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ENTHUSE

IIT CHEMISTRY
PHYSICAL CHEMISTRY
ATOMIC STRUCTURE

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 PHYSICAL CHEMISTRY
ATOMIC STRUCTURE
EXERCISE # (S-1) solutions
4
 
1. Fraction occupied = 3 = 2.7 × 10–14
4
 
3
1
2. (A) R = Ro (A)
3
1
= 1.3 × 10–15 × (125)
3
 R = 6.5 × 10–15 m.

4 k.z.e.2
(B) R=
mv 2
4.k.47.e 2
=
mv2
188.k.e 2
R=
m v 2

12400e v A
3. E=

 (A)
12400
= × 100
2000
= 620
hc
4. E=

1010



 A 
12400
5. 5 × 10–3 = × 1.6 × 10–19 × N

5103
N =

 × 1016 

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 PHYSICAL CHEMISTRY
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hc
6. 100 = N × ……..(1)
8000
hc
x=N× ……..(2)
4000
Divide (1) & (2)
100 4000
=
x 8000
 x = 200 watt.
7. 30 = N1 × 13.6 × (1)2 ……..(1)
40 = N2 × 13.6 × (2)2 ……..(2)
Divide (1) & (2),
30 N1 1
 
40 N 2 4
N1
 =3
N2
12400
8. 3.15 × 10–14 = N × × 1.6 × 10–19
8500
3.15 1014 8500
N=
124001.61019
 N = 1.34 × 105
9. 330 = N × 6.625 × 10–34 × 5 × 1013
330
N=
6.6251034 51013
  N = 10 × 10+21
 N = 1022
12400
10. E= × 1.6 × 10–19 × 6.023 × 1023
5000
= 239.4 × 103 J/mole.
KJ/mole.
12400
11. E= × 1.6 × 10–19 × 6.023 × 1023 × 10–3
854
1403 KJ/mole.

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 PHYSICAL CHEMISTRY
ATOMIC STRUCTURE
12400
12. 4.5 =


 12400
  =
4.5

   = 2755.56 
— 1 1010
 V = =
 
—
 V = 3.63 × 106 m–1
13. Let number quanta emitted = n1
Let number of quanta absorbed = n2
hc hc
 n1 × = n2 × × 0.47
50801010 45301010
n1 5080
 = × 0.47
n2 4530
n1
 = 0.527
n2

124001.61019
 192 × 103 = × 6.022 × 1023

12400 1.6 10 19 6.023 10 23
=
 

  = 6235 A

no.of molecules reacting

15. Quantum yield =
no.of quanta absorbed or photons

0.0161023
 number of photons absorbed = = 3 × 1022
0.2
z
 Vn = 2.18 × 106 × m/s
n
1
 V3 = 2.18 × 106 ×
3
  V3 = 7.27 × 105 m/s.

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 PHYSICAL CHEMISTRY
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17. rn = 16 × 0.529
n2
0.529 × = 16 × 0.529
1
 n=4
z2
 En =  13.6 × 2 er
n
 E4 = 0.85 × 1.6 × 10–19 J
 E4 = × 10–19 J

18. rn = 0.85 × 10–9 m.

n2 
0.529 × = 8.5 A
1
 n=4
z
Vn = 2.18 × 106 × m/s
n
1
 V4 = 2.18 × 106 × m/s
4
 V4 = 5.45 × 105 m/s.
Vn 1 1
19. =
Vc 275
2.18106 1 1
 =
n 310 8
275
  n=2
— 1 1 1 
now V = = R z2   
 1 9 

1
= 1.09 × 107 × 8/9

1 —
 i e. V = 9.68 × 104 cm–1

 2 r 
 4 2
T2  v   .529 
20. = (He )
= 2 2.18106  2
T4  2 r 
 16 4
 .529 
 v  2 3 2.18106 3
(Li )

T2 9
 
T4 32

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 PHYSICAL CHEMISTRY
ATOMIC STRUCTURE
 nh
21. L
2
as, n=2
h
 Angular momentum =  
  

k.ze2
22. K.E. =
zr
 ke2 
Log (k.e.) = log +   log z
 zr 

k.e2
Now, = 3.4
zr
k.z.e2
T.E = –
zr
as, Z=1
 T.E = 3.4 eV
n=2
23. E 2.55 i.e. E4 – E2 = 2.55
 orbit number of states A & B are 2 & 4.
24. 13.6.Z2

1st Excitation potential = 10.2 z2 v.
= 10.2 × (1.08)2
= 12 v
1 
25.
1
= Rz2   1 
  n 2 n 2 
1 2

1 8
 = 1.09 × 107 × 9 ×
 9

  A
V
26. V=
2r
2.1810 6 1010
=  
23.14 0.529
 V = 6530 × 1012 Hz

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 PHYSICAL CHEMISTRY
ATOMIC STRUCTURE
27. E2 = 10.2 eV
1 1 1 
= 1.1 × 107 × z2   
3108 1 4 

 Z=2 i.e. He+ .

