Atomic Structure 2.

Chapter 2 Atomic Structure

INTEXT EXERCISE: 1
1. Hydrogen atom contains 1 proton, 1 electron and no 8.
m
e = 1.5 × 10 e = 1.6 × 10 19
8
neutrons.
m = 1.5 × 10 8 × 1.6 × 10 19 = 2.4 × 10 27
kg
2. Cathode Rays have constant b m
e l ratio.
m = 2.4 × 10 24
g
(e/m) e e/me 3672 9. Charge on oil drop = 6.39 × 10 19
C
3. (e/m) = 2e/(4 # 1836m = 1
a e)
a × C is charge on one electron
4. Factual.
× C is charge on
5. rN + 10 -13 cm and ratom + 10 -8 cm
- 6.39 # 10 -19
Volume of nucleus = = 4 electrons.
Volume fraction = Total vol. of atom - 1.602 # 10 -19
10. From particle scattering experiment, distance of
(4/3) r (10 -13) 3
= = 10 -15 closest approach of particle with nucleus came out
(4/3) r (10 -8) 3 to be of the order of 10 14 m. This scattering followed
6. R = RoA1/3 = 1.3 × 641/3 = 5.2 fm Coulomb’s law and gave the size of the nucleus to
7. Speed of cathode rays is less than speed of light. be < 10 14m.

INTEXT EXERCISE: 2
c 3 # 10 8 7. According to Planck’s Quantum Theory the
1. m = y = = 0.75 m minimum energy which can be absorbed from an
400 # 106
EM wave
2. Violet colour has minimum wavelength so maximum
energy. hc
=
m
hc
3. I.E. of one sodium atom = 8. E \
1
m m
& I.E. of one mole Na atom = 2000 and 2 = 4000
1
hc 6.62 # 1034 # 3 # 108 # 6.02 # 10 23
NA = m2
m 242 # 10 -9 E1
E 2 = m1 = 2
= 494.65 kJ. mol.
9. = 6 × 1014 Hz
4. Energy absorbed = 40 J/s
Now, c =
Energy released (as EM waves) =0.8×40= 32 J/s 1 y
y= = c
32 × 20 =
nhc m
m
6×1014
n = 2 × 1021 y= = 2×106 m -1
3×108
1
5. y =
m hc
10. Eabsorbed = 500 = Ereleased
1
y= = 2 × 106 m 1
hc hc
500×10 -9 m Now, Ereleased = 800 +
m
6. 4 waves are passing through a given point in 2s. 1 1 1
= -
a Frequence = no. of waves / sec. m 500 800
Frequency = 4/2 = 2 Hz 1
=
3
m 4000
= 1333.3 nm
2.2 Chemistry
INTEXT EXERCISE: 3
b n l As Z increases, radius of 1st orbit decreases.
2 6. S1 : Potential energy of the two opposite charge
1. r Z system decreases with decrease in distance,
n2 c S4 : The energy of 1st excited state of He+ ion
2. Radius = 0.529 z A = 10 # 10 -9 m
= –3.4 Z 2 = –3.4×2 2 = –13.6 eV
So, n2 = 189 or n . 14 S2 and S3 are correct statement.
12 T n3 13 1
3. E1 (H) =- 13.6 # =- 13.6 eV ; 7. T1 = 13 = 3 = 8 . (for same Z)
12 2 n2 2
a bT = v l
22 2rr so, T \ 2
n3
E 2 (He +) =- 13.6 # =- 13.6 eV
22 Z
32 r n2 R
E3 (Li 2+) =- 13.6 =- 13.6 eV ; 8. r \ n2 and r \ n3 for same Z r12 = 12 = 4R
32 n2
n1 1
E 4 (Be3+) =- 13.6 #
42
=- 13.6 eV n2 = 2
42 T1 n13 1
E1 (H) = E 2 (He +) = E3 (Li 2+) = E 4 (Be3+) T2 = n32 = 8 .
9. Angular momentum J = mvr
Z
4. v = 2.188 # 106 n m/s J2 = m2 v2 r2
or 2 = b 2 mv 2 l mr 2 or K.E. =
Z Z /n 3/3 J2 1 J2
Now, v \ n So, = Z 1 /n1 = 1/1 = 1
2 2 2mr 2
v3(Li2+) = v1 (H) 10. a) Energy of ground state of He +

= –13.6×2 2 = –54.4eV (iv)

5. rn - rn = 24 # (r1) H
1 2 b) Potential energy of 1 orbit of H atom
st

= –27.2×1 2 = –27.2eV (ii)

0.529 # n12 0.529 # n 22
1 - 1 = 24 # 0.529 c) Kinetic energy of 2 excited state of He+
nd

22
(n12 - n 22) = 24 = 13.6× 2 = 6.04 eV (i)
3
So, n1 = 5 and n2 = 1 d) Ionisation potential of He+
= 13.6×2 2 = 54.4 V (iii)

INTEXT EXERCISE: 4
Z2 (1) 2 For last line of Pachen series
1. E n = E1 E5 =- 13.6 # =- 0.54 eV
y 2 = R H (3) 2 < 2 - F= R
n2 (5) 2 1 1
(3) (3) 2
hc 1
2. m = 9E ` ma 9E R
Thus, difference = 4
3. Infrared lines = total lines – visible lines – UV lines
6 (6 - 1) 8. (He+)2 4
= (Li 2+) n 4 " n3
Total lines = 2 = 15 Z1 n2 n1 2 2 4
Z 2 = n 4 = n3 or 3 = n 4 = n3
visible lines = 4 (6 2, 5 2, 4 2, 3 2)
UV lines = 5 (6 1, 5 1, 4 1, 3 1, 2 1) n4 = 3 and n3 = 6.
Transition in Li2+ ion = 3 6
4. When electron falls from n to 1, total possible
9. y1 = Rc Z 2 c 2 - 2 m = Rc Z 2 ,
1 1
number of lines = n – 1.
n1 3
5. Visible lines Balmer series (5 2, 4 2, 3 2)
y 2 = Rc Z 2 c 2 - 2 m = 4 Rc Z 2 .
1 1 3
So, 3 lines. 1 2
y3 = Rc Z 2 c 2 - 2 m = 4 Rc Z 2
6. According to energy, E 4 " 1 > E3 " 1 > E 2 " 1 > E3 " 2 . 1 1 1
2 3
According to energy, Violet > Blue > Green > Red. = 3.
1 2
Red line 2 transition.
10. Visible lines Balmer series only in H atoms.
7. For 1st line of Balmer series In H like species, e.g. He+, we cannot make
y1 = R H (3) 2 < 2 - F = 9R b 5 l = 5 R
1 1 generalizations of certain lines lying in the visible
(2) (3) 2 36 4 region.
 Atomic Structure 2.3
INTEXT EXERCISE: 5
1. For photoelectric effect to take place, 6. P.E.E. occurs only if in
> o

