CHEMISTRY (ATOMIC STRUCTURE)
ANSWERKEYS
1. (c) 2. (c) 3. (a) 4. (d) 5. (a)
6. (a) 7. (d) 8. (c) 9. (d) 10. (d)
11. (d) 12. (a), (c), (d) 13. (a), (b), (d) 14. (a), (b), (c), 15. (c)
(d)
16. (b), (c), (d) 17. (a), (b), (d) 18. (a), (b), (c), 19. (b), (c), (d) 20. (b)
(d)
21. (b) 22. (a) 23. (8*106) 24. (Z = 24) 25. (12)
26. (10 amp) 27. (300303) 28. (1233) 29. (3.00) 30. (3.00)
SOLUTIONS
SINGLE CHOICE QUESTIONS
Solution 1: (c)
𝒅[𝑼(𝒓)] 𝟑𝑲𝒆𝟐
= ⇒Magnitude of the force
𝒅𝒓 𝒓𝟒
3𝐾𝑒 2 𝑚𝑣 2
∴ =
𝑟4 𝑟
𝑛ℎ 𝑛ℎ
And we know 𝑚𝑣𝑟 = 2𝜋 or 𝑟 = 2𝜋𝑚.𝑣
8𝜋 3 𝑚3 𝑣 3 𝑛 3 ℎ3
3𝐾𝑒 2 × = 𝑚𝑣 2 , 𝑣 = 24𝐾𝑒 2 𝜋3𝑚2
𝑛 3 ℎ3
Solution 2: (c)
1
− × 𝑃. 𝐸 = 𝐾. 𝐸
2
1 1 1 𝑛ℎ
= − (− 𝑚𝑘𝑟 2 ) = 𝑚𝑣 2 , 𝑚𝑣𝑟 =
2 2 2 2𝜋
𝑛2 ℎ2 𝑛2 ℎ2
𝑣2 = ; 𝑟 4
=
4𝜋 2 𝑚2 𝑟 2 2𝜋 2 𝑚2 𝑘
𝑜𝑟 𝑟 ∝ √𝑛
Solution 3: (a)
1 𝑘(𝑞1 )𝑞2 𝑞2 𝑟. 𝑣 2
𝑚𝑣 2 = ⇒ =
2 𝑟 𝑚 2𝑘. 𝑞1 . 𝑍
𝑞2 2.5 × 10−14 × (2.1 × 107 )2
= ⇒ 4.84 × 107 coulomb/ kg
𝑚 2 × 9 × 109 × 79 × 1.6 × 10−19
Solution 4: (d)
1
Out of 6 electrons in 2p and 3p must have one electron with 𝑚 = +1 and 𝑠 = − 2 but in 3d –
1 1
subshell an orbital having 𝑚 = +1 may have spin quantum no. − 2 or + 2
Therefore, minimum and maximum possible values are 2 and 3 respectively.
Solution 5: (a)
𝑛ℎ 3ℎ
Orbit angular momentum 2𝜋 = 2𝜋 ⇒ 𝑛 = 3
ℎ 3ℎ
Orbital angular momentum, √𝑙(𝑙 + 1) 2𝜋 = √2 𝜋 ⇒ 𝑙 = 2
Hence, electron is in 3d-orbital. For 3d-orbital, radial nodes = (𝑛 − 𝑙 − 1) = 0
Angular nodes = 𝑙 = 2
Solution 6: (a)
1
H = 1s1 , one unpaired electron, S = 2
ℎ 1 1 ℎ √3ℎ
∴ Spin angular momentum = √𝑆(𝑆 + 1) 2𝜋 = √2 (2 + 1) 2𝜋 = 4𝜋
Solution 7: (d)
5×4
No. of spectral lines given by H = = 10
2
4×3
No. of spectral lines given by He+ = =6
2
3×2
No. of spectral lines given by Li2+ = =3
2
However, 𝜆2→1 (𝐻) = 𝜆4→2 (𝐻𝑒 2+ )
Total no. of spectral lines = 10 + 6 + 3 - 1 = 18
Solution 8: (c)
Conceptual
Solution 9: (d)
Conceptual
Solution 10: (d)
Conceptual
MULTIPLE CHOICE QUESTIONS
Solution 11: (d)
Splitting of spectrum lines in presence of electric field is known as Stark effect
Solution 12: (a), (c), (d)
Bohr gave concept of stationary orbits having fixed energies of electrons.