2r 23.140.529 41010  2
28. T= =
v 2.18106 1
= 12.19 × 10–16 .
108
 Number of orbits =
12.191016
= 8 × 106
29. (a) 2.55 z2 = 16.52
z=3
k.z.e 2
 (b) K.E =
zr
9109 3(1.61019 )
2

=
20.5291010
 K.E = 122.9 eV
& P.E = eV
(d) E2 = 12.172
= 12.1 × 9
= 108.9 eV
1 
(d) `
1
= R. z2   1 
 12
 


1 1
 = =
R.z 2
1.1107 9
 × 10–8 m.
k.z.e 2
(e) K.E =
zr
 eV.
 1 1 
30.
1
= 1.1 × 107 × 1    = 1.1 × 107 × 8
  4 36  36
c  3108 1.1107 8 
Now. v = =    V = 7.3 × 1014 Hz
  36 
It will lie in visible spectrum. 
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 PHYSICAL CHEMISTRY
ATOMIC STRUCTURE
31. E = 1.89 × 6.022 × 1023 × 1.6 × 10–19 = 1.82 × 105 5/mole.
32. E = 12.08 er
Possible transitions are from (n = 3 to n = 1), (n = 3 to n = 2) & (n = 2) to (n = 1)
  emitted :

(1) (n = 3) to (n = 1)   = 1026 A

(2) (n = 3 to n = 2)   = 6563 A

(3) (n = 2 to n = 1)   = 1216 A
33. 3 Spectral lines are possible
i.e. 3 1 ;
2 1 &
3 2 respectively .
n(n 1)
34. =6
2
 n = 4 or 3
 Also n = n2 – n1
 n2 = 6.
35. 2 4 6
1 3 5
Max. 1 line possible 4
2
For 2 1 Transition 3
1 2
+
He ion 1
4(4 1) Li+ion
Max. i.e.
2 6(6 1)
Max. i.e. 15
lines possible for 2
4  1 transition. lines possible for
6  1 transition.
But, (H2) 2 = (He+)4 = (Li+2)6 are lines of same energy & 12 each other.
 Total lines observed = (1+6+15) – 2 = 20
36. 4 spectral lines are possible
i.e. 7 3
6 3
5 3    
& 4 3.

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 PHYSICAL CHEMISTRY
ATOMIC STRUCTURE
1 1 1 1 
37. R × 4  2  2  = R × 1 ×   
 n n 2  1 4 
1

1   
   1  =  1  1    1  1 
 
 n 2
1 n 2 
2  4 10   (2) 2
(4) 
2

  n1 = 2 & n2 = 4
 Transition is from (n = 4) to (n = 2)
3
38. DE = × 0.85
4
3 13.6
 E = ×
4 (4) 2
13.6 1 1 
 Or, DE =   
(4) 2 1 4 

 1 1 
 DE = 13.6  2  2 
 (4) (8) 
Thus, this photon comes ponds to transition from (n = 8) to (n = 4) -: (x = 8)
n
39.
10.2 eV n=3
78.2 eV n=2
1 1
DE = 68 eV = 13.6 × z2   
 4 9 

 Z=6
 180.69103 
40. V =  
 6.6251034 6.0221023 

 V = 4.5 × 1014 51
41.  = 0.8 × 1015 × 6.625 × 1013 × 6.022 × 1023
 = 319.2 KJ/mole 
  h × 3.2 × 1015 =  + 2 K E
h × 2 × 1015 =  + K. E
_______________________
 × 1015× h
1
42. E = 270eV = K.E. = mv2  V = 3.09 × 108 cm/sec.
2

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 PHYSICAL CHEMISTRY
ATOMIC STRUCTURE
43. hv = hvo + K. E.
1240061023 
 1.61020  = 430.53 + K. E.
 253.7 
 K.E. = 469.21 – 430.53
= 38.68
 % of enerrgy converted into K.E.
 38.68 
=  100
 469.21 
= 8.68 %
44. = 40 er = hvo
–19 6.6261034 3108
40 × 1.6 × 10 =
o
 o = 31 mm
45. Stopping potential will be 3.06 v
e m v
46. = p p
 p me ve

e 1836 v p
 =
p ve
  ve = 1836 vp
150 
47.  = A
4

  = 6.135 A
12.27 
48. = A
6.8

  = 4.71 A
3   2
49.
1
1 1

= 7 9
1
10
3   2 20
 = .
1 63
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50. (n = 6) to (n = 1)
 Number of paschen lines emitted are,
6 3
5  3 i.e. 3 lines
4 
51. As, me = 3 , which belongs to f–orbital
 minimum number of waves made by a Bohr electron is 4.
h
52. a ×  × 0.529 =
my
6.6261034  4
 a =
3.140.5299.11031  2.18106
 a=8
h
53. =
2.m.e.v
h2
 V=
2.m.e. 
 V = 0.08 volt.
h
54. As, 
m.v.
6.6251034
 
61024 3106
  = 3.68 × 10–65 m.
h
55. x =
.m.v
 x = 1.05 × 10–13
56. x = p
h
v  ? , As, x. p =
4
h
 m2 . DV2 =
4
h 1
 V = 
4 m
 V = 8 × 1012
 x=8

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h
57. x. p 
4
 m = 100 g
58. 0.85 × 4 = 1.4 × K. E.
 K. E. = 2
Total K. E. = 6 ev
4(4 1)
 =
2