Elight > K.E. in

not velocity of photoelectron.
hc hc 7. K.E.max = h
$ or m # m 0 . in
m m0
2. Photoelectric effect is a random phenomena. So, 8. incident
= 1

electron may come out with a kinetic energy less hc

K. E. = -z
than or equal to (h – w) as some energy is lost m1
hc z
while escaping out. stopping potential = -
m1 e e
3. If > 0, emission takes place with a maximum K.E. when incident = 2
of h h o. The K.E. is independent of the intensity hc z
but the number of photoelectrons increases with stopping potential = -
m2 e e
intensity.
stopping potential increase by e c
hc 1 - 1 m
hc m 2 m1
4. = 1+z ...(1)
m
hc 9. | Max K.E. | = | stopping potential |
3# = 4+z ...(2)
m K.E.max = 1.5 eV also = 2.5 eV
from, e.q., (1) and (2) z = 0.5 eV Eincident = 1.5 + 2.5 = 4 eV
5. Number of lines in Balmer series = 2 10. K.E.mzx = Ein =6 2.1 eV
n = 4 (lines will be 4 2, 3 2). = 3.9 eV
KE of ejected photoelectrons stopping potential = 3.9 eV
13.6
= Ephoton En = 13 - 2 = 13 0.85 = 12.15 eV.
4
INTEXT EXERCISE: 6
-34
h 6.625 # 10 # h
7. 9p $ 9x = 4r
1. m = mv = 0.2 # 5 3600 . 10 -30 m.
6.62 # 10 -34
2.
m1
= V2 =
V 200 2 9x = = 5.27 # 10 -30 m.
m2 1 50 = 1 . 4 3.14 # 1 # 10 -5
#

3. r1 = 0.529 A c my mx vx my m vx 16
8. = & 1 = (0.25m )x (0.75v = 3 .
r3 = 0.529 # (3) 2 Ac = 9x mx my vy x x)

2rr 2r (9x)
So, m = n = 3 = 6rx. h
9. m = mv
o
12.3 m p ma va
4. m = A gives the De-Broglie wavelength of an
V = m v m = 4mp
ma p p
electron accelerated by V volts.
mp 4m v 1 va vp 8
n n n 2 4 = m av a 2 = 4 # vp va = 1
5. m \ Z ` Z1 = Z2 or 3 = 6 (n = 4 of C5+ ion) ma p p
1 2

h 10. =v
6. For a charged particle m = h h
2mqV then m = mv or m2 = m
1
m\ . h
V So, m= m
INTEXT EXERCISE: 7
h No. of unpaired electron = 4.
1. Orbital angular momentum = , (, + 1) 2r = 0.
X26 : 1s22s22p63s23p63d84s2.
= 0 (s orbital).
2. Cu:1s 2 2s 2 2p6 3s 2 3p6 3d10 4s1 . will be 3d6.
Cu :1s 2s 2p 3s 3p 3d or 6Ar@ 3d .
2+ 2 2 6 2 6 9 9
No. of electrons lost = 2 (from 4s2).
3. Magnetic moment = n (n + 2) = 24 B.M. n = 2.
2.4 Chemistry
4. Zn2+ : [Ar]3d10 (0 unpaired electrons). h
8. Orbital angular momentum = , (, + 1) 2r
Fe 2+
: [Ar]3d (4 unpaired electrons) maximum.
6
Now for 2s orbitals, l = 0
Ni 3+
: [Ar]3d7 (3 unpaired electrons). Orbital angular momentum = 0
Cu+ : [Ar]3d10 (0 unpaired electrons). 9. 17
Cl : [Ne]3s23p6
5. d7 : 3 unpaired electrons Last electron enters 3p orbital.
n 3
Total spin = ! 2 = ! 2 . , = 1 and m = 1, 0, - 1.
10. n = 3 can have = 0, 1, 2
6. X23 : 1s22s22p63s23p63d34s2.
if =0 orbital angular momentum = 0
No. of electron with , = 2 are 3 (3d3) .
2h
if =1 orbital angular momentum = 2r
7. Cr (Zn = 24)
6h
1s 2 2s 2 2p6 3s 2 3p6 4s1 3d5 if =2 orbital angular momentum = 2r
So, no. of electron in , = 1 i.e., p subshell is 12 and
no. of electron in , = 2 i.e., d subshell is 5.
INTEXT EXERCISE: 8
1. For 6g orbitals, n = 6 and = 4. 6. Spherical node = n 1
Radial nodes = n 1=6 4 1 = 1 and non spherical = .
Angular nodes = = 4 7. The dual nature of electrons is the premise on which
Total 5 nodes. this model is based.
2. The radius of maximum probability of 1s orbital of 8. i) Electron density in the XY plane in 3d x - y 2 2

H atom has a value of 0.529Å. orbital is not zero

ii) Electron density in the XY plane in 3d z orbital
2

3. A has 0 radial nodes and B has 1 radial node

is not zero
A is 1s and B is 2s iii) 2s orbital has one nodal surface it is a spherical
4. Dumbell lies at 45o to x & y axis represents dxy node.
orbital. iv) For 2pz orbital, XY is the nodal plane
5. XZ is the nodal plane of px orbital 9. Factual.
10. n, and m, are obtained from .