Solution 13: (a), (b), (d)
The energy of an electron in an atomic orbital of multi-electron atom depends upon principal
quantum number as well as azimuthal quantum number (n+l) rule.
Solution 14: (a), (b), (c), (d)
Conceptual
Solution 15: (c)
Number of radial nodes = (𝑛 − 𝑙 − 1)
Number of angular nodes = 𝑙
Solution 16: (b), (c), (d)
Heisenberg’s principle is applicable for moving electrons.
Solution 17: (a), (b), (d)
2 (𝑟)
Radial probability density is 𝑅𝑛,𝑙
Solution 18: (a), (b), (c), (d)
Total nodes = (n – 1)
Number of maxima in radial probability distribution function = (n – l)
For given orbital, n = 3, l = 1, m = -1 to +1
Solution 19: (b), (c), (d)
Conceptual.
COMPREHENSION # 1 (FOR Q. 20 TO Q.22)
Solution 20: (b)
One orbital can accommodate 4 electrons. Therefore, in second period number of elements 8 +
12 = 20.
Solution 21: (b)
n value l values m values (n+l)
1 1
A) l = 1 − ,+ 2
2 2
n=1
B) l = 2 −1, 0, +1 3
1 1
A) l = 1 − ,+ 3
2 2
n=2 B) l = 2 −1, 0, +1 4
3 1 1 3
C) l = 3 − ,− ,+ ,+ 5
2 2 2 2
1 1
A) l = 1 − ,+ 4
2 2
B) l = 2 −1, 0, +1 5
n=3
3 1 1 3
C) l = 3 − ,− ,+ ,+ 6
2 2 2 2
D) l = 4 −2, −1, 0, +1, +2 7
1 1
A) l = 1 − ,+ 5
2 2
n=4
B) l = 2 −1, 0, +1 6
1A8 , 1B12 , 2A8 , 2B12 , 3A8 2C16 , 3B12 4A8 , 4A8 , 3C16
Solution 22: (a)
For E orbital, number of sub-orbitals = 6
Number of electrons = 6 × 4 = 24
NUMERIC ANSWER TYPE
Solution 23: (𝟖 × 𝟏𝟎𝟔 )
The velocity of the electron n in the second state of H atom is v = 1.09 × 108 cm/s
velocity of e− 1.09×108 cm/s
Orbital frequency = = = 8.2 × 1014 𝑠 −1
2πr 2×3.14×0.529×10−8 𝑐𝑚
The number of orbits made by the electron = 8.2 × 1014 𝑠 −1 × 10−8 𝑠 = 8.2 × 10−6 ≃ 8 × 106
Solution 24: (Z = 24)
𝑐
The Moseley’s law is √𝑣 = √𝜆 = 𝑎(𝑍 − 𝑏)
3×108
For copper √15.42×10−9𝑚 = 𝑎(29 − 𝑏) …………. (1)
3×108
For, Mo, √7.12×10−9𝑚 = 𝑎(42 − 𝑏) ……………. (2)
6.58 × 107 = 42𝑎 − 29𝑎 = 13𝑎
a = 5.06 × 106
Substitute the value of a in equation (1)
3 × 106
√ = 5.06 × 106 (29 − 𝑏)
15.42 × 10−9 𝑚
3×108
For impurity, √22.852×10−9 𝑚 = 5.06 × 106 × 𝑍(29 − 1.44)
Z= 24
Solution 25: (12.00)
Since electron goes the state where the path length is 5 times de-Broglie wavelength
⇒ 2𝜋𝑟 = 5𝜆
2𝜋𝑟
Also =𝜆⇒𝑛=5
𝑛
Hence electron goes to the 5th state
2nd highest energy line will be 4 → 1
1 1 1
13.6 (1 − 2
) = 13.6 × 𝑧 2 ( 2 − 2 )
4 𝑛1 𝑛2
𝑛1 𝑛2
⇒ 3 → 12
Solution 26: (10 amp)
Power 90 W=90 J/s
ℎ𝑐 6.626×10−34 ×3×108
The energy of one photon = = = 4.8 × 10−19
𝜆 4000×10−10
90
No. of photons emitted per sec = 4.8×10−19 = 1.875 × 1019
120
No. of photoelectrons emitted per sec = 360 × 1.875 × 10+19 = 6.25 × 1019
Current = 6.25 × 1019 × 1.62 × 10−19 = 10 𝐴
Solution 27: (300303)
𝜓(𝑟) = 0 at radial nodes
∴ 𝑟 2 − 5𝑘3 𝑟 + 6𝑘32 = 0 𝑘3 = 1(given)
𝑟 2 − 5𝑟 + 6 = 0
⇒ 𝑟 = 2, 3 ⇒ two nodes
Radial node = 𝑛 − 𝑟 − 1 = 2 𝛹𝑟 given is for ‘S’ orbital
𝑛−0−1=2 ⇒𝑙=0
𝑛=3 𝐶=0
∴ 𝐴 = 3 principal quant no.