 =5 A
59. (a) 55 R. N  4
(b) 3 dyz  A. N 
(c) 4 dxy (R. N + A. N) = (1+2) = 3
(d) 3P A. N = 1
60. (n 4) & 2 Radial node possible non-spherical orbital’s = (4Px, 4Py & 4Pz ) i.e. 3
A.N3d x 2
61. = =
(A.N)3p 1 1

 x = 2
62. For 25 , only 1 Radial node.
 value of x = 1
63. At node, R = 0
  – 6  + 6 = 0
 9  3 3   9  3 3 
  =   ao &  
 2  ao .
 2   

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 PHYSICAL CHEMISTRY
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EXERCISE # (S-II)
1. Potential difference = 2×106 V; Charge of alpha particle=2e; Charge of silver = 47e
−19
KE of alpha particle = qV=2×1.6×10 ×2×106=6.4×10−13 J
K.E at A = K.E at B + P.E at B
−13 9 109  2 1.6 10 –19  47 10 –19
6.4×10 = K.E at B +
5 10–14
K.E at B = 2.1×10−13 joules
2. Since H atom is a bounded system U cannot be positive
ke 2 dU ke 2
U= – 3 ; F= – = – 4 ………….1
3r dr r
mv 2 ke 2 ke 2 1 ke 2
 4 ; mv 2  ; KE  mv 2  3
r r r3 2 2r
ke 2 ke 2 ke2
TE = KE + U = –  –
2r 3 3r 3 6r 3
3. Energy of emitted photons cannot be greater than 13.6 eV (otherwise He+ will ionise) therefore
single electron specie must be hydrogen energy emitted = E3 – E1
= –1.51 + 13.6 = 12.09
For He+ ion this energy corresponds to excitation from 2 to 6.

n  6.625 10 –34

4. L ; n=3
2  3.14
1 1 
 R  2  2  = R  
1 8
 1 3  9
12400
5. IE = 13.6 eV ;   910A0
13.6
6. (i) Total number of H atoms =1.8 × 6.023×1023l= 1.084×1024
Number of H atoms in 2nd energy level = 0.15×1.08×1024=1.62 ×1023 atoms,
Number of H atoms in 3nd energy level = 0.27×1.08×1024=2.92×1023 atoms,
(ii) Energy evolved for n =2→1
1 1 
E1  21.7 10 –12   –   1.63 10 –11
1 4 
Energy evolved for n = 3→1
1 1 
E 2  21.7 10 –12   –   1.93 10 –11
1 9 
Total energy= 1.63 10–11 ×1.62×1023l+ 1.93 10–11 ×2.92 ×1023l = 8.32×1012 erg = 8.32 × 102 KJ
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ATOMIC STRUCTURE
1 1 
7. E = 13.6×    eV = 12.75 eV
 1 16 
12400
= = 972.5 Å
12.75
8. RH = 2.18×10−18
hc
E2−E1 =

E1 =−4RH=−4RH
4R H
E2 = = −RH
4
hc
E2−E1= 3RH =3×2.18×10−18J =

−10
 = 303.89×10 m
27.2  Z2 27.2  4
– –
U n2 –8 12
9. (i)  ;  ; Z=1
K 13.6  Z2 1 13.6  Z2
n2 12
 n2  12 
   
r1  Z 1 1  Z 1
(ii)  2 ;  2 ; Z=2
r2  n  8 2 
Z 1
 2  2
2 2 K 2 Z 2 e 4 m 22 K 2 Z2 (2e)4 (2m)
10. TE  – = –
n 2h 2 n 2h 2

 22 K 2 Z2 (e) 4 (m) 

 32   –   32  (–13.6)  – 435.2 eV
 n 2h 2 

1240
11. (a) Ephoton = W + KEmax ; Ephoton = = 100eV ; KE max = 75 eV
12.4

150 150
(b)  = Å= = 1.414 Å
V 75

h h
(c) P = ; dP = d
 2

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 PHYSICAL CHEMISTRY
ATOMIC STRUCTURE
150
12. For an electron, de-Broglie wavelength  = Å
KE eV
2 150 150 150 13.6 11
 = ; KE = = = eV (Using given relation)
KE eV  2
12.016 144

E 
n 2 6 Li 2  =  E 3 H + KEelectron

 1 1  1 1  13.6 11
13.6 (3)2  2  2  = 13.6 (1)2  2  2  +
6 n2  3   144
On solving, we get n2 = 12.
1 nhc
13. P
3 t
90 4000 10 –10
Number of photoelectrons emitted = 
3 6.4 10 –34  3 108
1
Magnitude of charge passing per second = 1020 1.6 10–19 = 10Å
1.6
14. He atom can be excited to 1s1 2p1 by  = 58.44 nm. If lowest excited state for He lies 4857cm–1
below the above. Calculate the energy for the lower excitation state.
15. A; n–  – 1 = 2, but  = 0, so value of n = 3

B; This equation belongs to s-orbital so, number of angular nodes = 0

C; This equation belongs to s-orbital so, = 0

D; 8s, 7p, 6d, 5f and 8p

E; Orbital angular momentum = 0 , because = 0.

