[a]  o =

6.6 1034  3 108
   o )sodium= = 6188 Å
2 1.6 1019
1 ( ) ()
 o   0 sodium  copper  (  o )copper = (2/4) × 6188 = 3094 Å
 ( 0 )copper ()sodium
To eject photo-electrons from sodium the longest wavelength is 6188 Å and that for copper is 3094 Å.
Hence for light of wavelength 4000 Å, sodium is suitable.
6.[d] If the incident light be of threshold wavelength (  o ), then the stopping potential shall be zero. Thus
hc 6.6 1034  3 108
o = , o = ,
 4.2 1.6 1019

 o = 2.946 × 10–7 m = 2946 Å

hf hf 0
7.[b] Relation between Vo and f is: Vo = 
e e
Put it in the form of y = mx – c,
here Vo = y, f = x, = c
y = (h/e)x – c  m = h/e
8.[b]  = 1.07 eV = 1.07 × 1.6 × 10–19 J
 = 3320 × 10–10 m
hc hc 
eV0   0  V0   0
 e e
6.62 1034  3 108
Vo =  3.74 eV
3320 1010 e
Vo = 3.74 V – 1.07 V = 2.67 V.
9.[c] hf = h f o + Kmax
6.6 × 10-34 × 3 × 108 = 4 × 1.6 × 10–19 + Kmax
19.8 × 10-19 – 6.4 × 10-19 = Kmax

Raman Niwas, Near Akashwani, Mahmoorganj, Varanasi, Ph (0542) 2363455. www.catjee.in

STRUCTURE OF ATOM Page No.[81]
1
 Kmax = 13.4 × 10–19 J  (½ ) 2
mVmax = 13.4 × 10–19
2
2 13.4 1019 2 13.4 1019
 Vmax = = = 1.73 × 106 m/s
m 9 1031
10.[a] Kmax = Ephoton – 0 = 6.2 eV– 4.2 eV= 2.0 eV,
Kmax = 2 × 1.6 × 10–19 = 3.2 × 10–19 J

In chapter exercise -4 (Radius and velocity of Hydrogen atom)

Subjective:
1. Bohr model is applicable on : H, He , Li 2 , Be3 , B4 etc
2. Electrostatic force exerted by protons in nucleus.
h
3. m V rn
2
Where, m = mass of electron, V= velocity of electron, n =orbit number, h= planck‟s constant
h h 6.626  1034 J.s
4. Angular momentum ( m V r ) = n = 1   1.055  1034 Js
2 2 2  3.14
n2 o
5. Radius of nth orbit (rn )  ro  ; n= orbit number, z = atomic number , ro = 0.529 A
z
z
Velocity of nth orbit (Vn )  Vo  ; n= orbit number, z = atomic number , Vo = 1.8  106 m
n s
Objective
1.(c) Bohr‟s atomic model is valid for H-like species, i.e. 1e– system.
2.(a) Linear momentum = mass × velocity
n2
3.(a) rn  0.529 Å
Z

12
r1  r  0.529   0.529 Å
1

n2
rn  0.529  0.529 n 2 Å  rn  r.n 2
1
nh
4.(d) mvr 
2
5 h h
Angular momentum for (n = 5) an electron  .  2.5
2  
5.(a) For hydrogen
rn  r.n 2 (Å) ; where r = radius of H-atom in ground state

21.2 1011
rn  21.2 1011 m  (5.3 1011 m).n 2  n 2  4n2
5.3 1011
Z 1
6.(a) vn  2.18 106  ms
n
For hydrogen atom, Z = 1
1
vn  2.18 106 
n

Raman Niwas, Near Akashwani, Mahmoorganj, Varanasi, Ph (0542) 2363455. www.catjee.in

STRUCTURE OF ATOM Page No.[82]
2.18 106
 v4  v 
4

v1  2.18 106  4v

 Z
7.(a) vn  2.18 106   ms 1
n

Z
vn  .
n
1
vn  (in case of hydrogen atom)
n

v2 1 v 2.19 106
  v2  1  = 1.095 × 106 ms– 1
v1 2 2 2

Z
8.(a) vn  2.18 106 
n

1 2.18 106
vn  7.27 105  2.18 106  (for H-atom)  n   n 3
n 7.27 105

n2
 rn  0.529 Å
Z

32
 r3  0.529  Å
1
Shifting distance = r3– r1  (9  1)0.529 Å = 4.232 Å away from nucleus.

n2 12
9.(b) rn  0.529  Å  0.529  1010 m  0.529 1010 102 cm = 0.529 × 10– 8 cm
Z 1
nh
10.(c) Angular momentum (mvr) 
2
h
So, minimum „mvr‟ is for n = 1 
2

 Z
11.(d) vn  2.18 106   ms 1
n

1
r1  0.529  Å
Z
So, r1 is minimum for maximum value of „Z‟ (atomic number) i.e. Li2+
n2
12.(d) rn  0.529 1010 
Z
For shortest radius (n = 1)
0.529 1010 0.529 1010
r1   18 1012 m  Z   2.938  3
Z 18 1012
So, it is Li2+ ion.
n2
13.(d) rn  0.529  Å
Z
r1, H  0.529Å

Raman Niwas, Near Akashwani, Mahmoorganj, Varanasi, Ph (0542) 2363455. www.catjee.in

STRUCTURE OF ATOM Page No.[83]
 n2 
We need to check for   1 for given options

 Z 

n 2 22
So, for Be3  1
Z 4
Z
2.18 106
v n
14.(a) Angular speed  
r n2
0.529 1010 
Z

Z2 4.12 1016
 4.12 1016   (for H-atom Z = 1)
n3 n3
So, maximum angular speed is for n = 1 = 4.12 × 1016 rad/s
15.(b) Radius of 3rd orbit in H-atom = x
n2
 rn  0.529 1010
Z

 9
r1   0.529   Å  x
 1

Radius of 4th orbit in Li2+ atom

 16  r (16 / 3) 16 16 16
r2   0.529   Å  2    r2  r1  r2  x
 3 r1 (9 /1) 27 27 27

In chapter exercise – 5 (Energy and other parameter calculation)

Subjective:
1. Number of revolutions per second by an electron in a shell is called orbital frequency.
Velocity
frequency( f ) =
Circumference
2. It is the time taken by electron ton complete one revolution. Time period of revolution of electron in nth
orbit (Tn) is given by:
circumference
Tn 
velocity
1
3. If T= time period and f = frequency, then T 
f
V2
4. Centripetal acceleration =
r
z2 z2 z2
5. E  Eo  2
, P  2  (E o  2 ), K  E o  2
n n n
Where E= Total energy, P= potential energy, K -= Kinetic energy , Eo = –13.6 eV

Objective:
2 rn n3 T1 (13 /12 ) 1
1.(d) Tn   1.5 1016  2 second   
vn Z T2 (23 /12 ) 8

n3 n2
2.(c) Tn  1.5 1016 second  rn  0.529  Å
Z2 Z
r1 1 n12
Given,   (for H-atom Z = 1)  n 2  2n1
r2 4 n 22

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STRUCTURE OF ATOM Page No.[84]
3
T1 n13 T1  1  1
Now,  (for H-atom Z = 1)    
T2 n 32 T2  2  8
2 r
3.(b) Tn  …(i)
v
nh nh
mv r   v …(ii)
2 2 m r
2 r 4 m r 2
From Eqs. (i) and (ii)  Tn   2 m r  Tn 
nh nh
Z2 13.6
4.(a) E n  13.6   En  (for H-atom)
n 2
n2
13.6
For n = 2  E2   3.4 eV
22
Energy cannot be in between (– 13.6) and (– 3.4) and energy cannot be positive in orbits (Bound system).
13.6 13.6
5.(c) E n   (second excited state, n = 3) = – 1.51 eV.
n2 32
E 
 He , n  2  (22 / 22 )
Z2
6.(b) E n  13.6  2 eV     4 :1  E   4  (3.4)  13.6 eV
n E H, n  2 (12 / 22 ) 
He

7.(b) E n  13.6 
Z2
eV 
 EH, n 2  
(12 /12 )

4
n2 E  (32 / 22 ) 9
 Li2 , n  2 
 

8.(a)
 EH,n 1  
(12 /12 )

4 1

E  2
(4 / 2 ) 2
16 4
 Be3 ,n  2 
 
K.E. 1
9.(b) P.E.  2  (K.E.) 
P.E. 2
Z2
10.(b) v  6.67 1015  rev / s
n3
 Z2  27.2 1
11.(b) P.E.  2  (Total Energy)  2  13.6  2  eV  eV
n   n2
1
P.E.  i.e. as „n‟ increases, P.E. also increases
n2
Z2
12.(c) E n  13.6  eV  For ground state, n = 1
n2
54.4
E1  13.6  Z2  54.5eV  Z2   4  Z = 2 i.e. He atom.
+
13.6
13.(d) For H-like, „Z‟ is different for different atoms.
Parametric independent of „Z‟ is
n2 Z 1 Z2
rn  0.529  Å …(a) vn  2.81106 ms …(b) E n  13.6  eV …(c)
Z n n2
nh
mvr   So, angular momentum will be same for all H-like atoms.
2
14.(b) Using above (a), (b), (c) equations and replacing them in given expressions.
The quantity independent of „n‟ will be „E.r‟.
1 Ze2 1 3e2
15.(a) P.E.      ['z ' (for Li 2 )  3]
40 r 40 r

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STRUCTURE OF ATOM Page No.[85]
n3
16.(c) Tn 
Z2
T1 (13 / 32 ) 1
For Le2+ (Z = 3)   
T2 (23 / 32 ) 8
17.(b) Revolution in one second = frequency „v‟
Z2
and v  6.67 1015  rev / s
n3
Putting n = 2 and Z = 1 (H-atom)
12
v  6.67 1015  3
 8.33 1014 rev / s
2
18.(a) K.E. = – T.E.
| T.E. |
 | K.E. |  | T.E. |  1
| K.E. |
19.(b) Sum of (K.E.) and (P.E) = Total energy
Z2 32
 13.6  2
eV  13.6  2
[1st excited state, (n = 2), Li2+(Z = 3)]
n 2
= – 30.6 eV
 30.6 1.6 1019 J (1eV  1.6 1019 J)  4.89 1018 J
20.(8) Number of revolutions (in 10– 8 seconds)
= orbital frequency (i.e number of revolution in 1 s) × time
 15 Z
2  8
  6.66  10    (10 ) (Read theory to get this formula of frequency)
 3
 n 
 Putting n = 2, Z = 1, we get
6
 8.325  10  8million  n = 8