EXERCISE 1

1. Cathode rays are made up of electrons and have 8. Urea CO (NH2)2

mass and charge both Atomic no. of C=6
2. It is average isotropic weight O=8
3. Isotones same value of A Z i.e. same number of 2N = 7 x 2 = 14
neutrons. 2H2 = 4
6 + 8 + 14 + 4 = 32
4. A nucleus has a much smaller volume than that of an
9. In the equation E = h , E is the energy of a packet
which discribes the particle nature and is the
5. The fraction of particles undergoing a deviation
frequency of the EM wave and describes the wave
of 180o is proportional to the ratio of volume of
nature.
nucleus to that of the atom.
10. Photons denote the particle nature of light.
6.
electrostatic forces of repulsion. 11. Red has the largest wavelength and hence smallest
frequency among the visible light.
7. Nucleon are the particles in the nucleus.
12. A packet of energy of EM waves is called quantum.
 Atomic Structure 2.5
13. = 600 nm 29. Lyman series emits highest energy lines and 2nd line
c of any series has more energy than 1st line. So 3 1
m has highest energy and lowest .
3 ×108
= 30. Max number of spectral lines
600 ×10 -9
= 5 × 1014 Hz
(n 2 - n1) (n 2 - n1 + 1) ]4 - 1g]4g
= 2 = 2 =6
n2 31. As atom is excited so energy of electron >
14. rn = 0.529 × Z rn \ n2
r1 : r2 : r3 = 1 : 4 : 9 13.6 eV

1 32. When electron is in excited state in H atom,

15. K.E. = T.E. = - 2 P.E.
E> 3.4 eV. Thus, I.E. < 3.4 eV
For n = 3 and Z = 1
33. A quantum having energy equal to the difference
T.E. = 1.51 eV of energy between the two energy levels is emitted
K.E. = + 1.51 eV and P.E. = 3.02 eV during de excitation.
2
16. E =
Z
13.6 34. E in L shell (n = 2) = 3.4 ev. If it loses 10.2 eV then
n2 new energy = ( 3.4 10.2) eV
1
= 13.6 × 9 = 1.51 eV = 13.6 eV.
17. rn = ron2 r3 = 9ro 35. E1 = 54.4 eV
18. E at n = 1 = 13.6 eV - 54.4
E2 = 4 =- 13.6 eV
E at n = 2 = 3.4 eV I. E. = 13.6 eV.
E at n 3 = 1.51 eV 36. Theoretical.
1st excitation potential = 10.2 37. Free electron at rest has 0 energy. When the electron
2nd excitation potential = 12.09 eV is bound to an atom, its energy is therefore negative.
19. I.E. from n = 3 is 1.51 eV 38. Shortest line of Paschen n= 3$ n=3
E3 = 1.51 eV = R3 2 : 9 - 3 D
1 1 1
m
E1 =1.51 × 9 = 13.6 eV
1
13.6 m= R
E2 = 4 = 3.4 eV
39. Z = 2
20. L shell — n = 2
n = 2 n = 1 (Longest for lowest E)
E = 3.4 eV
= R × 4 :1 - 4 D = R × 4 : 4 D
1 1 3
P.E. = 2 × 3.4 eV = 6.8 eV m
- P.E. 1
m = 3R (b)
21. K.E. =- T.E. = 2
22. K.E. decreases and total energy increases. 40. Z = 1
23. The charge on the nucleus of atomic no. Z n = 3 $ n = 1 (Shortest for highest E)
1
24. 3.4 eV (When n = 2). The possible value of energy = R x 1[1] = R
m
13.6
are - 2 eV where ‘n’ is an integer. 1
m= R =x
n
25. Bohr said that electrons neither gain nor lose energy Z=2
when they are at particular orbits and hence these
n=3 n=2
orbits are called stationary states.
x × 4: 4 - 9 D
1 1 1 1
26. Emission spectra is diserect, unequally spaced with =
m

x × 4 : 36 D
varying intensity. 1 1 5
=
m
27. Electrons reaching n = 4 from any state emits EM
1 1 5
waves in the Brackett series. = x×9
m
28. The energy of the orbits keep changing with Z. Thus 9x
m= 5
line spectra of no two elements are indetical.
2.6 Chemistry
41. Photo electric emission occurs when > o
61. spin Q.N. is not obtained from .
42. Refer Q. 41 above 62. Theoretical
V I B G Y OR 63. Degenerate orbitals are such orbitals which have
43.
decreasing frequency same energy.
So only V, I, B, G can cause emission
64. For m = 2, can be from 2 to 2.
44. It establishes the existence of quantum of energy,
65. If n = 2 then can be 0 or 1.
which is a packet of energy.
66. An orbital can have maximum 2 electrons.
45. h ( 1 0
) = K.E.
then K.E. - 67. For principal Q.N. n, number of possible values of
1
is also n. Hence, number of subshells = n.
1242
46. E =
m (nm) 68. No. of subshells = n = 3.

4=
1242 No. of orbitals in 3s, 3p, 3d = 1 + 3 + 5 = 9.
m (nm) o
69. d x - y orbitals are double dumbbell shaped with its
2 2

(nm) = 310.5 nm = 3105 A

two lobes lying along the x and y axes.
47. KE1 = E1 70. Since m = 1, therefore it cannot be s orbital
KE2 = 2E1 becuase for s orbital m = 0.
K.E.2 = 2K.E.1 71. Orbital anular momentum = 2r , ], + 1g
h
48. Changing frequency changes the K.E. of the 72. m can be to + . So no. of values possible
photoelectron, not the number of electrons ejected.
= 2 + 1.
Photocurrent increases on increasing intensity to
and attains a maximum value. 73. 19th electron goes to 4s orbital in Chromium.
49. Theoretical. 74. Fe3+ : [Ar] 3d5
50. Co2+ : [Ar] 3d7
0.101 c n = n (n + 2)
51. For an particle ( ), m = A.
V
52. r1 = x r4 = 42 x = 16 x. n Fe3+
5×7
nCo =
2+
3×5
circumference = 2 (16x) = 4 3

=8 x = 35 : 15
3

53. According to Heisenberg it is impossible to 75. For g subshell = 4

determine both the position as well as the momentum No. of e = 2 ( 2 × 4 + 1) = 18.
of a particle simultaneously and accurately. 76. Two spectral lines of an element cannot have the
54. d orbital has =2 same wave number.