F; r2 – 5k3r + 6k23 = 0
So, r = 3 and 2 , but for farthest node r = 3

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 PHYSICAL CHEMISTRY
ATOMIC STRUCTURE
EXERCISE # (O-I)
1/3 1/3
1. R = R0 A = 1.3 × 64 = 5.2 fm
2. Rutherford's alpha particle scattering experiment eventually led to the conclusion electrons
occupy space around the nucleus
E1  2 4000 2
3.   
E 2 1 2000 1

nhC 80 n  6.62 10 34 3 10 8

4. Power = 40 × = n = 2 × 1021
 t 100 620 10 9 20
r1 n12 4 n1 2
5.   ; 
r2 n 22 1 n2 1
 n2 
6. r  
 Z
7. r1 – r2 = 24 × (r1)H

0.529  n12 0.529  n 22

– = 24 × 0.529
1 1
 n 2
1 – n 22  = 24
So, n1 = 5 and n2 = 1

1 1 2 1 1
8. E = 13.6 Z2  2 – 2  = 13.6×5  – 
 n1 n 2   9 16 

1 1
9. E = 13.6 Z2  2 – 2 
 n1 n 2 
2 1 1
12.75 = 13.6×5  – 2  
1 n 
1 1 2 1 1
10. E = 13.6 Z2  2 – 2  = 13.6×5  – 
 n1 n 2   4 16 

13.6  Z2
11. KE 
n2

12. En for A+( Z–1) = Z2 × En for H

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 PHYSICAL CHEMISTRY
ATOMIC STRUCTURE
27.2  Z2 27.2
13. PE  – 2
= – 2 –3.02eV
n n
1 1 1 1
14. E = 13.6 Z2  2 – 2  = 13.6× Z2  4 – 9  = 47.2 eV
 n1 n 2 

15. (E2 – E1) > (E3 – E2) > (E4 – E3)

E1 Z12
16. 
E 2 Z22
17. In one direct transition, one quantum of energy is emmited
1 1 1 1 
18. E = 13.6 Z2  2 – 2  = 13.6×4 1 –   =54.4 eV
 n1 n 2 
1 1 
E = 13.6×4  –  = 13.6 eV
4 
1 1 
E = 13.6×4  –  = 6.04 eV
9  
2
19. (a) Energy of ground state of He+ = – 13.6 × 2 = – 54.4 eV (iv)
2
(b) Potential energy of I orbit of H-atom = – 27.2 × 1 = – 27.2 eV (ii)
22
(c) Kinetic energy of II excited state of He+ = 13.6 × = 6.04 eV (i)
32
(d) Ionisation potential of He+ = 13.6 × 22 = 54.4 V (iii)
nh L1 n1
20. L ; 
2 L2 n 2

r1 n12 R n1 1 T1 n 13 1
21. = 2=  =  = 3 = .
r2 n 2 4R n2 2 T2 n2 8
22. Angular momentum L = mvr
J2 = m2v2r2
J2 1  J2
or =  mv 2  mr 2 or K.E. =
2 2  2mr 2

1 1 1 1  1 1 
23. E = 13.6 Z2  2 – 2  ; 13.6 1  –   13.6  Z22  – 
 n1 n 2  1    4 16 
Z=2

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 PHYSICAL CHEMISTRY
ATOMIC STRUCTURE
1 1 1
24. E3 – 1 = E3–2 + E2–1 ;   ; 3 = 2 + 1
 3  2 1
1 1 1
25. = +
3 1 2
26. An electronic level with lowest energy (1s) would allow the hydrogen atom to absorb a photon
but not to emit a photon
27. 52
1 1  1 1 
28. Shortest wave length of Lyman series of H-atom, = = R 2  2
 x  (1) () 
1
so, x=
R
1  1 1 
For Balmes series, = R (1)2  2  2
  (2) (3) 
1 1 5 36x
= × so, = .
 x 36 5
1 1 1 1 1 1  1 1 
1 – 1  n2 – n2  –  n2 – n2  1 – 1 1 – 4  – 1 – 9 
1 2  1 2 1  1 2 2 1 2
29.  ;  1 2
1 – 1 1 1 1 1 1 – 1 1 1  1 1 
3 4  2 – 2  –  2 – 2  3 4  –  –  – 
 n 1 n 2  3  n1 n 2  4 1 9  3 1 16  4

1 1 
1  – 
30.
v1
 1 4  ;
v1 1

v2 1 1  v2 1
4  – 
 4 16 
31. The total number of lines belonging to Balmer series are two so, n = 4
13.6 1
TE of electron = =0.85 eV.
16
Then the kinetic energy of the ejected photoelectrons = 13 – 0.85 = 12.15 eV
32.  
(n2 + n1) = 4 and n 22  n12 = 8, so, n1 = 1 and n2 = 3

1  1 1  1 1 1 
=R H Z2  2  2  ; =R H  4   
  n1 n 2   1 9 
9
  
32R H
33. Total lines = (n2–n1) + (n2–n1 –1) + (n2–n1 –2) + …….
= 1 + 2 + 3 ...... (x - 1)
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 PHYSICAL CHEMISTRY
ATOMIC STRUCTURE
(n – n1 )(n 2 – n1  1) (6 – 3)(6 – 3  1)
34. Total spectral lines (without Balmer series)= 2  6
2 2
35. Total spectral lines in Bracket series = 10 – 4 = 6
12400 12400
36. Energy of photon E = eV =  40eV
 310
Eincident = Ethreshold + KE max
40 = 12.8 + KEmax ; KEmax =27.8 eV = 27.8 × 1.6×10–19 J
1 1
KE = mv2 ; 27.8 × 1.6×10–19 = ×9.1×10–31×v2
2 2