In chapter exercise -6 (Electronic transition)

 2.18 1018 J atom1  – 19 –1
1. E  E  E 2  0     = 5.45 × 10 J atom
 2
 2 
c
E  hv  h

hc (6.626 1034 Js)(3 108 ms 1 )
or    19
= 3.647 × 10– 7 m = 3.647 × 10– 5 cm
E 5.45 10 J
hc 6.626 1034  3 108 6.626 1034  3 108
2. E  = 4.4 1019 J   
  4.4 1019
 4.51107 m  0.45 10x m  x = 6
21.8 1019
3. En   2
J atom1
n
For ionization from 5th orbit, n1 = 5, n2 = 
 1 1 
 E  E 2  E1  21.8 1019  2  2 
n 
 2 n1 
 1 1  19  1 1
 21.8 1019  2  2 – 20
  21.8 10  2   = 8.72 × 10 J
n 5  
 1 n2 
For ionization from 1st orbit, n1 = 1, n2 = 

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STRUCTURE OF ATOM Page No.[86]
1 1
E '  21.8 1019  2    21.8 1019 J
1  
E ' 21.8 1019
  25
E 8.72 1020
Thus, the energy required to remove electron from 1st orbit is 25 times than that required to remove electron
from 5th orbit.
1 1  1 1
= RZ2  2  2  =109678(1)2  2  2  cm1 = 20564.625 cm–1
1
4.
λ  n1 n 2  2 4 

   4.86 × 10–5 cm = 4.86 × 10–5 × 107 nm = 486 nm

1 1 
5. Energy required = 2.18 1018  2  2  = 2.09 × 10–18 J
1 5 
hc 6.626 1034  3 108
Also, for wavelength, = 2.09 1018  λ= = 95.1 nm
λ 2.09 1018
Objective :
1 1
1.(c) E  2.18 1018 Z2  2  2  J / atom
2 6 
 36  4 
E for 1 mole  2.18 1018  22  3
  6.022 10 10 kJ / mol
23
= 1166 kJ/mol
 4  36 
nh 3.1652 1034  2  3.14
2.(b) mvr   3.1652 1034 kg m2s 1  n  n  3.14  3
2 6.626 1034
1 1 1
So,  R.22  2  2  (first excited state, n = 2)
 2 3 
1  4  5  5R
 R  
  36  9
Z2 hc Z2 6.626 1034  3 108
3.[b] E n  13.6  E  hv   13.6 2   Z2  4  Z  2
n2  1 228 1010 1.6 1019
912Å 912  1010 m
4.[d]   = 1026 × 10– 10 m = 1.026 × 10– 5 cm
 1 1   1 1 
Z2  2  2  1  2  2 
2

 1
n n 
2
1 3 

So, (3 – log ) = 3 + 5 = 8
912Å
 1216  1010 m = 1.216 × 10 m
–7
5.[c] 
21 1
Z  2  2
1 2 
= 0.1216 µ m    0.1216  50  6

6.[a] The process, He+ (g)  He+2 g) + e–

indicates the removal of electron from He+ ion. The energy required in this process will be same as energy
of He+ ion in ground state with opposite sign.
2.18 1018
Now, energy of He+ ion in ground state =  22 J
12
2.18 1018
 Energy required = 2
 22 J = 8.72 × 10–18 J
1
c 3  10 8
7.[a] f1    5.093  1014
 589  109

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STRUCTURE OF ATOM Page No.[87]
c 3 108
f2  = =5.088 × 1014
 589.6
E = h (f1  f 2 )
=6.626 × 10–34 (5.093×1014 – 5.088 × 1014) = 3.313 × 10–22 J
 1 1  5 –1
8.[c]   109677cm1   2   109677  36 = 15232.9 cm
2 3 
2

c
E  hf  h  hc  (6.626 1034 Js)(3.0 1010 cms 1 )(15232.9cm1 ) = 3.028 × 10– 19 J

  c  3.0 1010 cms1 15232.9cm1 = 4.57 × 1014 s– 1.

In chapter exercise – 7 (Hydrogen spectrum)

1. For Balmer series, n1 = 2, Hence,
 1 1  1 1
= 109678  2  2  cm1 =1.523 × 104 cm–1 = 1.523 × 106 m–1
1
  R  2 ν=
2
2
n2  λ  2 3 

1  1 1 
2. =RZ2  2  2 
λ  n1 n 2 
For He,
1  1 1 
=R(2)2  2  2  . . . (1)
λ 2 4 
For H,
1  1 1 
=R  2  2  . . . (2)
λ  n1 n 2 
By (1) and (2),

 1 1   1 1  1 1 1 1 
(2)2  2  2    2  2   2  2   2  2 
2  
4   n1 n 2  n1 n 2  1 2 

This means that n1 = 1 and n2 = 2

Thus, the transition is from n2 = 2 to n1 = 1 in case of hydrogen spectrum.
3. For 1285 nm,

c 3  108
   2.33  1014
 1285  109
Now, by
 1 1   1 1 
  3.29  1015  2  2   2.33×1014 = 3.29 1015  2  2 
3 n  3 n 

1 1 2.33 1014
  =  n = 4.98  5
32 n2 3.29 1015
The wavelength 1285 nm is found to be in infrared region.
4. Radius of initial orbit  r0  n 2  0.529Å ( Where, r0 =Bohr‟s radius)

 1.3225 109  0.529 1010  n 22

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STRUCTURE OF ATOM Page No.[88]
 n 22  25
or n2  5

Similarly 211.6 1012  0.529 1010  n12

or n12  4
or n1  2
1  1 1   1 1 
by =R  2  2  =109678  2  2  cm1
λ  n1 n 2  2 5 

 =4.34 × 10–5 cm =434 nm

Since this is the transition from n2 = 5 to n1 = 2, this transition belongs to Balmer series.

 1 1   1 1  1 1 
5.   109677cm1   2   109677   2  2   109677    cm1  20564.4cm-1
2 4   4 16 
2
 n1 n 2 
6. The line spectrum of any element has lines corresponding to definite wavelengths. Lines are obtained as a
result of electronic transition between the energy levels. Hence, the electrons in these levels have fixed
energy, i.e. quantized values.
Objective:
1 1 1  1
1.(a) Hydrogen like spectrum will be for 1 electron system.  RZ2  2  2    Z2
  n1 n 2  

One fourth wavelength will be for Z2 = 4 i.e. Z = 2 (He+ atom)

2.(d) For Balmer series

1 1 1  1
 RZ2  2  2    Z2
  2 n 2  

1 1 1 1
   2      3  9 15200 cm  136800 cm
2
 Li  H
3.(b) Temperature of hydrogen is much smaller in laboratory than on star.
4.(a) Transitions may be 4  2 ; 4  3  2 (3 wavelength possible)
912Å

1 1 
Z2  2  2 
 n1 n 2 
912Å
1   486.4 nm
 1 1 
12  2  2 
2 4 

912Å
2   656.6 nm
 1 1 
1  2 2
2
2 3 

912Å
3   1876 nm
2 1 1 
1  2 2
3 4 

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STRUCTURE OF ATOM Page No.[89]
In chapter exercise – 8 (de-Broglie equation)
Subjective:
6.626 1034
= 3.55 × 10–11 m
h
1. By de Broglie equation,   = 31
mv 9.110  2.05 10 7

h 6.626 1034
2. λ= = = 8967 Å
2 m K.E. 2  9.11031  3.0 1025

h 6.626 1034
3. λ= = = 4.55 Å = 455 pm
mv 9.11031 1.6 106

h 6.626 1034
4. λ= = = 332 pm
mv 9.11031  2.19 106

6.626 1034
= 1.51 × 10–38 m
h
5. λ= =
mv 0.1 4.37 105

h
6. According to Bohr postulate of angular momentum, mvr = n
2π

h  h  nh
According to de Broglie equation, λ =  2πr
 = n    mvr 
mv Circumference mv  2
de-Broglie wavelength

6.626 1034
= 495.95 m s–1
h h
7. λ=  ν= =
mv mλ 1.67 1027  800 1012

8. m = 100 g = 0.1 kg ,  = 100 km/hr

100 1000m 1000 1
  ms
60  60s 36

h 6.626 1034 kg m2 s 1
  = 2.385 × 10– 34 m
m (0.1kg)(1000 / 36 ms 1 )

h h h
9.  . For same value of l for two different particles,  , i.e., m12  m22 . Thus, less the
m m11 m 22
mass, greater will be the velocity. Hence, electron.
Objective:
h
1.(b)  . For same value of u, larger the value of mass m, shorter is the wavelength, . Here, -particles
m
have the largest mass.

h h  6.63 1034  n 
2.(b)      metres    n  (3.342Å)
p mv  9.11031  2.18 106
 

So, possible values of „‟ are integral multiple of 3.342 Å.