So, the orbital is 3s
ℎ
Orbital angular momnetum = 𝐿 = √𝑙(𝑙 + 1) 2𝜋 = 0, ∴ E = 0
Angular nodes: azimuthal quantum number (l) = 0 for 3s, ∴ B = 0
(𝑛 + 5)𝑠 to (𝑛 + 5)𝑝 ⇒ 8𝑠 to 8𝑝
Energy = 𝑛 + 𝑙 ⇒ 8 + 0 𝑡𝑜 8 + 1 ⇒ 8 𝑡𝑜 9
7d also has energy n + l = 9
∴ total 3 ⇒ 𝐷 = 3
𝐹 = 0 for 3s spherical node
∴ ABCDEF = 300303
Solution 28: (1233)
𝐾. 𝐸𝑛 = −(𝐸𝑛)
−𝑃𝐸𝑛 𝑃. 𝐸
𝐾. 𝐸𝑛 = − ⇒ 𝐸𝑛 = ⇒ 𝑃. 𝐸 = 2𝐸𝑛
2 2
−13.6 × 22
𝐸𝑛 = 𝑒𝑣
𝑛2
𝑃.𝐸. (−13.6×22 )
𝑈1,2 = 2𝐸𝑛 = 2 × 𝑒𝑣 … (1)
12
13.6×12
𝐾1,1 = −𝐸𝑛 = … (2)
12
𝑈1,2 /𝐾1,1 = −8/1 ⇒ 𝑍 = 1
𝑟12 /𝑟21 =?
0.53 × 𝑛2 0
𝑟= 𝐴 ⇒𝑧=2
𝑍
0.53 × 12 0.53 × 22
𝑟12 = , 𝑟21 =
2 1
1
𝑟12 /𝑟21 =
8
𝑍
𝑉𝑛 = 2.18 × 106 𝑚/𝑠
𝑛
3
𝑉1,3 = 2.18 × 106 ×
1
1
𝑉3,1 = 2.18 × 106 ×
3
𝑉1,3 9
= ⇒𝑧=3
𝑉3,1 1
𝑛3
𝑇∝ 2
𝑍
13⁄
𝑇1,2 22 9
Therefore, 𝑇 = 23⁄
= 32 ⇒ 𝑧 = 3
2,3
32
∴ 1233 is the answer.