On solving, v = 2.18 2 × 106 m/s

37. Photoelectric effect is a random phenomena. So, electron It may come out with a kinetic energy
less than (h – w) as some energy is lost while escaping out.
hc
39. =1+W ...(1)

hc
3× =4+W ...(2)

from, e.q., (1) and (2) f = 0.5 eV
40. As the frequency of incident radiations increases, the kinetic energy of emitted photoelectrons
increases.
Decreasing order of n : Violet > Blue > Orange > Red
Decreasing order of KE of photoelectrons : Violet > Blue > Orange > Red
41. The maximum KE of potoelectron is corresponding to maximum stopping = 22 eV
Eincident = Ethreshold + KEmax = 40 eV + 22eV = 62 eV
12400 Å
lincident = = 200 Å
62

h 6.625 1034
42. = = × 3600  10–30 m.
mv 0.2  5
43. KE of electron = 122.4 –13.6 = 108.8 eV
An electron in a hydrogen atom in its ground state absorbs energy equal to the ionisation
energy of Li+2. The wavelength of the emitted electron is:
(A) 3.32 ×10–10 m (B) 1.17 Å (C) 2.32 × 10–9 nm (D) 3.33 pm
y mx vx y mx vx 16
44. = ; = = = 5.33 Å
x my vy 1 (0.25m x ) (0.75 v x ) 3

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 PHYSICAL CHEMISTRY
ATOMIC STRUCTURE
1 1 1
45. e :  p :  : : :
me 16E mp  4E 4m p  E

So, e > p = 
46. 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 × 10–24 m (B) 9.28 × 10–7 m (C) 9.28 × 10–8 m (D) 9.28 × 10–10 m
h 6.62 10 –34
47.  
mv 9.1  10 –31  1.2  105
48. Circumference = 2r = n 
h
49. 
2mqV
hc
50. = E1 – E2 = KE2 – KE1

2
h h 1 h2
 = 2
(mV) =   ; mV = 2
mV  2m  2

hc h2 h2 2mc  12  22 
 = – .  =   .
 2m  22 2m 12 h  12   22 

h h
51. P= ; dP = d
 2
h h h 2 1
dx × dP = ; dx × 2 
d = ; dx = 
4  4 4  d
2 1
Slope = = ;  2= 4 Å
4 
150 150
 = Å; V= = 37.5 V
V 4
52. r1 = 0.529 Å
r3 = 0.529 × (3)2 Å = 9x
2r 2 (9x)
so, = = = 6 x.
n 3
h 0.101
53. For an -particle accelerated with potential difference V volt,  = = Å
2mqV V

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 PHYSICAL CHEMISTRY
ATOMIC STRUCTURE
n
54. 
Z
h 1 0.001
55. x = × v = v × = 300 × 10–5 m/s
4 me v 100
1
x = 5.8 × 10–5 × 5
= 1.92 × 10–2 m
300  10

2 1
56. d= 
4 dx
150 150
57.  = Å 5 Å
V 6
h h
P= ; dP = d
 2
h h h 2 1
dx × dP = ; dx × 2 
d = ; d = 
4  4 4 dx
58. m = +2, So,  = 2 and n = 3

62. For single electron species energy of a subshell depends on only value of n.
So, E1 = E2 = E3
h h h
63. L  (  1)  2(2  1)  6
2 2 2
64. Number of radial node = n – – 1 = 1

h h
So, =1; L  (  1) = 2
2 2
65. Value of m = 0 for s subshell

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 PHYSICAL CHEMISTRY
ATOMIC STRUCTURE
EXERCISE # (O-II)
More than one may be correct
c 3 108 12400
3. = = = 5 × 1014 sec–1 ; E= = 2.07 eV.
 600 10 –9
6000

nh
5. Angular momentum =
2
h h
Change in angular momentum for 3  2 transition = (3 – 2) = .
2 2
h h
Change in angular momentum for 4  2 transition = (4 – 2) = .
2 
6. 1st excitation potential = 10.2 Z2 = 24 V 
2
Z = 24/10.2
13.6  24
 IE = 13.6 Z2 = = 32 eV.
10.2
0.85  24
Binding energy of 3rd excited state = 0.85 Z2 = = 2eV.
10.2
12.09  24 32  8
2nd excitation potential of sample = 12.09 Z2 = = V.
10.2 9
7. Transition is taking place from 6  2
 n = 4
4(4  1)
Hence maximum number of spectral line observed =  10 .
2
Number of lines belonging to the Balmer series = 4 (6  2,5  2,42, 42)

Number of lines belonging to Paschen series = 3 (6  3,5  3, 5  3).

9. IE3 = 13.6 × 96.3 × Z2 kJ/ mol = = 13.6 × 96.2 × 9 kJ/ mol = 11775 kJ/ mol
H = IE1 + IE2 + IE3
h h h
10. = = = .
mv 2mKE 2mqV
When v, KE and V are same, as m increasing,  decreases. e > p >  (if v, KE and V are
same).