So, 4.98 Å is not possible.
h 6.63 1034
3.(a)   = 11.05 × 10– 34 = 1.105 × 10– 33  10– 33 m
mv 0.060 10

h 6.63 1034
4.(c)   = 6.63 × 10– 34  10– 30 m
mv 0.2  5
[Approximation as per the options]

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STRUCTURE OF ATOM Page No.[90]
h 1 mn 1.67 1027 kg
5.(c)  ,   31
= 1835.16  1.76 × 103
mv  2 me 9.110 kg

h 1 E1 200 2
6.(d)      i.e. 2 : 1
2m.E 2 E2 50 1

h
7.(c)  and E = q V = 1.6 × 10– 19 × 10000 = 1.6 × 10– 15 J
2m.E

6.63 1034 6.63 1034

So,     1.23 1011
2  9.110 31
1.6 10 15 5.39 1023

= 0.0123 × 10– 9 m = 0.0123 nm

h h 6.6 1034
8.(a)   p   3 1023 kg ms 1
p  2.2 1011

hc hc E 6  1.6  1019  106 J

9.(d) E   pc  p    3.2  1021 kgm / s
 h c 3  108m
p s

In chapter exercise – 9 (Heisenberg uncertaintly principle)

Subjective:
h h 1 h 1
1. P·x  , P  ·  
4π 4π x 4π 0.002 109

2. m = 10 g = 10 × 10– 3 kg = 10– 2 kg
4
Uncertainty in speed ( )  4% of 90 ms– 1   90  3.6 ms-1
100
h
x  (m   ) 
4

h 6.626 1034 kg m2 s 1
 x   =1.46 × 10–33 m.
4 m 4  3.14  (10 kg)(3.6ms )
2 1

3. Like de Broglie equation, although Heisenberg‟s uncertainty principle holds good for all objects but it is of
significance only for microscopic particle. The reason for this is quite obvious. The energy of the photon is
insufficient to change the position and velocity of bigger bodies when it collides with them. For example,
the light from a torch falling on a running rat in a dark room neither changes the speed of the rat nor its
direction, i.e., position.
This may be further illustrated with the following examples :
For a particle of mass 1 mg, we have
h 6.626 1034 kg m 2s 1 – 28 2 –1
x.    10 m s .
4 m 6
4  3.14  (10 kg)

Thus, the product of x and  is extremely small. For particles of mass greater than 1 mg, the product
will be still smaller. Hence, these values are negligible.
For a microscopic particle like an electron, we have
h 6.626 1034 kgm2s 1
x.    104 m2s1
4m 4  3.1416  (9.111031 kg)

Thus, if uncertainty in position is 10–4 m, uncertainty in velocity will be = 1.0 ms– 1 which is quite
significant. It is for this reason that Bohr‟s concept of fixed circular path with definite position and
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STRUCTURE OF ATOM Page No.[91]
momentum of the electron have been replaced by stating that the electron has the probability of having a
given position and momentum. This forms the basis of quantum or wave mechanical model of atom,
discussed in the next section.
Since in everyday life, we come across big object only, the position and velocity of which can be measured
accurately. Heisenberg‟s principle has no significance in everyday life.
6.63 1034
4. x  = 1.933 × 10– 2 m
31  300  0.001 
4  3.14  9.110   
 100 
h
5. x.p 
4

6.63 1034
 0.5278 1029 = 5.278 × 10
– 30
x  5
m
4  3.14 1.0 10
Objective:
h
1.(d) x.p  , x  0 and p = infinite
4

2.5 1019
p  2.5 1019 g cm s1  kg m s 1 = 2.5 × 10
– 24
2.(a) kg m s– 1
1000 100

h 6.6 1034
 x   = 0.210 × 10– 10 m = 21.0 × 10– 12 m
4p 4  3.14  2.5 1024

 3n = 21, n = 7

h 6.6 1034
3. (b) (i) x   = 52.54 × 10– 31 m = 5.254 × 10– 20 Å  x = 5
4mv 4  3.14 1103  0.01

6.6 1034
(ii) x  = 5.7 × 10– 2 × 10– 3 m  6 × 10– 5  x = 5
4  3.14  9.11031 1

h 6.6 1034
4.(c) x.v   = 5.7 × 10– 5 m2 s– 1
4m 4  3.14  9.11031
= 5.7 × 10– 5 × 106 mm2 s– 1 = 6 × 101 mm2 s– 1  x = 1
h 6.6 1034 1 30
5.(d) x.v  m 10 24
 9.97 102 100   m 3
4m 4  3.14 10  5.7 10 10 10

In chapter exercise – 10 (Schrondinger equation)

1.(c) Schrodinger‟s wave equation
2 2  2 82 m
   (E  V)  0
x 2 y2 z 2 h2

2.(d) Wave mechanical model is dependent on De Broglie concept, Heisenberg‟s principle and Schrodinger
wave equation.
3.(a) Solution of "  " corresponds to definite energy state and is called orbital.

4. (b) At radial node  |  |2  0 ie 2s  0

 r 
 2 0   0 ; [as other terms cannot be taken zero]  r0 = 2a0
 a 0 
5.(d) For 1s orbital, probability of finding the electron at the nucleus is zero.]

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STRUCTURE OF ATOM Page No.[92]
In chapter exercise – 11 (Quantum numbers)
Subjective
1. The sequence in which the g–orbitals come is s, p, d, f, g. Since it comes at fifth place, hence the lowest
value of n which allows g–orbitals to exist is n = 5.
2. Possible value for the given electron is: n =3, l =2, m = –2, –1, 0, +1, +2
3. (i) n  3l  0 m  0
 l  1  m  1, 0,  1
 l  2  m  2,  1, 0,  1,  2
(ii) For 3d, l=2 and ml= –2, –1, 0, +1, +2
(iii) 2s and 2p are possible orbitals and 1p and 3f are not possible.
4. (a) n = 1, l = 0 represents 1s orbital.
(b) n = 3, l = 2 represents 3d orbital.
(c) n = 4, l = 2 represents 4d orbital.
(d) n = 4, l = 3 represents 4f orbital.
5. (a) It is not possible as n can never be zero.
(b) This set of quantum numbers is possible.
(c) It is not possible because for n = 1, l can be zero only.
(d) This set of quantum numbers is possible.
(e) It is not possible because for n = 3, l can never be 3.
(f) This set of quantum numbers is possible.

6. (a) Since a shell contains at most 2n2 electrons half of which have ms = –1/2 and

another half have ms = +1/2. So for ms = –1/2 number of electrons = n2

 For n = 4 it is 42  16
(b) l = 0 corresponds to s orbital.
 For n = 3 and l = 0, number of electrons = 2
7. (n + l) value for 1 = 4+2=6
(n + l) value for 2 = 3+2=5
(n + l) value for 3 = 4+1=5
(n + l) value for 4 = 3+2=5
(n + l) value for 5 = 3+1=4
(n + l) value for 6 = 4+1=5
As we know for higher value of (n + l), energy of electron is high and for same value of (n + l), electron
with high value „n‟ has high energy.
 The order of increasing energy will be: E5  E2  E4  E3  E6  E1
8. (a) Number of sub–shells = Principal quantum number = 4
(b) Total number electrons associated with n = 4 is 2n 2  2(4)2  32
half of them, i.e., 16, will have ms = –1/2.
Objective
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STRUCTURE OF ATOM Page No.[93]
1.(b) Only XY plane is nodal plane..
2.(c) As d z2 has a ring in shape.

3.(a) Px has one nodal plane yz.

4.(d) All have four lobes.
5.(a) Spherical nodes are radial nodes = n – l – 1. = 3 – 1 – 1 = 1.
6.(a) Radial nodes = n–l–1
in “3s” 
 3–0–1=2
in “2p” 
 2–1–1=0
7.(d) d x 2  y2 has diagonal node, d xy , d yz , d xz has axial node.

8.(a) 3d z2 has two positive lobes along ± z – axis and a negative doughnut in xy plane.

9.(a) Angular nodes or nodal planes = l = 3 (for f –orbital)

10.(c) No. of orbitals in 3rd shell (n = 3) = n2 = 32 = 9.
h
11.(a) Orbital angular momentum  (  1) . Hence, it depends only on „l‟.
2
12.(c) There are 7 orbitals in f –subshell and hence a total of 14 electrons can be accommodated.
13.(a)
14.(d) Total number of subshell = principle quantum no.
15.(c) For l = 1, „m‟ cant be equal to 2
16.(c) (ii) Shape of orbital is given by azimuthal quantum number.
(iv) Electron have different velocities according to their shell to which they belong.
1 1
17.(d)  and  are representing relative rotation.
2 2
m 1
18.(c) As m = (– l) to (+ l)  m = 2l + 1   
2
19.(c) In nth shell total electrons are = 2n2  n2 orbitals as each orbital has 2 electrons.
20.(d) Higher the value of (n + l), higher is the energy.
21.(b) n
22.(b) maximum number of electron in a subshell (like s, p, d, f)  2(2  1)  4  2
23.(d) Shapes of d x2  y2 , Px , Py , PZ are axially oriented.

24.(c) „m‟ describes the orientation or distribution of electron cloud.

25.(c) For g-orbital,   4  n  5  no. of orbitals = 1(s) + 3(p) + 5(d) + 7(f) + 9(g) = 25.

26.(a) Pz is axially aligned to z-axis. And xy plane is nodal plane for p z orbital.
27.(c) Higher the value of (n + l), higher is the energy.
28.(d) “Spin” is not obtained from Schrodinger‟s wave equation
29.(d) No. of orbitals in a subshell (s, p, d,..) = (2l + 1) and for principle quantum no. n, l varies from O to (n – 1).
30.(b)
31.(a) Radial nodes = n – l – 1 = 13 – 0 – 1 = 12.
32.(c) Nodal plane for spherical „s‟ orbital = zero.