Solution 29: (3.00)
1 1 1
= RZ 2 ( 2 − )
λ n (n + 1)2
1 (n + 1)2 − n2
= RZ 2 ( 2 )
λ n (n + 1)2
1 (𝑛 + 1 + 𝑛) − (𝑛 + 1 − 𝑛)
= RZ 2 ( )
λ n2 (n + 1)2
1 (2𝑛 + 1)
= RZ 2 ( 2 )
λ n (n + 1)2
𝜆 ∝ 𝑛3
𝑥=3
Solution 30: (3.00)
For radial node
1 1 3/2 18r 2r2
Ψ3s = 0 = 81√3π (a ) [27 − + ] e−r/3a0
0 a0 a20
18r 2r2
27 − + =0
a0 a20
−(18a0 ) ± √(−18a0 )2 − 4 × 2 × 27a20
r=−
2×2
18a0 ±10.39a0
= 4
Distance between two radial nodes = (d)
d 2×10.39a0
= =3
1.73a0 4×1.73a0
SUBJECTIVE ANSWER TYPE
Solution 31:
𝑘𝑒 2
Given, potential energy, 𝑈 = − 3𝑟 3
𝑑𝑈 𝑘𝑒 2
The electrostatic force between electron and proton at a distance r is given by 𝐹 = =
𝑑𝑟 𝑟4
𝑚𝑣 2 𝑘𝑒 2
According to Bohr’s first postulate, =𝐹= ……(1)
𝑟 𝑟4
𝑛ℎ
According to Bohr’s second postulate, 𝑚𝑣𝑟 = 2𝜋………….(2)
4𝜋 2 𝑒 2 𝑘𝑚
From (1) and (2), 𝑟 =
𝑛 2 ℎ2
1 𝑘𝑒 2 𝑘𝑒 2
Total energy of the electron, 𝐸 = 𝐾 + 𝑈 = 2 𝑚𝑣 2 − 3𝑟 3 = using (1)
6𝑟 3
𝑛 6 ℎ6
Substituting the value of r, we get 𝐸 = 384𝜋6𝑚3 𝑘 2 𝑒 4
Solution 32:
From Heisenberg’s uncertainty principle
ℎ ℎ
𝛥𝑥 × 𝛥𝑝 = 4𝜋 or 𝛥𝑥 × (𝑚𝛥𝑣) = 4𝜋
The value of 𝛥𝑥 will be of the order of size of nucleus i.e. 10–15 m.
m = mass of electron = 9.109 × 10–31 kg. Putting these values, we get
6.625 × 10−34
𝛥𝑣 = ≈ 5.785 × 1010 𝑚/𝑠
4 × 3.14 × 9.109 × 10−31 × 10−15
However, the maximum value of 𝛥𝑣 can be 3 × 108 m/s (speed of light)
Thus, the obtained value of 𝛥𝑣 is not practically possible.
Hence, it can be said that the moving electron cannot exist within the nucleus.
Solution 33:
En – En –1 = hv, where v is the frequency of radiation emitted by H-atom due to transition of
electron from n to (n – 1)
2𝜋 2 𝑚𝑒 4 𝑘 2 𝑧 2 1 1
∴𝑣= 3
[ 2
− 2]
ℎ (𝑛 − 1) 𝑛
2𝜋 2 𝑚𝑒 4 𝑘 2 𝑧 2 2𝑛 − 1 2𝜋 2 𝑚𝑒 4 𝑘 2 𝑧 2 2 − 1/𝑛
𝑣= [ 2 ]= [ ]
ℎ3 𝑛 (𝑛 − 1)2 ℎ3 𝑛(𝑛 − 1)2
For very large values of n,
4𝜋 2 𝑚𝑒 4 𝑘 2 𝑧 2
∴𝑣= ….. (i)
𝑛3 ℎ 3
The frequency of revolution of electron in nth orbit, fn is given by :
2𝜋𝑘𝑧𝑒2
𝑣𝑛 𝑛ℎ 4𝜋 2 𝑚𝑒 4 𝑘 2 𝑧 2 4𝜋 2 𝑚𝑒 4 𝑘 2 𝑧 2
𝑓𝑛 = 2𝜋𝑟 = 𝑛2 ℎ2
= = ….. (ii)
𝑛 𝑛3 ℎ 3 𝑛3 ℎ 3
4𝜋2 𝑚𝑒4 𝑧𝑘
From (i) & (ii) for very large values of n, the frequency of radiation emitted by H-atom due to
transition of electron from n to (n – 1) is equal to frequency of revolution of electron in its orbit.
Solution 34:
1
𝑅3𝑠 = 0 ⇒ (6 − 6𝜎 + 𝜎 2 )𝑒 𝜎/2 = 0
9√3𝑎0 3/2
⇒ 6 − 6𝜎 + 𝜎 2 = 0
+6 ± √36 − 24 6 ± 2√3
∴𝜎= = = 3 ± √3
2 2
2𝑟
= 3 ± √3 solving this gives
3𝑎0
9 ± 3√3
𝑟=( ) 𝑎0
2