12. The difference in angular momentum associated with the electron present in consecutive orbits
h
of H-atom = (n2– n1)
2

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 PHYSICAL CHEMISTRY
ATOMIC STRUCTURE
2 2
14. Radial distribution function ( ·4r dr ) give probability at a particular distance along all the
direction spherically
2 (r) give only radial probability density at a particular distance over a spherical surface
15. Number of maxima when a curve is plotted between 4r2R2(r) vs r are '2' because it has two
radial nodes.
16. Statement (2) alone is sufficient to concludes that its not 3px orbital because 3px orbital has one
angular node.
19. (A) s-orbital ; r = 0,   0 and 3 radial nodes ; 4s
(B) 3 radial nodes (s, p, d) ; 4s, 5px 6dxy
(C) Angular probability is dependent of q and f for 5p y, 6dxy
(D) Atleast one angular node ; 5Px (1); 6dxy (2)
20. Column-I Column-I

150 150 2.188 106  Z 2.188 10 6

(A)   Å = Å (B) v  = m/sec
V 13.6 n 3

13.6  Z 2 0.529  n 2
(C) TE =  – = –13.6 × 9eV (D) r  Å = 0.529 Å
n2 Z
h h
21. = =
mv 2mKE
When v, KE and V are same, as m increasing,  decreases. H > D > T
h h
22. = =
mv 2mKE
h 2 h 2 2 h 1 h
23. x p = p =  m v =  v =
4 4 4 2m 

24. Multiply angular part and radial part of 1s orbital and square this.
26. s- orbital is spherically symmetric.

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 PHYSICAL CHEMISTRY
ATOMIC STRUCTURE
EXERCISE # (JEE-MAINS)

h 6.6 10–34
1. x. v = x = =2.86× 10–28 m
4m 4  3.14  9.218  10 –6

13.6 13.6
2. 2nd excited state will be the 3rd energy level. En = 2 eV or E = = 1.51 eV.
n 9
h 6.6 10 –34 –28
3. x. v = v = 5
 v = 2.1 × 10 ms–1.
4m 4  3.14  25 10
4. The value of  (azimuthal quantum number) for s -electron is equal to zero.
h
Orbital angular momentum = (  1).
2
h
Substituting the value of l for s-electron = 0(0  1). 0
2
5. 26Fe = 1s2, 2s2, 2p6, 3s2, 3p6, 3d6, 4s2,
++
Fe = 1s2, 2s2, 2p6, 3s2, 3p6, 3d6
The number of d -electrons retained in Fe2+ = 6.
h 6.63 1034 1000
6. =  = 11.05 × 10–34 = 1.105 ×10–33 metres.
mv 60 10
7. The electron has minimum energy in the first orbit and its energy increases as n increases. Here
n represents number of orbit, i.e., 1st, 2nd, 3rd..........The thired line from the red end corresponds.
To yellow region i.e., 5. In order to obtain less energy electron tends to come 1 st or 2nd orbit. So
jump may be involved either 5  1 or 5
8. For 4 orbital electrons, n = 4
 = 3, m = + 3, + 2, + 1, 0, –1, –2, –3 s = + 1/2.

1  1 1  1 1 1 
9.  R 2  2  ; = 1.097 × 107  2  2  m–1   = 91 × 10
–9
m = 91 m.
  n1 n 2   1  
10. For hydrogen the energy order of orbital is 1s < 2s = 2p < 3s = 3p = 3d < 4s = 4p = 4d = 4
nh
11. Angular momentum of the electron, mvr = where n = 5 (given)
2
5h h
 Angular momentum =  2.5 
2 
12. According to Heisenberg's uncertainty principle
h
x × p =
4
h h 0.001
x × (m.v) = ; x = v = × 300 = 3 × 10–3 ms–1
4 4m.v 100
34
6.63 10
 x = = 1.92 × 10–2m.
4  3.14  9.11031  3 103

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 PHYSICAL CHEMISTRY
ATOMIC STRUCTURE
13. I.E. = 1.312 × 106 J mol–1
The energy required to excite the electron in the atom from n1 = 1 to n = 2.
 1
= 1.312 × 106 1   = 9.84 × 105 J mol–1
 4
0.005
14. v = × 600 = 3 × 10–3 ms–1
100
6.63 1034
x = 31 3
= 1.92 × 10–2m.
4  3.14  9.110  3 10
h 6.63 1034
15. =  = 3.97 × 10–10 = 0.397 nm.
mv 1.67  10–27 1000
242 103
16. Cl–Cl(g) 
 2Cl(g)  H = 242 KJ mol = J molecule–1
6.02 1023
hc 242 10 23 10 3 6.6 10 34  3 108
E= = =
 6.02 
6.6 1034  3 108 6.6  3  6.02 –6 –6 –9
= 23
=  10 = 0.494  10 = 494  10 m = 494 nm
242 10 10 3
242

17. I.E. of He+ = 19.6  10–18 J atom–1

I.E. = – E1
E1 for He+ is = – 19.6 × 10–18 J atom–1
(E1 ) He (Z He ) 2
=
(E1 ) Li3 (Z Li2 ) 2

19.6 1018 4
=
(E1 ) LI2 9

19.6  9 1018
2+
E1(Li ) = = – 44.1  10–18 = – 4.41  10–17 J atom–1
4

18. E = E1 + E2
hc hc hc 1 1 1 1 1 1
  ;   ;  
 1  2  1  2 355 680  2
2 = 742.76 nm.

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 PHYSICAL CHEMISTRY
ATOMIC STRUCTURE
 1 1 
19. h = E = 13.6 z2  2  2 
 n1 n 2 
   