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STRUCTURE OF ATOM Page No.[94]
33.(a) Radial nodes = n – l – 1
Angular nodes = l
Total nodes = n – 1
In chapter exercise – 12 (Electronic configuration)
Objective Questions
1.(i) Electronic configurations of
(a) H is 1s2 (b) Na  is 1s2 , 2s2 2p6 (c) O2 is 1s2 , 2s2 2p6 (d) F is 1s2 , 2s2 2p6

(ii) (a) Orbital which are filled before 3s1 is: 1s2 , 2s2 2p6
 Total number of electrons (i.e., atomic number) =2 + 2 + 6 + 1 =11

(b) Orbitals which are filled before 2p3 is: 1s2, 2s2
 Atomic number = 2 + 2 + 3 = 7

(c) Orbital which are filled before 3p5 is: 2s2 2p6 , 3s2
 Atomic number = 2 + 2 + 6 + 2 + 5 = 17
(iii) (a) Li (b) P (c) Sc
1s 2s 2p

2.
O=
8

3. 28Ni = [Ar]18 3d8 4s2. To form Ni2+ ion, it will lose electrons from 4s.
4. Degenerate orbitals are the orbitals of the same subshell of the same main shell. Hence, these are
(3d xy , 3d z , 3d yz ) and (4d xy , 4d yz , 4d z ) .
2 2

5.I. (a) (n + l) values are 1s = 1 + 0 = 1, 2s = 2 + 0 = 2, 3s = 3 + 0 = 3, 2p = 2+ 1 = 3

Hence, increasing order of their energy is 1s < 2s < 2p < 3s.
(b) 4s = 4 + 0 = 4, 3s = 3 + 0 = 3, 3p = 3 + 1 = 4, 4d = 4 + 2 = 6. Hence, 3s < 3p < 4s < 4d.
(c) 5p = 5 + 1 = 6, 4d = 4 + 2 = 6, 5d = 5 + 2 = 7, 4f = 4 + 3 = 7, 6s = 6 + 0 = 6.
Hence, 4d < 5p < 6s < 4f < 5d.
(d) 5f = 5 + 3 = 8, 6d = 6 + 2 = 8, 7s = 7 + 0 = 7, 7p = 7 + 1 = 8. Hence, 7s < 5f < 6d < 7p.
II. (a) 4d = 4 + 2 = 6, 4f = 4 + 3 = 7, 5s = 5 + 0 = 5, 7p = 7 + 1 = 8. Hence, 5s has the lowest energy.
(b) 5p = 5 + 1 = 6, 5d = 5 + 2 = 7, 5f = 5 + 3 = 8, 6s = 6 + 0 = 6, 6p = 6 + 1 = 7.
Hence, 5f has highest energy.
6. Configurations with completely filled and half filled orbitals have extra stability. In 3d 104s1, d-orbitals are
completely filled and s-orbital is half filled. Hence, it is a more stable configuration.
7. 15P = [Ne] 3s2 3p3 i.e. n = 3 [n = number of unpaired electrons]

14 Si  [Ne] 3s2 3p2 ; n=2

24 Cr  [Ar]4s1 3d5 ; n=6

26 Fe  [Ar] 4s2 3d6 ; n=4

8. Energy is decided by (n+l ) rule. Higher the value of (n+l ), higher will be the energy.
Hence (1)  4+2 > (3)  4+1 = (6)  4+1 > (2)  3+2 = (4)  3+2 > (5)  3+1
Objective Questions:

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STRUCTURE OF ATOM Page No.[95]
1.(b) Correct configuration (b) should be : 1s2 , 2s2 2p6 , 3s2 3p6 3d9 4s2
2.(b) Cr3+ = [Ar]18 3d3, Fe3+ = [Ar]18 3d5, Mn2+ = [Ar]18 3d5
Thus, Fe3+ and Mn2+ have the same electronic configuration.
3.(c) For Fe  Z  26; [Ar] 4s2 3d6
4.(a) Same electron configuration is for isoelectronic species.
5.(a) For Mn  [Ar]4s2 3d5  5 unpaired electrons.
–
6.(b) m  0 , can be for s, p, d, etc orbitals and d orbital can accommodate max. 10 e .

7.(d) Increasing value of (n + l) decides increasing energy value.

8.(d) Spin quantum number.
9.(d) Highest (n + l) value corresponds to (d) option.
10.(d) In degenerate orbitals.
11.(a) 1s is ground state for H-atom.
–
12.(a) 31 Ga  [Ar] 4s2 3d10 4p1 last e is in 4p.

13.(a) (n + l) rule
14.(d) Cr 6  [Ar] 4s0 3d0 no unpaired electron.

15.(c) Co2  [Ar] 4s0 3d7 electron is removed from outershell first.
16.(b) Violates Auf bau principle.
17.(a) Mn 4  [Ar] 4s0 3d3 i.e. 3 unpaired electron.
18.(a) Aufbau principle
19.(d) m  1  min. azimuthal quantum no. l = 1
 l = 0 not possible (s orbital)
20.(d) Electron is removed from outer shell first.
21.(a) In (b) and (c) Hund‟s rule is violated.
22.(c) „s‟ can have maximum 2 electrons.
23.(d) Fe2  [Ar]4s0 3d6 ; 3d-electron are 6.

24.(d) For Cr  [Ar] 4s1 3d5

25.(d)
26.(d) Fe2  [Ar] 4s0 3d6 i.e. 2(1s) + 2(2s) + 2(3s) = 6 s electrons i.e. P-atom.

In chapter exercise -13 (Magnetic properties and miscellaneous)

h
1.(a)   (  1).
2

h 6h
For d-orbital, l = 2, i.e. 2(3) 
2 2
2.(b) For s-orbital l = 0,    0

h 2h
3.(d) For 2p electron ,   (  1) 
2 2

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STRUCTURE OF ATOM Page No.[96]

h 1 11  h 3 h
4.(c) Spin angular momentum  s(s  1) ; put s     1  .
2 2 2  2  2 2 2

5.(a) Cu  :1s2 , 2s2 2p6 , 3s2 3p6 3d10  it is diamagnetic as it has no unpaired electron.

6.(d) 1s2 , 2s2 2p6 , 3s2 3p6 3d1

  n(n  2)  1.73  n = 1

23 V  [Ar]4s2 3d3 ; n = 3

V4  [Ar]4s0 3d1 ; n = 1

So, it in V4 + ion.
7.(a) Mn 2  [Ar]4s0 3d5 ; n = 1

Fe2  [Ar]4s0 3d6 ; n  4

Ti2  [Ar] 4s0 3d 2 ; n  2

Cr 2  [Ar] 4s0 3d 4 ; n  4

  1  p-orbital e–  6(2p) + 6(3p) = 12 electron.

  2  d-orbital e–  5(3d) = 5 electron.

8.(a) Ni2  [Ar]4s0 3d8 i.e. n  2 (unpaired electron)

  n(n  2)  2.84 BM

9.(c)   n(n  2)    number of unpaired electron.

V  [Ar]4s2 3d3 n = 3

Cr  [Ar]4s1 3d5 n = 6

Mn  [Ar] 4s2 3d5 n = 5

JEE MAIN PREVIOUS YEARS ASKED QUESTION

1.(a)
2.(c) Second excited state  n = 3
13.6
E  1.51 eV
32
h 6.626 1034
3.(a) x.v   v  5
= 2.11028
4m 4  3.14  0.025 10
4.(b) Visible range transition corresponds to Balmer series (n1 = 2).
So, 1st line in 3  2 (red end belongs to least energy)
2nd line is 4  2
3rd line is 5  2
n 6.63 1034
5.(a)    1033 metres
mv 0.06 10
6.(b) s-orbital  l = 0  momentum = 0
7.(d) As in solution to Q.23.
8.(c) For 4f ; n = 4, l = 3, m [3,  3]
i.e. m  4,  4
9.(d)

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STRUCTURE OF ATOM Page No.[97]
912Å 912Å
10.(a)     9.12 108 m  91 nm

2 1 1  21 1 
Z  2  2 1  2  2
 n1 n 2  1  
11.(a) (n + l) rule.
nh 5h
12.(d) mvr  
2 2
h
13.(c) x  [v  300  0.001%  3 103 ]
4 m v
6.63 1034
  1.92 102 m
4  3.14  9.11031  3 103
14.(a) Isoelectronic species have same no. of electrons.
15.(a)
16.(c) (n + l) rule.
1 1 
17.(a) E  E H .  2  2  when EH = ionization enthalpy of H-atom.
 n1 n 2 
h 6.63 1034
18.(b)  
mv 1.67 1027 1103
 3.97 1010 m  0.397 nm  0.40 nm
19.(a) B.E. (for 1 mole) = 242 kJ
242 103
For (1 Cl – Cl atom)  J  4.011019 J
6.02 1023
Longest wavelength belongs to least energy.
6.63 1034  3 108
  494 nm
4.011019
Z2 E 2 Z 2
20.(c) E  2  Li  Li (for same value of n)
n E He ZHe
9
E Li2  19.6 1018 J atom1  4.411017 J atm1
4
hc hc hc
21.(c) By energy conservation   (emitted 1 &  2 )
absorbed 1 2
1 1
2   nm  743 nm
1 1   1 1 
    355  680 
  1   
22.(a) (n + l) rule.
23.(b) Given, atomic number of Rb, Z = 37
Thus, its electronic configuration is [Kr]5s1. Since, the last electron or valence electron enter in 5s
subshell.
So, the quantum numbers are n = 5, l = 0, (for s-orbital) m = 0
( m = + l to – l), s = + 1/2, or – 1/2.
 Z2 
24.(b) Given, in the question E  2.178 1018 J  2 
 n 
For hydrogen Z = 1,
1
So, E1  2.18 1018 J  2 
1  
1
E 2  2.18 1018 J  2 
2 
Now, E1  E2
1 1  hc
i.e., E  2.178 1018    
 12 22 

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STRUCTURE OF ATOM Page No.[98]
34
1 1  6.62 10  3.0 10
8
2.178 1018  2  2 
1 2  
   1.21107 m
13.6
25.(b)  E n   eV where, n = 1, 2, 3…..
n2
13.6
In excited states, E 2   3.4 eV
4
h h h h
26.(b)       2m eV
P 2mE 2m eV 

n2
27.[b] r  a 0  0.529  4  2.12Å
Z
28.[c] n  2r
n2 2a 0 n 2 2a 0 n 2
r  a0  n   
z z z
n n 3
1.5 a 0  2a 0    0.75
2 z 4
1
29.[b] For electron,  DB  (de broglie wavelength)
2mK.E.
By photoelectric effect h0  KE ,
KE  h  h0
h 1
 DB    DB 
2m  (h  h 0 ) (   0 )1/2
Z2
30.[a] (E)n th  (E GND ) H .
n2
22
E3rd (He )  (13.6eV).  6.04eV
32
31.[d] An electron in an orbital of high angular momentum stays away from the nucleus than an electron in the
orbital of lower angular momentum.
h
According to wave mechanics, the ground state angular momentum is h equal to .
2
1  1 1  1 1   1 1  1 1
32.[d]    R H Z2  2  2    R H  2  2   R H   2  2     R H  2  R H  2
  i f  8 nf   8 nf   8
33.[b] In photoelectric effect, E = w + KE
It is given that KE of ejected electron is very high in comparison to work function w.
hc P 2 1
E = KE    P2 
 2m 
2 2
 P2  1  1.5P1  1
     