55. For 2 electrons in same orbital, n, , m are same but 77. s orbital is spherically symmetric. The probability
s is different. distribution is uniform in all directions independent
of the angle.
56. No. of orbitals in a subshell = 2 + 1. Since each
orbital can have a maximum of 2 electrons therefore, 78. No. of radial nodes = 4 2 1 = 1.
maximum no. of electrons = 2 (2 + 1). Thus (d) is correct.
57. n = 2 may have one s and 3 p orbitals with a maximum 79. Radial nodes = 5 3 1=1
of 8 electrons.
58. n = 2 = 1 for 2 p orbitals. Angular node = 3
Total number of nodes = 5
59. f subshell has 7 orbitals and can accomodate a
maximum of 14 electrons. 80. No. of radial nodes for 5d orbitals = 5 2 1=2
60. p orbital is dumbell shaped. Number of maxima in graph = no. of nodes + 1 = 3.
 Atomic Structure 2.7
EXERCISE 2
1. Isotopes have same atomic number and different 13. N shell n=4
mass number. - 13.6 × 4 2
E4 (Bi3+) = = 13.6 eV
2. The particles (He2+ 42
Now, P.E. = 2 T.E. = 27.2 eV
positively charged nucleus due to the electrostatic
forces of repulsion. - 13.6
14. P.E. of n = 2 of H atom = 2 × 4 = 6.8 eV
3. Rutherford discoverd the nucleus by this experiment. 6.8
Now, for He+ if K.E. = 2 , T.E. = 3.4
4. rnu = 1.25 × 10 13
× 641/3 cm = 5 × 10 13
cm - 13.6×4
=- 3.4 & n = 4
n2
ratom = 10 cm 8
0.529×9 o 0.529×16 o
VNu 3
r nu 125×10 -39 15. r3 (He+) = A and r4 (He+) = A
= = = 1.25 × 10 13 2 2
3
Vatom r atom 10 -24 0.529 o o
r4 r3 = 2 (16 9) A = 1.851 A
5. A = 39 n + p = 39 and n = (p+1)
(p + 1) + p = 39 p = 19 0.529×16
16. r4 (Z) = Z
Also, e = 19 r1 (H) = 0.529
Now, n = (p + 1) = 20.
Z = 25 from the given options
6. In an element ZA X ,
Note: for Z = 16 it overlaps and doesn’t fit inside
no. of protons = electrons = Z the 1st Bohr orbit of H.
no. of neutrons = A Z ro $ 4 RZ
28×60 + 29×30 + 30×20 17. r2 = R = Z & ro - 4
Mavg = 110 RZ 9 9
= 28.64. r3 = 4 × Z = 4 R = 2.25R
7. Atomic electrically neutral as well as nucleus n2
18. 0.529× 4 = 0.529
contains neutrons but neutrality is due toequal
number of protons and electrons. `n=2
hc
8. Eabsorbed = Ereleased =
hc hc
+ 19. rn \ n 2
^n 22 - n12h
m m1 m 2
Spacing is maximum when is
hc hc hc mm maximum.
= + &m= 1 2
m m1 m 2 m1 + m 2
1
9. Let no. of quanta absorbed and emitted be na and ne 20. E n \
n2
respectively. spacing in terms of energy is maximum when
n a hc n e hc 1 1
Ea = 4500 and Ee = 5000 - is maximum.
n12 n 22
ne 1 na
Now, Ee = 0.5 Ea & 5000 = 2 × 4500 21. r \ n 2 and time period \ n3
ne 5000 5 r T
na = 9000 = 9 = 0.55
1 1
since r12 = 4 & T1 = 8
2
10. Rest mass is not property of photons as they never 22. Bohr’s model cannot explain emission spectrum of
come to rest. multi electron species.
hc
11. E of quanta able to ionize Na = 23. More the energy of an electron, for ther a way from
2414 ×10 -10
the nucleus it can stay.
hc 6.02×10 23
I. E. of Na = -10 × kJ/mol
2414×10 103 24. E3 E1 = 12.09 eV for H atoms.
. 497 kJ/mol.
Other permissible values of energy absorbed may be:
12. P.E. = 2 T.E. T.E. = 3.4 eV. Z = 2 : 12.09 × 4 = 48.36 eV
- 13.6
3.4 = Z = 3 : 12.09 × 9 = 108.81 eV
n2
n=2 and so on.
1 excited state.
st
2.8 Chemistry
= R ×1 : 9 - 16 D
25. From III to I, 1 1 1
hc m
2E E=E= .....(1)
m 1 7R
From II to I =
m 144
4E E hc 144
3 - E = 3 = m1 ..... (2) m = 7R

Divide (1) and (2) 36. I.E. = x E1 = x

m x x
E2 = - 4 and E3 = - 9
3= 1
m
` m1 = 3m (d) x x 5x
E2 3 = 4 - 9 = 36
Z
26. v \ n & lower the value of n, higher the speed. 37. K.E.1 = h i = and K.E.2 = 2h i

27. Since EC B + EB A = E C A K.E.2 = 2 K.E.1 +

hc hc hc Now, as intensity is doubled, the number of ejected
+ =
m1 m 2 m3 electrons increases and hence photo current increases
m1 + m 2 1 but it might not necessarily double.
=
m1 m 2 m3 38. As is doubled, Eincident is halved and hence stopping
mm potential decreases provided Eincident > .
m3 = 1 2
m1 + m 2
39. The number of photons emitted per unit time
28. I.E. of He+ = (I.E. of H) Z2 = 13.6 × 4 eV increases incident as higher intensity EM waves of
= 54. 4 eV suitable are
29. He(g) — H(g)+ + e 24.5 eV (given) 40. As intensity remains constant, the number of
electrons emitted are constant. But as increases
He (g)
+
— H(g)2+ + e 54.4 eV (Bohr’s Model)
Ein decreases and hence K.E.max and magnitude of
He(g) — H +
(g)
+ 2e 78.9 eV (Adding the 2) stopping potential decrease.
30. Second series is Balmer series (n1 = 2) fourth line 41. = 4 × 1015 Hz
i
would be 6 2.
K.E. = 10.33 eV
31. 4 excited state is n = 5. So, 5
th
3 and 4 3 i.e., 2 =h K.E.
i
lines in the Paschen sereis.
4×1015 ×6.6×10 -34
= 10.33 +
32. n2 n1 = 2 and n2 + n1 = 4 1.6×10 -19
= 6.2 eV
n2 = 3 and n1 = 1
hc
= R4 ; 2 - 2 E & = 9
1 1 1 1 32R 42. = + 3qVo
m
m 1 3 m hc
= + qVo
= RZ 2 ; 2 - ]n + 1g2 E
1 1 1 2m
33. hc
m n Solving we get = =4
4m o