   
2  1 1   1  1 
He+ = H × z  = H
  n1  2  n 2  2    2 2  4 2 
         
 2   2   2 2 
For H-atom
n1 = 1, n2 = 2
20. (a) 4 p (b) 4 s (c) 3 d (d) 3 p
Acc. to (n + ) rule, increasing order of energy (d) < (b) < (c) < (a)

h
21. =
2mKE

22. 2r = n  2(9 a0) = 3

6  a0

1  1 1  1  1 1 5
23.  R 2  2  ; =R  2  2 = R
  n1 n 2    2 3  36

h 6.63 1034
24. = 
mv 1000  36 1000

25. For macro particles (having larger mass) will be most difficult to experimentally verify the de-
Broglie relationship.
13.6 Z2 13.6  9
26. E = = =30.6 eV
n2 4

 1 1 6.63 10 –34  3 108

27. E = –2.0 × 10–18 J    = 1.5× 10–18 J =
 4 1 
 = 1.325 × 10–7 m

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 PHYSICAL CHEMISTRY
ATOMIC STRUCTURE
28. KE = Ep – W

1 hc hc 2hc   0   
mv2 = – ; v=  
2 0  m   0 

2hc
(4)  0   
m
495.5  103 6.63 10 –34  3 108
29. E= =
6.023  1023 
12
30. (En)H = – 13.6× eV
n2
n=2  E2 = – 3.4 eV
3 1
31. KE = KT = mv2
2 2
h
=
mv
h
=
2mK  E
h
=
3
2m  KT
2
1

m
n 2h 2
32. r=
42 me2 k
22 (6.6262 1034 Js) 2
r=
4  (3.1416) 2  9.109110 31 kg  (1.60210 10 19 C) 2  9 109
r = 2.12 × 10–10 m
r = 2.12 Å
 1 1 
33.  = RH Z2  2  2 
 nf ni 

 1 1
= RH × 12 ×  2  2 
 nf 8 
1 1
 = RH × 2
– RH × 2
nf 8

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 PHYSICAL CHEMISTRY
ATOMIC STRUCTURE
1
curve of  vs is linear
n2
with slope = RH
34. An electron in an orbital of high angular momentum stays away from the nucleus than an
electron in the orbital of lower angular momentum since angular momentum(L)  n .
The plot of  Vs r for various azimuthal quantum numbers, shows peak shifting towards higher
r value.

35.  Graph (2) is wrong

(KE)max = hv - hv
Y = mx + C
Because this graph have a negative intercept.
z 2 ev
36. ET = –13.6 2
n atom
+
For He
22
ET = –13.6 × = – 6.04 ev
32
124 1240
37. Energy of wave = eV = eV = 1.37 eV
(nm) 900
This wave belong to paschen series of atomic spectra
for paschen series
1
E = 13.6 × = 1.51 eV
9
So transition should be  3
38. hv = hv0 + K.E. ...(1)
h2
K.E. = ...(2)
2m 2
Putting (2) in (1)
h2 h2
 hv = hv0 +  h(v – v0) =
2m 2 2m 2
1 1
 2   
(v – v0 ) 1
(v – v0 ) 2

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 PHYSICAL CHEMISTRY
ATOMIC STRUCTURE
hc
39. = kE + Wo

1
kE =  9 10–31  36 1010
2
162 10–21
= 162 × 10–21 J = = 1 ev
1.6 1019
12400
Energy of incident light = ev = 3.1 ev
4000
 Wo = 3.1–1 = 2.1 ev
n2
40.  2 rn = nr & rn = ro ×
z
 n2 
 2  ro   = n (1.5ro)
 z 
n 1.5
 = 0.75
2 2
41. (I) n = 4 l = 2 ml = –2 ms = –1/2 represents e– present in 4d orbital
(II) n = 3 l = 2 ml = 1 ms = +1/2 represents e– present in 3d orbital
(IV) n = 4 l = 1 ml = 0 ms =+1/2 represents e– present in 4p orbital
(V) n = 3 l = 1 ml = 1 ms = –1/2 represents e– present in 3p orbital
According to (n+l) rule,order of energy will be
3p < 3d < 4p < 4d
42. K·E = hv – w0
 K.E > > > w0
 hv > > > w0
hc
 K.E = hv =

1
 K·E 

p2 1
 K·E =  p2 
2m 
2 2
 2  p1   p1  4
      2 = 1
1  p 2   1.5p1  9

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 PHYSICAL CHEMISTRY
ATOMIC STRUCTURE
43. For Lyman series maximum frequency of photon will be observed when electron makes
transition from n =  to n = 1 and a photon of minimum frequency will be observed when
makes transition from n = 2 to n = 1
1 1
= RCZ2  2 – 2 
 n1 n 2 
1 1  1 1  3R C Z2 R C Z2
Lyman = RCZ2    –RCZ2 
1 4  = RCZ2
– 
1   4 4
For Balmer series
Maximum frequency n =  to n = 2
Maximum frequency n = 3 to n = 2
  1 1 1 1 R Z2 5R Z 2 R Z 2
Balmer = RCZ2  2   –RCZ2  2  2  = C – C  C
2  2 3  4 36 9
R C Z2
 Lyman 9
 4 2 
 Balmer R CZ 4
9
44. Total energy of electron will be maximum at n = 
45. There is only one radial node and probability of finding the electrons is maximum near nucleus,
graph belongs to 2s orbital.
46. For Lyman series
1 1 1 
= RHZ2 ×  2  2 
 max 1  
1
 R H Z2
 max
1 1 1 
For Pachen series =  R H Z2  2  2 
 max 3  
1 1
 R H Z2 
 max 9
1
(max) pachen =
9
(max) Lyman = 1
( max ) Pachen 9

( max ) Lyman 1
47. We are getting maxima at point a & c
Electrons are more likely to be found in the region a & c.
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 PHYSICAL CHEMISTRY
ATOMIC STRUCTURE
EXERCISE # (JEE-ADVANCE)
1. The quantum numbers +1/2 and –1/2 for the electron spin represent two quantum mechanical
spin states which have no classical analogue.