 P1   2  P1  2
2
3 1 9  4
     1  2  1
2 2 4 2 3
34.[d] Smaller the value of (n+l), smaller the energy. If two or more sub-orbitals have same values of (n+1), sub-
orbitals with lower values of n has lower energy. The (n+l) value of the given option are as follows:
I. = n    6 II. n    5 III. n    5 IV. n    4
The correct order of their increasing energies will be: IV < II < III < I
n2
35.[d] 2r  n  2 a 0  n
Z
2
4
2 a 0  4    8a 0
1
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STRUCTURE OF ATOM Page No.[99]
1 1 
36.[d]   R H  2  2
 n1 mn 2 
(I) As the wavelength decreases the energy increases therefore the spectrum lines become bond and
formed a converging series.
(II) For balmer series always started ground state n1  2
(III) At longest wavelength, the higher state energy will be minimum therefore excited state will be
n 2  3 nest to the ground always.
z2
(IV) E  13.6 for H atom z=1
n2
So, we cannot find ionization energy directly by only wave number, we also required transition state
(n) value. According to the above observation: only I, II and III are correct.
1
37.[b] n  5, ms  
2
Thus, values of  are from 0 to (n–1)
  0 to 4
Now, the total number of orbitals  n 2  52  25
n2
38.[c] r  0.529 Å
2
0.529
For He (rHe )n 4  (rHe )n 3  [16  9]  y
2
0.529 y 3
For Li 2 (rLi2 )n 4  (rLi2 )n 4  [16  9]  z  
2 z 2
39.[a] Number of radial nodes: n  1  1
Number of angular nodes : 2
1  2;  d  orbital
n   1  2
n  2 1  2
n  5  5d
40.[b] Radial node =  n    1  3  0  1  2

41.[b] Based on "n   " rule only (B) has pair of electron in degenerate orbitals.
a n2
42.[c] (r3 )H  0  a 0  32  9a 0
Z
2r  n
 2 9a 0  3
  6a 0

Raman Niwas, Near Akashwani, Mahmoorganj, Varanasi, Ph (0542) 2363455. www.catjee.in

STRUCTURE OF ATOM Page No.[100]

Solution to Question Bank for JEE Advanced Aspirants

Exercise -1
Topic -1 : Thomson and Rutherford Model:
1.(a) -particle can never get attracted towards the nucleus of any atom.
q1  q 2
2.(b) r
 40  KE


9 10    2 1.602 10    79 1.602 10   4.22 10
9 19 19
14
m
5.4 10 1.602 10 
6 19

1 q q
3.(c) For the distance of closest approach, mv 2  1 2
2  40  r
2q1  q 2
or v 
 40  mr


9 10   2   2 1.602 10    29 1.602 10   6.35 10 m / s.
9 19 19
6

 4 1.66 10  10 27 13

Topic -2 : Planck’s quantum theory:

1. [c] nhv = (330 J/g) × 1g
330
 n
6.626 1034  5 1013
n  9.96 1021  1022
Now, 10x  1022  x  22  x  7

hc 6.626 1034  3 108

2. [a] Energy needed to ionize one Na atom    8.2 1019 J
 242 109
(8.2 1019 )  6.02 1023
Ionization energy in (kJ/mol)  kJ / mol = 493.64 kJ/mol = y
1000
 log10 (2  493.64)  log10 (987.28)  log10 (103 )  3
3.(a) Let n1 quanta (photons) of radiation are absorbed by the dye and n2 quanta of radiation are emitted out.
Given  energy emitted = 47% of energy absorbed
hc 47 hc
 nemitted   nabsorbed
emitted 100 absorbed
o
n 47  emitted  47 5080 A
 emitted     o
 0.527
nabsorbed 100  absorbed  100
4530 A

Topic -3 : Photoelectric effect

hc
1. [a] – 0 = 3V0 .....(1)

hc
–  0 = V0 .....(2)
2

Raman Niwas, Near Akashwani, Mahmoorganj, Varanasi, Ph (0542) 2363455. www.catjee.in

STRUCTURE OF ATOM Page No.[101]
hc  1
eq. (1) – eq.(2) :
 1  2  = 2V0
 
hc hc hc
= 2 V0  =  4=
2 4V0 V0
2.[d] Suppose threshold wavelength = 0 nm= 0×10– 9 m
1 1 1
Then K max  h(f  f 0 )  h c (h(v v0 )  mu 2
 0 2

Putting given values in the following equation:

hc  1 1  1
9 
   m(2.55 106 ) 2 …(i)
10  500 0  2

hc  1 1  1
9 
   m(4.35 106 )2 …(ii)
10  450 0  2

hc  1 1  1
    m(5.20 10 )
6 2
…(iii)
109  400 0  2
Dividing eqn. (ii) by eqn. (i), we get
0  450 5000   450 450  4.35 
2 2
 4.35 
    0    2.619
4500 0  500  2.55  0  500 500  2.55 
 0 – 450 = 2.619 0 – 1309.5  1.619 0 = 859.5  0 = 531 nm
Substituting this value in eqn. (iii), we get 
h  (3 108 )  1 1  1 31 – 34
 400  531   2 (9.1110 )(5.20 10 ) h = 6.66 × 10
6 2
9
Js
10  

Topic -4 : Radius and velocity of Hydrogen atom

 Z
1.(c) vn  2.18 106   ms 1
n

2.18 106
vn 
n
1
vn  ; so, the graph is hyperbolic
n
2.(d) (rn 1  rn )  rn 1
Put Z = 1 (for hydrogen atom)
 (n  1)2 n2   (n  1) 2 
 0.529   0.529     0.529  
 1 1   1 
 (n  1)2  n 2  (n  1)2  2n  1  n 2  1  2n

 n 2  4n  0 n4 (as n  0)

n2
3.(a) rn  0.529  Å
Z
for hydrogen atom, Z = 1
rn  0.529n 2 Å

An  (rn )2

Raman Niwas, Near Akashwani, Mahmoorganj, Varanasi, Ph (0542) 2363455. www.catjee.in

STRUCTURE OF ATOM Page No.[102]
2
 A n  (rn2 )  0.529n 2 
Then,   
 0.529 
 n4
 1
A (r1
2
)  
A 
ln  n   4ln(n) i.e. (graph similar to y = mx)
 A1 
It is a straight line with slope 4, passing through origin.
Topic -5 : Energy and other parameter calculation:
1.(b) In ground state, n = 1
For H-like atom
Z2
I.E.  13.6  eV
n2
If (I.E.)A  (I.E.)B
Then, ZA  ZB (I.E.  Z2 )
Now using equation (a), (b), (c)
We get u A  u B .
Z2
2.(a) B.E.  13.6  eV
n2
For H-atom
13.6
B.E.   3.4 eV
22
1 Z2
3.(a) K.E.   (P.E.)  (T.E.)  13.6  2 eV
2 n
 Z
v  n   2.18 106   n  2.18 106 Z
 n

Z2
v  (6.67 1015 ) rev / s
n2
k.q1q 2 mv2 (Z / n)2 Z3
  C. 2 
r2 r (n / Z) n 4
So, correct options are (i, iii, iv)
4.(c) (I.E1 )He  24.6 eV
 I.E
He 
2  He2  1e

As He+ is H-like atom.

Z2 13.6  22
So, I.E 2  13.6  eV   54.4 eV
n2 12
So, total energy required = I.E.1 + I.E.2 = 24.6 + 54.4 = 79.0 eV
1 1 1 Ze2  Ze2
5.(a) K.E.   (P.E.)     .  
2 2  40 r  80 r

Z2 13.4 1
6. [a] E  13.6  eV   3.4   n2  4
n2 n2
n=2
nh 2  6.626 1034
So, angular momentum (m v r)    2.111034  
2 2  3.14

Raman Niwas, Near Akashwani, Mahmoorganj, Varanasi, Ph (0542) 2363455. www.catjee.in

STRUCTURE OF ATOM Page No.[103]

2  log 5 2  log(5  2.111034 ) 2  log(1033 ) 2  33

Value of    7
5 5 5 5

z2 z2
7.[b] E  KE  Eo 2  6.04 eV  (13.6eV)  2  6.04 eV  z 2  3.99  z  2
n 3
n2 2 o o 32 2 o 2
Area of orbit   rn  3.14  (0.529 A )  3.14  (0.529 A )  1.78 10 A
2 1

z 2
o 2 o 2
Now, 1.78 10n A  1.78 101 A  n  1
2 2 mZ2 e4
8.[c] For H-like particles, E n 
n2h2
 2 2 me4  2 2 me4
For H-atom, I.E.  E  E1  0    2 
  2.18 1018 J atom1 (given)
2
  2
 1 h  h

 2 2 m  22  e4  2 2 me4
Energy required  E  E1  0    

 4  = 4 × 2.18 × 10– 18 J = 8.72 × 10– 18 J
 1 h
2 2
 h 2

Topic -6 : Electronic transition:

1.(b) As given, let transition be from n1 to n2
 n1  n 2  4 …(i)
and n1 – n2 = 2 ….(ii)
From Eq. (i) and (ii), we get, n1 = 3 and n2 = 1
1 1 1 
  RZ2  2  2 
  n 2 n1 

1  1 1  32R
 R  22  2  2  
 1 3  9
13.6
2.(b) In H-atom, BE  eV
n2
For 0.85 eV  n = 4
& state with excitation energy 10.2 eV belongs to (n = 2)
912Å
emitted (4  2)   486.4 nm
 1 1 
12  2  2 
2 4 

3.(b) Number of H-atoms present 

w
A
 NA 
1.8
1

 6  1023  1.08  1024
From question, electrons are in 3rd orbit in
27
100
 
 1.08  1024  2.916  1023 atoms

and electrons in 2nd orbit in

15
100
 
 1.08  1024  1.62  1023 atoms.
When all atoms will de-excite to the ground state, the amount of energy released.
E  E1  E2
1 1 1 1 
      
 2.188  1018  2.916  1023  12  2  2   2.188  1018  1.62  1023  12  2  2 
1 3  1 2 

 832971.6 J  832.97 kJ
 1 1
4.(d) Ionization energy = E   E1  13.6 eV  Z2  2  2   (13.6 eV )  Z2
 1 

Raman Niwas, Near Akashwani, Mahmoorganj, Varanasi, Ph (0542) 2363455. www.catjee.in