or y = = RcZ 2 c 2 ]n + 1g2 m
c 2n + 1
hc
m n 43. E = mc2 and also E =
m
if n > > 1 then (n + 1) . n and (2n + 1) . 2n mc =
2 hc
m
2RcZ 2
y= h
n3 m=
cm
= R ;1 - 2 E & 2 = 1 -
1 1 1 1 1
34. 44. m =
h
& more the charge lesser the
m n n Rm
2mqV
=b l& n =
1 Rm - 1 Rm
or, m1 q2 2
n2 Rm Rm - 1 = q = 1
m2 1
nh 2h
35. 2r = r n=4 = 1.414 2
1
n=4
n2 = 4 n1 = 3 is the transition that takes place.
 Atomic Structure 2.9
45. p= x p
h ` n 2 + 2n - 15 = 0 n = 3 or 5
4r
`n=3
h
p=m v= Mn +x = 1s 2 2s 2 2p6 3s 2 3p6 3d3
2 r
1 h x = + 4.
v = 2m r
56. By Aufbau Principle. {(n+ ) rule}
h
46. 0.1 × 10 = p 9
1 1
57. The quantum numbers + 2 and - 2 for electron
6.6 ×10 -34 spin represent two quantum mechanical spin states
`p=
0.1×10 -9 which have no classical analogue.
p = 6.6 × 10 24 kg m/s 58. By convention d z and pz are the orbitals which are
2

h assigned m = 0 for = 2 and = 1 respectively.

47. m = p . Hence is inversely proportional to p.
59. No. of values of m is the no. of orbtials present in a
48. Eabsorbed = 1.5 × 13.6 eV given subshell. Thus, m = 2 +1 = 2
m-1
K.E. of emitted electron = 6.8 eV
60. Hund’s Rule says that pairing of electrons in an
h 6.625×10 -34
2m ]K.E.g
= atomic orbital will take place only after all the
2×9.1×10 -31 ×6.8×1.6×10 -19 degenerate orbitals have been singly occupied.
o
= 4.70 A 61. Greater the atomic number smaller is the size of the
species. Thus, the graph with the highest probability
h 6.625 × 10 -34 at the least value of ‘r’ represents Li2+ while the one
2m ]KEg
49. m = =
2×9.1×10 -31 ×4.55×10 -25 with the peak at largest value of ‘r’ represents H.
= 7.28 × 10 -7 m 62. For radial node, =0
50. E A - WA = K A ` E A - 2 = 4K B 6 ! 36 - 24
EA - 2 = KA E A + 0.5 - 4 = K B 6 6 + 2
=0 = 2
EB - 4 = KB E A - 3.5 = K B 2rZ
= 3! 3 3a o 3! 3
h2
m a2 = 2m × K ` E A - 2 = 4E A - 14
r1 = 2Zo ^3 + 3 h and r2 = 2Zo ^3 - 3 h
A 3a 3a
2
h
4m 2A = m 2B = 2m × K ` E A = 4eV 3 3 ao
B 3a
EB = 4.5eV (r1 r2) = 2Zo ×2 3 = Z
1 K
1 :ZD 2
3
` 4 = K B ` K A = 4K B VA = 2V, VB 0.5 V v
A 63. } = [(v - 1) (v 2 - 8v + 12)] e - 2
16 4 a o
h
51. Orbital angular momentum = , (, + 1) 2r (v - 1) (v 2 - 8v + 12) = 0
for d orbital =2 v = 1 or v 2 - v6 - 2v + 12 = 0
h
Orbital angular momentum = 2r 6 v (v - 6) - 2 (v - 6) = 0
52. No. of electrons for given value of = 2 (2 + 1) v = 2 or v = 6
and can very from 0 to (n 1) min
=1
, = n-1
No. of electrons = / 2 (2, + 1) a
& rmin = 2Z0
,=0

53. All p orbitals and d x - y , d z are located along the

2 2 2 and max = 6
axis. 3a
& rmax = Z0
54. s orbitals are spherically symmetric hence the
64. Since becomes 0 for one value of r, therefore
is same in all directions. number of radial nodes = 1.
65.
55. Mn = 1s 2 2s 2 2p6 3s 2 3p6 4s 2 3d5
zero.
3.873 = n (n + 2)
15 = n2 + 2n
2.10 Chemistry
EXERCISE 3

1. For He+ : x = R $ 4 ; - E & Rc 2 - 2 m = x

1 1 1 1 10. 12
6 C contains 6 protons and 6 neutrons and weighs
n12 n 22 n1 n 2 4 12 amu. Mass of electron is negligible.
Now, if mass of neutrons is halved, total mass = 9
= R $ 16 ; 2 - 2 E & = 16× 4 = 4x
1 1 1 1 x
For Be3+ : amu.
m n1 n 2 m
3
2. Note that the question states that there is a single H reduction in mass = 3 amu 12 × 100 = 25%
atom. Thus, the maximum number of spectral lines 11. Factual.
emitted may be 3 for the transitions 5 4, 4 3
and 3 2. 12. Red end we are talking about visible region of the
EM spectrum Balmer series in an H atom.
3. The lowest value of ‘n’ for which d orbital exists Thus, 3rd line from red end 5 2
is 3.
13. Balmer series lines of only H atoms lies in the visible
6
4s2
region of the spectrum
4th period.
14. K shell n=1
E2 1=13.6 b 1 - 4 l eV and E3 2=13.6× b 4 - 9 l eV
1 1 1 1
4. L shell n=2
3 5 M shell n = 3 and so on
= 13.6× 4 eV = 13.6× 36 eV
Since electron makes transition into n = 2, therefore
3 E2 " 1 3/4 27 it is Balmer series.
3 E3 " 2 = 5/36 = 5
15. Lyman series is in UV region and Balmer series is in
5. Factural : K. E.max = h incident visible region in H atom.
6. Orbital angular momentum = 2r , ], + 1g = 2r The 4 lines in uv region are : 2 1, 3 1, 4 1, 5 1
h 6h