2.  - particles are He nuclei.

3. Cobalt is present as Co +2 which has [Ar] 4s03d7 configuration, which means it has 3 unpaired
electrons. So the spin only magnetic moment of the compound is 3(3  2)  15

n2 o
4. rn = 0.529 A
Z
For hydrogen, n = 1 and Z = 1 ;  rH = 0.529 Å
0.529  2 2
For Be3+, n = 2 and Z = 4 ;  r
Be3
= = 0.529 Å
4

5. (a) 22s = probability of finding electron with in 2s orbital

2at node = 0 (probability of finding an electron is zero at node)
For node at r = r0 , 2 = 0
3
1 1  r0 
So,  =0=
2 r / 2a
  2 –  × e 0 0
4 2  a 0   a 0 

 r0  r
  2 –  = 0 or 2 =
 a0  a0
 r = 2a0

h 6.626  10 –34 6.626 10–34

(b) = = = = 6.626 × 10–35 m or 6.626 × 10–25 Å
mv 100  100  10 3 10, 000 10 3

6. (a) For hydrogen atom, Z = 1, n = 1

Z
v = 2.18 × 106 × ms –1 = 2.18 × 106 ms–1
n
h 6.626 10 –34
(b) de Broglie wavelength,  = = = 3.32 × 10–10 m = 3.3 Å
mv 9.110 –31  2.18 106
(c) For 2p, l = 1
h h
 Orbital angular momentum =  (  1) = 2 ..
2 2

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 PHYSICAL CHEMISTRY
ATOMIC STRUCTURE
KZe2 
Kn   Vn 1
7. 2r  so, = – 2 and En  .
 Kn r
KZe2
Vn   
r 
KZe2 
En   
2r 
8. Magnetic moment of orbital angular momentum of the electron in a hydrogen-like atomic
orbital depends on azimuthal quantum number and its direction depends on magnetic quantum
number

9. For lower state (S1)

Number of radial node = 1 = n – l – 1
Put n = 2 and l = 0 (as higher state S2 has n = 3)
So, it would be 2s (for S1 state)
 32 
10. Energy of state S1 = – 13.6  2  eV/atom
2 
 32 
=  2  (energy of H-atom in ground state)
2 
= 2.25 (energy of H-atom in ground state).
11. For state S2
Number of radial node = 1 = n – l – 1 ....... (eq.-1)
–
Energy of S2 state = energy of e in lowest state of H-atom
 32 
= – 13.6 eV/atom = – 13.6  2  eV/atom ; n = 3.
n 
Put in equation (1) l=1 so, orbital is 3p (for S2 state).
1
12. Electrons with spin quantum number = – will be 1(in s) + 3(in p) + 5(in d) = 9.
2
12400
13. Ephoton = = 4.13 ev
3000
Photoelectric effect can take place only if E photon  
Thus,
Li, Na, K, Mg can show photoectric effect.

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 PHYSICAL CHEMISTRY
ATOMIC STRUCTURE
h
14. mv (4a0) =

h
so, v=
4m a 0

1 1 h2 h2
so, KE = mv2 = m. =
2 2 16m 2 2 a 02 32m2 a 02
h
15. = KE  T
2m (KE)

 He m Ne KE Ne 20 1000
= = = 5.
 Ne m He KE He 4  200
16. n = 4, ml = 1, –1
Hence l can be = 3,2,1
i.e. Hf ; 2 orbitals
Hd ; 2 orbitals
Hp ; 2 orbitals
1
Hence total of 6 orbitals, and we want ms = – , that is only one kind of spin. So, 6 electrons.
2
17. 1s orbital does not have any spherical node.
18. Number of radial nodes in 2s orbital = n –  – 1= 1

r / a0
So,
19. 1s orbital cannot have angular part of wave function so, (D) is incorrect.
3
 Zr 
 Z   a 
2
20. For H – atom  n,l .m1   e  0 
 a0 
1 1
13.6   – 
E4 – E2  4 9   27

E6 – E2  1 1  32
13.6   – 
 4 36 

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 PHYSICAL CHEMISTRY
ATOMIC STRUCTURE
z2
21. Total energy = –13.6 × eV
n2
22
–3.4e = –13.6 × eV
n2
13.6 
n2 =  2  16 ; n=4
3.4
Value of  = 2, So, it’s a 4d orbital.

Number of angular nodes =  = 2

Number of radial nodes = n– –1 = 4–2–1 = 1

Effective nuclear charge at this electron will be equal to 2e since no shielding effect.
22. (1) Radius of the nth orbit  n2
(2) Angular momentum of the electron in the nth orbit  n
1
(3) Kinetic energy of the electron in the nth orbit 
n2
1
(4) Potential energy of the electron in the nth orbit 
n2

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