STRUCTURE OF ATOM Page No.[104]
Given I.E.  13.6 eV  (13.6 eV )  Z  Z  1
2

 1 1
Energy involved during transition  E  13.6 eV  Z2  2  2   12.75eV
4 1 
 1
5.(d) Transition energy  13.6 1   eV  10.2eV
 4
 KE of ejected electron  10.2  2.4  7.8 eV
= 7.8 1.6 1019 J = 1.248 1018 J

Topic -7 : Hydrogen spectrum:

1.(b) Balmer series of lines in H-atom lie in visible range. So, red end corresponds to highest wavelength i.e.
lowest energy in the series.
Third line from red end will correspond to
3  2 red line (1st line)
4  2 (2nd line)
5  2 (3rd line)
So, Ans. = 5  2
2.(d) In H-atom, 12.1 eV belongs to transition (n = 1)  (n = 3)
10.2 eV belongs to (n = 1)  (n = 2)
1.9 eV belong to (n = 2)  (n = 3)
In one atom, photon is released in de-excitation
(n = 3)  (n = 1) & in another atom = (n = 3)  (n = 2)  (n = 1).
So, 2atoms only
* (n = 3)  (n = 2) cannot be in a separated 3rd atom, as e- will come surely to ground state (n = 1).
3.(d) From first information given, electron jumps from nth orbit to the second orbit emitting two photons. As
each electronic transition results the emission of a single photon, emission of two photons is possible only
when the electron is jumping from nth orbit to some intermediate orbit, emitting the radiation of energy
10.2 eV and then from this intermediate orbit to the second orbit, emitting the radiation of energy 17.0 eV.
From orbit, the energy of liberated photon  10.2  17.0  27.2 eV.
 1 1 
 E  13.6 Z2  2  2  eV
n 
 1 n2 
 1 1 
27.2  13.6 Z2  2  2  ...(1)
2 n 

Similarly, from the next information given, electron may jump directly from nth orbit to third orbit by
emitting radiation of energy 4.25 + 5.95 = 10.2 eV.
 1 1 
 E  13.6 Z2  2  2  eV
n 
 1 n2 
 1 1 
10.2  13.6 Z2  2  2  ...(2)
3 n 
From equation (1) and (2), n = 6 and Z = 3.

Topic -8 : de-Broglie equation

1
1.(a) The kinetic energy of electron, qV  mv 2
2

v
2qV
m
 
 2  1.76  1011  200  8.39  106 m /s

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STRUCTURE OF ATOM Page No.[105]
2.(b) r1 = x
r3 = 9x ( r  n2)
h
also = ……(i) (from de Broglie equation)
m
nh
and mr = ……(ii)
2
from (i) and (ii)
2r
2r = n   
n
 Wavelength for 3rd orbit.
2r3 2 9 x
3 = = = 6x.
n3 3
Topic -9 : Heisenberg uncertainty principle:
1. (a)
Topic -10 : Schrodinger equation:
1.(b) At radial node |  | = 0

From given equation,  x – 1 = 0 and x2 – 8x + 12 = 0

2 a
x–1=0  x=1  1; r  0 (Minimum)
a0 2

x2 – 8x + 12 = 0  (x – 6) (x – 2) = 0
2r
when x – 2 = 0  x =2   2, i.e., r  a 0 (Middle value)
a0
2r
when x – 6 = 0  x = 6   6  r = 3a0 (Maximum)
a0
2.(c) Number of nodes  n  l  1
3.(a)
Topic -11 : Quantum numbers:
1.(d) 4d z 2  Number of radial node = n  l  1  4  2  1  1

But d z 2 has no planer node, rather it has two nodal cone or angular node.
Topic -12 : Electronic configuration:
1.(d) Maximum number of electrons in a subshell = 2(2l  1)
Half of them will have same spin.
2.(a) O has configuration 1s2 ,2s2 2p2x 2p1y 2p1z ;
(AB) (CD) E F

3.(c) 24 Cr is : 1s2 ,2s2 2p6 ,3s2 3p6 3d5 ,4s1; 15 electrons in one direction (may be clockwise or anticlockwise)
and 9 electron in other direction.
Topic -13 : Magnetic properties and miscellaneous:
1.(a) Mn 2 has five unpaired electron. Rest all possess either no unpaired electrons (Sc3 , Zn 2 ) or have one

unpaired electron Ti3 . 
2.(a) Magnetic moment  n  n  2   4.9,
n=4
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STRUCTURE OF ATOM Page No.[106]
Thus Mn ion has four unpaired electron (n). Mn3 :1s2 ,2s2 2p6 ,3s2 3p6 3d 4
Exercise – 2 [JEE Advanced asked question]
h h
1.(a) The orbital angular momentum (L)  l(l  1)  6 (l  2for d-orbital)
2 2
2. 1s2 , 2s2 2p6 , 3s2 3p6 3d1
Magnetic moment  n(n  2) BM  1.73 BM

 n(n  2)  3  n  1 i.e. 1 unpaired electron.

So, 23 V  [Ar] 4s2 3d3

 for vanadium ion V2 i.e. [Ar] 4s2 3d1 .

3.(a) The energy of an electron in a Bohr atom is expressed as
kZ2
En   where, k  costant, Z  Atomic number, n  Orbit number ,
n2
= – 13.6 eV for H (n – 1)
13.6
When n = 2, E 2  eV  3.40 eV (n can have only integral value 1, 2, 3,…  )
22
4.(a) Cr = [Ar]3d5 4s1, an exception to aufbau principle.
(b) For a given value of l, m can have any value from (– l to + l), so can have negative value.
(c) Ag is in copper group with d10 s1 configuration, i.e., 46 electrons are spin paired.
5.(a) (i) n = 4, l = 1  4d-orbital
(ii) n = 4, l = 0  4s-orbital
(iii) n = 3, l = 2  3d-orbital
(iv) n = 3, l = 1  3d-orbital
According to Aufbau principle, energies of above mentioned orbitals are in the order of
(iv) 3p < (ii) 4s < (iii) 3d < (i) 4p
6.(a d) Both (a) and (d) are correct. The three electrons in the 2p-orbitals must have same spin, no matter up spin or
down spin.
7.(a) Nodal plane is an imaginary plane on which probability of finding an electron is minimum. Every p-orbital
has one nodal plane

px
YZ  plane, a nodal plane
9.(c) Using the de-Broglie‟s relationship
h 6.625 1034
   2.3 1030 m
mv 0.2  5
60  60
1 1
10.(d)  and  just represents two quantum mechanical spin states which have no classical analogue.
2 2
11.(c) 1s7 violate Pauli exclusion principle, according to which an orbital cannot have more than two electrons.
12.(d) Rutherford used -particle (He2+ nuclei) in his experiment.
13. The general Rydberg‟s equation is
1  1 1  1 (He ) Z(H) 2 1
v  R(Z) 2  2  2    Z2   
    (H)  2
4
 n1 n 2  Z(He )

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STRUCTURE OF ATOM Page No.[107]
(H) 91.2
 (He )   nm  22.8nm
4 4
a0n2
14.(b) Expression for Bohr‟s orbit is, rn   a 0 when n = 2, Z = 4.
Z
15. At radial node,  2 must vanishes, i.e.
2 2 r0
 1   r0   a 0 r
 22s 0   2   e  2  0  0  r0 = 2a0
 4 2   a0  a0

h 6.625 1034
 6.625 1035 m = 6.626 × 10 Å
–25
16.  
mv 100 103 100
17.(a) The number of radial nodes is given by expression (n – l – 1).
For 3s, number of nodes = 3 – 0 – 1 = 2
For 2p, number of nodes = 2 – 1 – 1 = 0
 6 h
18. (a) 2.19×10 m/s (b) 3.32 Å (c) 2 × 2π 
 
nh
(a) mvr 
2
nh 6.625 1034
 v  = 2.18 × 106 ms– 1
2 m r 2  3.14  9.11031  0.529 1010

h 6.625 1034
(b)     0.33 109 m
mv 9.11031  2.18 106
(c) Orbital angular momentum
h  h 
(L)  (  1)  2 
2  2 
[ For p-orbital, l = 1]
19.  A  R, B  Q, C  P, D  S

1  Ze2 
(a) Vn    
40  r 

1  Ze2  V
Kn     n  2 --(r)
80  r  Kn

Ze2
(b) E n   r 1  x  1 --(q)
80 r
h
(c) Angular momentum  (  1)  0 in 1s-orbital --(p).
2
a0n2 1
(d) rn   Z --(s)
Z rn
20.(b) S1 is spherically symmetrical state, i.e. it correspond to a s-orbital. Also, it has one radial node.
Number of radial nodes = n – l – 1
 n – 0 – 1 = 1  N = 2 i.e. S1 = 2s-orbital.
21.(c) Ground state energy of electron in H-atom (EH)
kZ2
EH   k(Z  1, n  1)
n2
For S1 state of Li2 +,
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STRUCTURE OF ATOM Page No.[108]
k(3)2 9
E 2
 k  2.25 k
2 4
22.(b) In S2 state E(Li2 +) = K (given)
qk
K  n=3
n2
Since, S2 has one radial node.
3 – l – 1 = 1, l = 1
23.(4) Energy of light falling metal
hc 6.63 1034  3 108
 eV  0.0414 102  4.14 eV
 300 109 1.6 1019
Photoelectric effect will be shown be metals Li, Na, K, Mg.
So, 4 metals.
24.(9) For n = 3, no. of e– = 2 × 32 = 18 e–.
 1  18
So, e– with (n = 3 &  n  3 & ms      9 e
 2 2
25.(c) According to Bohr‟s model,
nh n2h2 1 n2h2
mvr   (mv)2  2 2  KE  mv2  2 2 …(i)
2 4 r 2 8 r m
Also, Bohr‟s radius for H-atom is, r = n2a0
Substituting „r‟ in Eq. (i) gives
h2
KE  when n = 2,
82 n 2 a 02 m

h2
KE 
322 a 02 m
1 3
26.(5) KE  mv2  RT
2 2
 m2 v2  2mKE  mv  2mKE
h h h
(wavelength)   
mv 2mKE 2m(T)

Where, T = temperature (in Kelvin)

h
(He at  37C  200K) 
2  4  200
h
(Ne at 727C  1000K) 
2  20 1000
(He) 2  20 1000
 M 5
(Ne) 2  4  200
Thus, M=5
27.(6) This problem is based on concept of quantum number. Follow the following steps to solve this problem.
Write all possible orbitals having combination of same principal, azimuthal, magnetic and spin quantum
number.
The count the all possible electrons having given set of quantum numbers.
For n = 4, the total number of possible orbitals are

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STRUCTURE OF ATOM Page No.[109]
4s 4p 4d 4f
0 1 0 1 2 1 0 1 2 3 2 1 0 1 2 3

According to question | m |  1 , i.e. there are two possible values of m , i.e. + 1 and – 1 and one orbital can
1 1
contain maximum two electrons one having s   and other having s   .
2 2
So, total number of orbitals having { | m |  1 } = 6
Total number of electrons having
1
{ | m |  1 and ms   }= 6
2
28.(c) K.E. = eV0 (V0 is stopping potential)
hc
K.E.   ( is work function)

hc
 eV0  

 hc  1
 V0    .  
 e  
1
So, graph (V0 ) vs   is a straight line with +ve slope.