3h In the visible region we will have: 3 2, 4 2, 5 2

angular momentum in 3rd Bohr orbit = 2r
In the IR region: 5 4, 5 3, 4 3 3 lines
6 2
ratio = 3 = 3 16. Rest mass of photon =
h
cm
= 1.73 = 3 = n ]n + 2g
= R :1 - 4 D = 4 R
7. 1 1 3
For 1st line of Lyman:
no. of unpaired electrons, n = 1. m1
= R : 4 - 9 D = 36 R
Now Vanadium has Z = 23 and E.C. of [Ar] 4s23d3 1 1 1 5
For 1st line of Balmer:
m2
for 1 unpaired electron V must be in + 4 state
m1 m2 m1 3 36 27
with an E.C. of [Ar] 3d1. m 2 = m1 & m 2 = 4 × 5 = 5
1
8. 4.25 A
= TA and A
\ 17. Series limit of any series & 3 $ n1
TA
= R :1 - 3 D &
1 1 1 1
1 For Lyman series: =R
4.2 = TB and \ mL mL
B B

= R; 2 - 3 E &
TB 1 1 1 1 R
a =2 For Balmer series: = 4
B A mB 2 mB
TA = 4 TB L
=4 B
Now, TB = TA 1.5 3 TB = 1.5 18. Theoretical
TB = 0.5 eV and TA = 2 eV
19. Spectral lines of an element are unique and no 2
A
= 4.25 TA = 2.25 eV lines of an element can have the same wavelength.
and B
= 4.2 TB = 3.7 eV 20. is the probability density i.e. probability per unit
2

9. 2.1 g ion of Cl 2.1 mole Cl ions volume.

Now, 1 Cl ion has 18 electrons 21. In H atom
2.1 mole Cl contains 18 × 2.1 × NA electrons Elyman > Ebalmer > Epaschen ..........
lyman
< balmer
< paschen

1
< 2
< 3
< 4
 Atomic Structure 2.11
o o 36. In H atom, or any other H like species, the energy of
22. For n = 10, r = 0.529 × 102 A = 52.9 A
the electron depends only on the value of ‘n’. Thus,
2× × 52.9 = 10 we can say that for such species (E4s = E4p = E4d =
= 33.22 A
o
E4f) > E3s = E3p = E3d and so on.

23. I : 1 radial node 3p 37. Factual.

II : Zero radial nodes 3d 38. Heisenberg’s uncertainty principle is valid for both
microscopic and macroscopic moving objects.
III : 2 radial nodes 3s
24. Longest wavelength of Paschen series 4 3 objects.
R $ 1 2 $ : 9 - 16 D = R $ 2 2 $ ; 2 - 2 E
1 1 1 1 h
n1 n 2 39. 3 x $3 p $ 4r
n1 = 6 and n2 = 8. dp
Now, dt = dF dp = dF.dt
25. 2
is maximum at nucleus and 3 r2 2
is zero.
dE
hc And dF $ dx = dE & dx = dF
26. E = h = = hc y
m dE
hc dp $ dx = dF $ dt $ dF
Also, Etot = n , but energy of 1 quantum is
m
= dE $ dt
independent of n.
27. \ particles being much heavier than the electrons Heisenberg’s principle may be written as
have a high penetrating power, which is also because h
3 E $3 t $ 4r
of the high speed of \ particles.
40. In option (c) if = 2 then ‘m’ cannot be 3.
28. All 4 statements were conclusions drawn from the
\ scattering experiment. 41. a) s orbital is spherically symmetric
29. Bohr’s model doesn’t talk about probabilities. Hence b) shape of orbital is given by ‘ ’ not ‘m’.
statement (a) is incorrect. c) Since = 0, therefore orbital angular momentum
30. Bohr derived that = 0 for 1s, 2s, 3s etc.
n2 Z Z2 d) Electrons in different orbitals have different
rn \ Z , v n \ n and freq \ 3 velocities.
n
Kq q KZe 2 Z3 42. For 3d orbitals: n = 3, = 2, m = 2, 1, 0, 1, 2 and
]n /Zg
Now, Force = 2 & F \ 2 2 F \ 4
1 2

r n s = + 0.5
31. 2nd I.E. of He = 13.6 × 22 eV 43. If ‘ ’ of two orbitals are same, then their orbital
3rd I.E. of Li = 13.6 × 32 eV angular momentum is also same.
1st I.E. of H = 13.6 eV 44. b) if n = 3 then can be 0 or 1 or 2.
o o
9
r3 of H = 0.529 × 9 A and r3 of Li2+ = 0.529 × 3 A d) if = 2 then m can be 0 or + 1 or + 2.
n, 45. All 3 statements are correct.
Z2 Z2 46. All 3 statements are correct.
32. K.E. K.E. \ 2 , P.E. \ - 2 , rn = ro $ n
2
n n
47. electron cloud density of px orbital
Energy levels or orbits are not equally spaced. The
distance between the orbits keeps increasing with n. 48.
33. Bohr’s model can be applied to all single electron 49. (b) For n = 2 we can have 4 orbitals but they all do
species. not have different energy levels. Out of the 4, 3
are degenerate and have different energy from
n3
34. Frequency \ the 4th.
Z2
(c) M n = 3 and can accommodate a maximum
35. For electronic transition from n 1, no. of spectral
n ]n - 1g
of 18 electrons.
lines is given by 1 + 2 + 3 + ..... (n 1) = 2
2.12 Chemistry
50. Quantum numbers are derived by solving the 2.178×10 -11
Schroedinger’s wave equation. For a multi electron 62. T.E.3 = - 9 ergs
species, the energy of an electron can be estimated a P.E. = 2 T.E.
by the value of (n + ). Azimuthal Q.N. does not 2
P.E. = - 9 ×2.18×10 -11 ergs
tell us anything about the motion of the electron.
= 4.84 × 10 12 erts
51. Shape of orbital is given by azimuthal Q.N. Also,
h
2m ]K.E.g
electrons in an atom move with different velocities. 63. m =
52. Due to the presence of electrons in them the orbital
h
ex orient themselves to minimize the energy in a 64. m =
2m qV
6.625×10 -34
53. Spin of electron does not affect the angular 5 × 10 12
=
2×1.67×10 -27 ×1.6×10 -19 ×V
momentum and can be represented as clockwise and
Solving we get V = 32.8 V
anticlockwise.
65. m = 75 × 10 3 kg
54. Factual.
h 6.625×10 -34
55. E4s < E3d. If n = 2 the there are 4 orbitals which can x = = mv x=
75×10 -3 ×4
accommodate a maximum of 8 electrons. If n = 5 h 6.625×10 -34
then maximum no. of electrons in it is 2n2 = 50. v = 4r m 3 x =
4×3.14×75×10 -3 ×2.2×10 -33
56. If n = 4 and m = 2, it may be a 4d or 4f orbital. The = 0.32 m/s
1 1
spin of the electron may be + 2 or - 2 . 66. No. of electrons possible in an orbital = 4
57. = 1 to (n + 1)
, ,
electron p q x y z m = - 2 to + 2
n 3 3 3 3 3 For n = 1 = 1, 2 i.e. 1A, 1B
m 0 0 1 1 1 For n = 2 = 1, 2, 3 i.e. 2A, 2B, 2C
0 0 1 +1 0 For n = 3 = 1, 2, 3, 4 i.e. 3A, 3B, 3C, 3D
s 1
2 + 1
2 + 1
2 + 1
2 + 1
2 Now, for = 1 : m = -1 2 , +1 2
58. K.E. of photo electron varies with and but is = 2 : m = 1, 0, 1
constant with intensity. 3 1 1 3
= 3 : m = - 2, - 2, + 2, + 2
59. A1 = r12 An = rn2 and rn = r1n2 = 4 : m = 2, 1, 0, 1, 2

b A n l = rr1 n2 & ln b A n l = 4ln (n)

2 4 A subshell has 2 orbitals
A1 rr1 A1 B subshell has 3 orbitals
Graph of ln b An l vs ln (n) is a straight line with
A E.C. would be as follows:
1
1A 8
1B 12
2A 8
2B 12
14444244443 14444244443 3A 8
.....
slope = 4 and this line passes through the origin.
1st period 2 nd period

60. Energy of electron depends on (n + 1) in case Therefore, number of elements in 2nd period are 20.
of multi electron species while in case of single
67. No. of elements in 1st period = 20
electron species, it depends on only the value of ‘n’.
2nd period beings with Z = 21. i.e. Sc.
P.E.1 = 2 K.E.1 and P.E.2 = 2 K.E.2 | P.E.|=
2| K.E.| 68. For Z = 100
It is practically not possible for an electron in an
excited state to absorb another photon.
o
61. r3 = 0.529 × 9 A
2 r3 = 3 2 0.529 × 9 = 3
= 9.96 × 10 10
m . = 10 9 m

8
3C16
 Atomic Structure 2.13
69. For E subshell, =5 h
83. 3 x = 3 p & 3 p = 4r
No. of orbitals = 6
No. of electrons = 24 (as 4 electrons in each h
` m3v = 4r
orbital)
1 6.625×10 -34
70. Shortest wavelength is emitted for highest energy. ` 3v = -31 × 4×3.14
9.1×10
D has shortest wave length emitted = 7.98 × 10 +12
y=8
71. Ionization potential is the amount of energy absorbed 84. No. of volues of m = 2 + 1
by a gaseous atom to lose the aoutermost electron. 7-1
= 2 =3
EB = 13.6 b 9 - 16 l eV
1 1
72. B = 4 3 85. 3 2, 2 1, 3 1.
7 86. 5.27 = + 0.27 =5
= 13.6 × 9×16 eV
= 1.983 eV 87. Cu+ has 3d10
EB = 1.983 × 1.6 × 10 19 J bs =- 1 l = 5
2
= 3.18 × 10 19 J energy is released.
= 1.09677×10 +7 ×Z 2 :1 - 4 D
1 1 1
88.
73. n = 2, = 0, 1, 2, 3 3×10 -8
for last subshell, n = 2 and = 3. 4
or, Z 2 =
3×3×1.09677×10 -8 ×10 +7
n+ =5
Z2 = 4 Z =2
74. 2nd line of Balmer series 4 2
89. Maximum m = + 3 =3 n =4
1 line of Lyman series 2 1
st
No. of waves by the electron in the fourth orbit = 4
= R : 4 - 16 D & m B = 3R
1 1 1 16
mB 90. n =2 r n 200 = 400 n =2
= R :1 - 4 D & m L = 3R
1 1 4 R R
mL 91. E =- 9H =- 2H & n = 3 .
n
mB
=4 No. of electrons that can be accomodated in n = 3 is
mL
2 × 32 = 18.
75. 4d orbital has 1 radial node, as (n 1) = 1
No. oforbitals presents in n = 3 is 9. All these
No. of peaks = no. of radial nodes + 1 = 2
orbitals are degenerate as of single electron
76. b ro n4 l = ]rogH & n = 2
2
species E3s = E3p = E3d and so on.
3+
Be