29.(a) For 1s orbital ; (P) vs (r) is as in (a) option.

Solution for Q. 30, 31, 32

We will be using following information in order to solve the following question.
3/ 2
 z 
1s  2   e zr / a 0
 a0 
3/ 2
 z   zr   zr / 2a 0
 2s  2    2  e
 a0   a0 
3/ 2
1  zr   zr   zr / 2a 0
 2p     e
3  2a 0   a0 
For 1s For 2s For 2p

r r r r

30.[D]
[A] I – for 1s
3/ 2
 z 
(i)     e zr / a 0 True.
 a0 
(P) - not true
Actual graph for 1s orbital is

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STRUCTURE
For 1s OF ATOM Page No.[110]

r
Hence option „A‟ is incorrect

[B]II- for 2s
3/ 2
 z 
(i)     e zr / a 0 - not true
 a0 
3/ 2
 z   zr   zr / 2a 0
Actual relation is     2   e
 2a 0   a0 
(Q) Probability density at nucleus
3/ 2 2
 z   zr   zr / 2a 0
|  |    2  e  
 2a 0   a0 

At nucleus r = 0
3
 z  2z3 1
  (2  0)e 0
 
 2a 0  8a 30 a 30
Hence, option „B‟ is not true.
[C] I – for 1s
(iv) xy–plane is nodal plane not true
(R) Probability density is maximum at nucleus  true.
Hence, option „C‟ is incorrect.
[D] I – for 1s
3/ 2
 z 
(i)     e zr / a 0  True
 a0 
(S) Energy needed to excite electron from n=2 to n=4.
1 1
E1  13.6z 2  2  2  eV
2 4 
 3 
 13.6z 2  eV 
 16 
Energy needed to excite electron from n= 2 to n = 6
1 1 8
E 2  13.6z 2  2  2  eV 13.6z 2  eV
2 6  36
E1 3/16 27
 
E 2 8/ 36 32
27
E1  E 2  True.
32
Hence option „D‟ is true.
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STRUCTURE OF ATOM Page No.[111]
31.[C]
[A] I - for 1s
3/ 2
 z 
(i)     e zr / a 0  true
 a0 
27
(S) E n 2 to n 4 = E n 2 to n 6   True.
32
So, option „A‟ is not incorrect.
[B] I - for 1s
3/ 2
 z 
(i)     e zr / a 0  True
 a0 
(R) Probability density is maximum at nucleus  True
So, option „B‟ is not incorrect.
[C] I – for 1s
5
 Zr 
 Z  2  2a 
(iii)  n,l,ml    re  0  cos   not true.
 a0 
(R) Probability is maximum at nucleus  True.
So, option „C‟ is incorrect and hence the correct option.
[D] II - for 2s
(ii) one radial node  True
1
(Q) Probability density at nucleus   True.
a 30
So, option „D‟ is not incorrect.
32.[D]
[A] III-for 2pz  orbital
5
 Zr 
 Z  2  2a 
(iii)  n,l,ml    re  0  cos   not true
 a0 

(P) = not true

Hence option „A‟ is incorrect

[B] I – for 1s
(ii) one radial node  Not true.
27
(S) E n 2, n 4  E n 2, n 6  True
32
Hence, option „B‟ is not correct.
[C] IV – for 3d 2z orbital.
(iv) xy–plane is nodal plane  not true.

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STRUCTURE OF ATOM Page No.[112]
(R) Probability is maximum at nucleus  not true

2
dz

Hence, option „C‟ is not correct.

[D] II – for 2s
(ii) one radial node  True
(P) Probability density maximum at nucleus
 True. Hence, option „D‟ is correct
33.(AB)
 2 2 13.6
E He  13.6   3.4 
n2 4
n 2  16 so n4
quantum number are
n  4,   2, m  0
so subshell is  d.
angular node    2
Radial node   n    1  4  2  1  1
34. (i) (3) (ii) 3
 n2 
rn  0.529   Å  rn  n 2
 Z
 nh 
Angular momentum ()       n1
 2 
2
1 1  Z
K.E.  mv2  m  2.18  106 
2 2  n
2
Z
 K.E.  2  K.E.  n 2
n
Z2
P.E.  2K.E.  P.E.  2
n
2
 P.E.  n
35.[9]

Ionization Enthalpy
Atomic number
I1 I2 I3
n 1681 3374 6050
n+1 2081 3952 6122
n2 496 4562 6910
n 3 738 1451 7733
By observing the value of I1 , I2 & I3 for atomic number (n+2), it is observed that I2  I1 .
This indicates that number of valence shell electrons is I and atomic number (n+2) should be an alkali metal.
Also for atomic number (n+3), I3  I2 .
This indicates that will be an alkaline earth metal which suggests that atomic number (n+1) should be a noble
gas and atomic number (n) should belong to Halogen family. Since, n < 10; hence n = 9 (F atom).

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STRUCTURE OF ATOM Page No.[113]
Exercise – 3 [Advanced Level Problems]
A. Single correct type
1.(a) Electron will pass undeflected only when the forces acting on electron by the electric and magnetic fields
are same, i.e.,
qE  qvB
E 6.6  105
 v   5.5  106 m / s
B 1.2
hc 0
2. (c) V0 =  ,
e e
hc 
2.4 =  0 ....(1)
6000 1010 e e
hc 
V0 =  0 ....(2)
4000 1010 e e
Eq. (1) - Eq.(2)
hc  1 1 
2.4 – V0 =  10
 10 
e  6000 10 4000  10 
6.62 1034  3  108  4  6 
2.4 – V0 =
1071.6 1019  24 
6.62 1034  3 108
V0 = 2.4 +
12 107 1.6 1019
V0 = 2.4 + 1.03 = 3.43 V
3. (a) X = 0.53 Å , Y = 2.6 Å
Y - X = ( 2.6 - 0.53 ) Å = 2.07 Å
4. (a) For (n=1)
U = – 27.2 eV
K = 13.6 eV
E = U + K = – 27.2 eV + 13.6 eV = – 13.6 eV
To make P = 0 in ground state, we have to add +27.2 eV (changing frame of reference) in the potential
energy of that state.
For (n=1)
E = U + K = (– 27.2 eV + 27.2 eV) + 13.6 eV = 3.6 eV
For (n=2 : first excited state)
K = 3.4 eV
E = U + K= (– 6.8 eV +27.1 eV) + 3.4 eV = 23.8 eV
hc
5.(b) E  2.9 1019 J [for  = 6850 Å]

Total energy of 10 Quanta = 10 × 2.9 × 10– 19 J = 29 × 10– 19 J
112  4.18 103
Energy stored for process   7.8 1019 J
6 10 23

19
(7.8 10 )
% efficiency  19
100  26.9%
(29 10 )
B. One or more than one correct type:
1.(b, c, d)

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STRUCTURE OF ATOM Page No.[114]
Wave number, frequency and energy of photon involved are additive for the successive transitions (Ritz
combination principle). It may be derived simply as:
 1 1 
v1  RZ2  2  2 
n 
 1 n2 
 1 1 
v2  RZ2  2  2 
n 
 2 n3 
 1 1 
and, v3  RZ2  2  2   v1  v2
n 
 1 n3 
As v  Cv, v3  v1  v2
and E  hv,
E3  E1  E2
2.(a, c, d)
Kinetic energy of photoelectrons is linearly related to frequency of incident radiation but has no relation
with intensity of incident radiation.
3.(a, b, d)
In Lyman series, the final orbit number is 1.
1  1   (m  1)2  1 1  (n  1)2  1
  R H Z2  2 
 R H Z2  2 
and M n  R H Z2  2 
 m
 (m  1)   (m  1)    (n  1) 
 m  (m  1)2   (n  1) 2  1 
   
 n  (n  1)2   (m  1) 2  1 

In photoelectric effect : E  E  E k where E = energy of incident light E = threshold energy, E k = kinetic

energy. In Rutherford's experiment, bouncing back of few -particles on its original path with same
momentum indicates that collision with nucleus is prefectly elastic in nature.
4.(c, d) x  15BM, y  48BM, z  35BM
5.(a, b, c, d)
  24 BM implies number of unpaired electrons = 4. all the ions have four unpaired electrons.
6.(b, d)
Is the given situation, electronic configuration of K is 1s2 2s2 2p6 3s2 3p6 3d1
7.(a, c, d)
h
The orbital angular momentum  l(l  1) 'b' is wrong. The number of orbitals in a shell = n 2
2
8.(a,b)
Energy of an electron depends on both prinicpal and azimuthal quantum numbers but independent of
magnitic and spin quantum numbers.
C. Integer type
Z 1 1 1
1.(3) vn  2.18 106 ms and vn  C   3 108 = 1.09 × 106 m/s
n 275 275
1
 1.09 106  2.18 106   n  2  n 1  3
n
So, wave number for transition from (3  1)

1 1 1   1 1  109678  8
is  R.Z2  2  2   109678 12  2  2   = 97491.5 m– 1 = 974.915 cm– 1 = N
  1
n n 2
  1 3  9

So, Log N ≈ 3

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STRUCTURE OF ATOM Page No.[115]
1 1 
2.(8) E  2.18 1018 Z2  2  2  J / atom
 n1 n 2 
1 1 
E31  2.18 1018  22  2  2 
1 3 
E31  7.64 1018 J / atom

Similarly E21  6.54 1018 J / atom

Total energy  (50%)NA .(E31 )  (25%)NA .(E21 )  NA 0.5  7.64 1018  0.25  6.54 1018 

E
 6.02 1023  5.455 1018 = 32.83 × 10 J/mol   E  108
5
30
 log E  8

1 1 
3.(3) E  2.18 1018  Z2  2  2  J / atom  hv
1 2 

.18 1018  3
 Z2   6.626 1034  2.467 1015
4
 Z2  9.99 10341518  9.99 101  0.99  1  Z  1

1 1 
2.18 1018 12  2  2 
So, v  1 3  = 0.2924 × 1016 = 2.9 × 1015 Hz
6.626 1034
 x 1015 Hz  x = 3
4.(9) The two transitions will be n = 3  n = 2 and n = 4  n = 2
912Å 912Å
So,    1 
 1 1   1 1 
Z2  2  2  12  2  2 
n  2 3 
 1 n2 
= 6566.4 × 10– 10 m = 656.64 × 10– 9 m = 656.64 nm
912Å
2   486.4 nm
 1 1 
12  2  2 
2 4 
So,  0.008 1  2  0.008  [1143.04]  9.1  9
5.(8) Excited states n1 and n2
So, energy difference   En1  En2 

 Z2   Z2 
  13.6  2 eV    13.6  2 eV   2.55 eV
   
 n1   n2 
 1 1  2.55
  2  2   0.1875
n 
 1 n 2  13.6 1
2

As we know,  E (n = 2 to n = 1) is 10.2 eV
So, n = 1 is not involved in this transition.
Again, by hit and trial
We get n1 = 4 and n2 = 2
 1 1 
As it gives   2   0.1875 which is true
2 2
4 
So, (n1  n 2 )  2  4  8
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STRUCTURE OF ATOM Page No.[116]
6.(5)  0 corresponds to energy = 13.6 eV
and H-atom in 1st excited state (n = 2)
Z2
is calculated by E n  13.6  eV  E2  3.4 eV
n2
So, K.E. = (13.6 – 3.4) eV = 10.2 eV = „2E‟ eV
10.2
 E  5.1  E  5
2
o
912 A 912  1010 m
7.(9) Smallest wavelength corresponds to maximum energy  Smallest  
1 1  z2
z2  1  2 
1  
912  1010 m 912  1010 m 912  1010 m
1  2
for H-atom,  2  2
for He +
-atom,  3  2
for Li2+-atom
1 2 3
 12  1  22  2  32  3  912 1010 m  12  1  22   2  32  3  912 1010 106 m
 (12  1  22  2  32  3 ) 100  912 1010 106 100 m  9.12 m  y
1 1 
8.(4) E n  2.18 1018 Z2  2  2  J / atom
 n1 n 2 
Let energy released in two successive transitions be E1 & E2 and intermediate state be „nth‟ orbit.
E1 1
Then,  ….(i)
E 2 27

1 1 
E1  2.18  1018.12  2  2  
n 6 
Now,  ….(ii)
1 1 
E 2  2.18  101812  2  2  
1 n  
From Eqs. (i) and (ii), we get
1 1  27 
 n 2  62  1  36 
   1  27  27  1  1  1     n4
1 1  27 n 2 62 12 n 2 n2 28
 12  n 2 
 
9.(5) Energy needed to ionize H-atom = 13.6 eV
 6.63 1034  3 108 
E hv   9 19 
eV = 2.48 × 101 = 24.8 eV
 50 10 1.6 10 
 K.E. of ejected electon = 24.8 – 13.6 = 11.2 eV = 2.25   =5
h h h2 1 (6.626 1034 )2
10.(3)    E   Joules
p 2m.E  2
2m (0.005 109 )2  2 1.67 1027

 5.26 1018 J
5.26 1018
 „V‟(potential difference)  eV  32.87eV  (V /11)  3
1.6 1019
11.(5) K.E. of emitted electron = 1.5 E – E = 0.5 E = 0.5×13.6 = 6.8 eV
Now, by de Broglie equation
h h 6.626 1034 – 10
   m = 4.708 × 10 m = 4.708 Å  5
31 19
P 2mE 2  9.110  6.8 1.6 10
12.(3) K.E.  hv  
Raman Niwas, Near Akashwani, Mahmoorganj, Varanasi, Ph (0542) 2363455. www.catjee.in
STRUCTURE OF ATOM Page No.[117]
240 103 – 19
 J / molecule = 3.9 × 10 J/molecule
6.02 10 23

hc 6.626 1034  3 108

E photon   = 4.4 × 10– 18 J
 450 1010
(E photon  ) 44 1019  3.9 1019 40.11019
K.Eatom    = 2.01 × 10– 18 J
2 2 2
= 2 × 10– 6 x  x = 3
h 6.626 1034
13.(7)    = 6.626 × 10– 35 = 6.626 × 10–5x
mv (0.1)(100)

 5x  35

i.e. x=7
h h
14.(4) Acc to de Broglie    M(mass equivalence) 
mv v

6.6 1034
 9
= 3.7 × 10– 36 kg
589 10  3 10 8

 0.9  log10 M  (0.9  (36) log 3.7) 36.33

So,    4
 9  9 9

h 6.6 1034
15.(5)    [3000 km/h = 833.3 m/s]
mv 1000  833.3

 0.8  log10   (0.8  40  log 7.92) 39.91

= 7.92 × 10– 40 m     5
 8  8 8

D. Assertion – Reason Type

1.(a) All isotopes of any element have same atomic number and hence same number of protons and electrons.
As electrons take part in a chemical reaction, atoms having same number of electrons show same type of
chemical behaviour.
2.(c) The path of an electron in an atom is not clearly defined because its position cannot be measured with
absolute accuracy.
3.(a) Rutherford's model of atom was discarded on the basis of classical theory of electromagnetic radiation.
4.(a) Quantised state of energy of atoms is responsible for the line spectrum of pure element.
5.(a)  2 is maximum at r = 0 for H-atom. However, probability is negligible due to negligible volume of
nucleus.
6.(a) For a given value of l, (2l+1) value of m e exist all having same energy.

E. Comprehension Type
Passage – 1:
m 9.1 1031
1.(a) m'  
2 2
v  2 106 
1   1   
c  3  10
8


9.11031 9.11031
 
1  (0.66 102 ) 2 1  0.4356 104

9.11031
  9.11031 kg
1

Raman Niwas, Near Akashwani, Mahmoorganj, Varanasi, Ph (0542) 2363455. www.catjee.in

STRUCTURE OF ATOM Page No.[118]
2.(b)
Passage – 2:
1.(c, d)
2.(b, d) Hund‟s rule forbids pairing unless all orbitals are singly occupied.
3.(a) 29 Cu has configuration [Ar] 4s1 3d10 (fulfilled 3d-orbital)
4.(a) 24 Cr has configuration [Ar] 4s1 3d5 (half filled 3d-orbital)
F. Matrix match Type
1. [a→r; b→q; c→p; d→s]
According to Bohr‟s theory
Ze 2
Kinetic energy (Kn) = 
2r
Ze 2
Potential energy (Vn) = 
r
Ze 2
Total energy (En) = 
2r
Vn Ze2 / r
(A)  2  2
Kn Ze / 2r
1 1
(B) rn  n2 and En  2
i.e., E n 
n rn
1
rn  or rn  E n1
En
x = - 1
h
(C) Angular momentum = (  1)
2
The lowest orbital is 1s for which   0 . Hence, angular momentum = 0
1 1
(D) rn  or  Z  Y=1
Z rn
2. [a→pq, b→pq, c→qr, d→ s]
3. [a→s, b→qs, c→qr, d→pr]
Photon has particle nature as well as wave nature. Electron also has particle nature as well as wave nature.
 2 represents probability density and always has positive values.
a→r; b→q; c→p; d→s a→pq, b→pq, c→qr, d→ s a→s, b→qs, c→qr, d→pr

G. Subjective:
Change in angular momentum
1. Torque 
time taken

 2h 3h 

dL  2 2  h 6.63  1034
    1.05 1028 Nm.
dt 10 6
2106 2  3.14  106
 Rate of change of angular momentum is equal to torque.
2. The line considered is  n  1  n.
The unit of the given interval of the extreme lines is cm1 and hence it is the difference between the wave
numbers of the lines.

Raman Niwas, Near Akashwani, Mahmoorganj, Varanasi, Ph (0542) 2363455. www.catjee.in

STRUCTURE OF ATOM Page No.[119]

1 1   1 1   2  1 1 
  21190 cm1  21190 cm1  RZ2      
 (n)2 2  
 RZ 
(n1) n   (n  1)2 2   
    

 1 1  1 1 21190 cm1
 21190 cm1  RZ2        0.0486
 (n  1)2 (n)2  (n  1)2 (n)2 1.09  105 cm1  22
 
 This give n = 3
Now, the wavelength of the electronic transition 4  3 is
 1 1 

1
 n   
 1
3
1 
 R Z2  2  2   1.09  107 m1  22   2  2 
4 
 1 n2 
   4.7182  107 m  4718.2Å
3. For I (Ground state)
1 1
Total spin s     0
2 2
 Spin multiplicity   2  0   1  1
For II (Single excited state)
1 1
Total spin s     0
2 2
 Spin multiplicity  (2  0)  1  1
For III (Triplet excited state)
1 1
Total spin s     1
2 2
 Spin multiplicity  (2 1)  1  3
4. If E1 = 13.6 eV
E2  13.6 1.50eV  20.4eV
E  (E2  E1 )  20.4 13.6  6.8eV
 6.8 1.6 1019 J
h

2m (K.E.)
6.626 1034 o
  4.711010 m  4.71 A
2  9.11031  6.8 1.6 1019
5. Since plate potentials 2V, minimum K.E will be 2eV for maximum K.E. use the following relations:
Absorbed energy = Threshold energy + K.E.
Lc 6.626  10 34  3  108
 4.5  1.6  10 19  K .E. =  4.5  1.6  10 19  K .E.
 200  10 9

K.E. = 2.739  10 19 J  1.7eV

Max K.E. = 2Ev + 1.7EV = 3.7 eV.
*****

Raman Niwas, Near Akashwani, Mahmoorganj, Varanasi, Ph (0542) 2363455. www.catjee.in