]5 - 2g]5 - 2 - 1g
92. 4 2 in He+ has same energy difference as 2 1 of H.
77. No. of lines = 2 =6 22
93. a) U1, 2 = 2 × 13.6 × = 13.6 × 8 eV
78. 13.6 Z = 217.6
2
Z = 16
2 12
K1, 1 = + 13.6 eV
Z=4
Ratio = 8:1
79. No. of radial nodes = (n 1) = 1
22 12 r
80. Any d subshell can have maximum of 5 unpaired b) r2, 1 = ro 1 = 4 ro and r1, 2 = ro 2 = 2o
electrons. so the maximum spin possible Ratio = 8 : 1
1
= 5× ! 2 = S 2 4
c) V1, 2 = Vo 1 = 2 Vo and V2, 4 = Vo 2 = 2 Vo
5
Spin multiplicity = 2 | s | + 1 = 2 × 2 + 1 = 6. Ratio = 1 : 1
81. Longest wavelength of any series is the lowest
n3 T1,2 1
energy line of that series and has the lowest energy. d) T \ 2 & T =8
z 2,2
For Lyman it is 2 1.
82. P.E. = 6.8 eV = 2 × T.E.
- 13.6
T.E. = 3.4 eV = 3.4 n2 = 4.
n2
n = 2 1 excited sate.
st
2.14 Chemistry
94. a) 3 radial nodes 4s / 5p but for p orbitals, <0 Z2
95. T.E. =- 13.6 eV as n increases, T.E. increases.
at r = 0 n2
Z2
b) 3 radial node 4s and 5 p Frequency of revolution \ 3 as n increases,
n
frequency decreases.
c) For p and d orbitals angular probability
distribution depends on and Z3
Acceleration \ 4 as n increases, acceleration
n
d) S orbital is spherically symmetric, hence no decreases
planar node. n2
radius \ Z as n increases, radius increases
96. a) Orbital angular momentum
= 2r , ], + 1g = 2 2r & , = 1 & p orbital.
h h

b) Bohr’s model classical mechanical

c) 5 degenerate orbitals d orbitals
d) N shell n=4 no. of waves made by the
electron = 4

1. v = R H c - m cm -1 J ; 2E
2
1 1 Z
82 n2 7. Given, in the question E = 2.178 × 10 18
n
R R R R For hydrogen Z = 1,
= 64H - 2H = 2H + 64H
J; 2E
n n 1
So, E1 = 2.178 ×10 18

Comparing it with general straight line equation, 1

E2 = 2.178 ×10 18 J ; 2 E
y = mx + c, we get 1
2
R Now, E1 E2
Slope (m) = – RH, Intercept (c) = 64H
i.e. E = 2.178 ×10 18 c 2 - 2 m =
1 1 hc
2. (i) Higher the value of ‘l’, lesser is the penetration
1 2 m
of the orbital. Thus, given statement is correct.
2.178 ×10 18 c 2 - 2 m =
-34
1 1 6.62×10 ×3.0×108
(ii) Size of orbit depends on value of ‘n’. Thus, 1 2 m
incorrect.
m . 1.21×10 -7 m
nh
(iii) Angular momentum = 2r and for ground state
8. According to Bohr’s model,
n=1. Thus, given statement is correct.
nh n2 h2
(iv) As value of azimuthal Q.N. increases, vs r mvr = 2r & (mv) 2 =
4r 2 r 2
graph has more number of peaks and hence 2 2
shift towards lower value of r. Thus, incorrect 1 n h
KE = 2 mv2 = ...(i)
8r 2 r 2 m
statement.
Also, Bohr’s radius for H atom is, r = n2a0
3. The graph given in option (c) is incorrect as the
Substituting ‘r’ in Eq. (i) gives
emission will begin only once > 0. The graph for
(c) should look similar to that of (a) because E . h2 h2
KE = When n = 2, KE =
8r n a0 m
2 2 2
32r 2 a02 m
4. Radius of nth Bohr orbit in H atom = 0.53 n2 Ao
9. The number of radial nodes is given by expression
Radius of 2nd Bohr orbit = 0.53 × (2)2 = 2.12 Ao (n ).
13.6 For 3s, number of nodes = 3 0 1=2
5. E n =- eV Where, n = 1, 2, 3...
n2
- 13.6 For 2p, number of nodes = 2 1 1=0
In excited states, E2 = 4 =- 3.4 eV r n2
10. Expression for Bohr’s orbit is , rn = 0Z
6. Given, atomic number of Rb, Z = 37
When n = 2, Z = 4.
1
.
So, the quantum numbers are n = 5, l = 0, (for
s orbital) m = 0 ( a m = + l to l), s = + 1 /2 or 1/2.
 Atomic Structure 2.15
11. 1s7 violates Pauli exclusion principle, according 12. Using the De Broglie’s relationship:
to which an orbital cannot have more than two h 6.625×10 -34
electrons because each electron is represented by a m = mv = 5 = 2.3×10 -30 m
0.2× 60×60
distinct set of 4 quantum numbers.

- 13.6 # 22 - 13.6×3 2
1. - 3.4 = 6. E2s (Li2+) =
n2 22
n=4 9
E2s (Li2+) = 4 E1 (H)
2
= 2.25
Subshell = 4d
7. S2 is 3 p orbital, for energy of nth shell of Li2+
Angular nodes = 2
= 13.6 eV, n = 3
Radial nodes = n 1 4 2 1=1
As it has 1 radial node hence it is 3p
2. n = 4 h
orbital angular momentum = 2 2r
|m|=1 may be 1 | 2 | 3 and m = +1 or 1
2 electrons each of 4p, 4d and 4f can have 13.6Z2
8, 9. KE = eV / atom
1 n2
n = 4, | m | = 1 and s = + 2
2 # 13.6Z2
Total 6 electrons PE = eV / atom
n2
1242
3. z = 300 = 4.14 eV n2 %
Radius 0.529 Z A
Li, Na, K, Mg show P.E.E. nh
Angular momentum of electron (mvr) = 2r
4. n = 3 can accommodate maximum of 18 electrons of
1 1
which 9 will have s = + 2 and 9 will have s = - 2 10. 2s orbital has are radial node and = 0 once
(r)
5. S1 is spherically symmetrical state, i.e. it correspond 11. 1s has zero radial nodes
to s orbital. Also, it has one radial node.
12. E2 = 2.55 eV E2 = 3.022
Number or radial nodes = n 1. 4 6

n 0 1=1
n = 2 i.e. S1 = 2s orbital.
2.16 Chemistry