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Solutions
SECTION - A
Objective Type Questions (One option is correct)
4. Lithium crystallizes in a body centred cubic lattice, how many next nearest neighbours does each Li has?
(1) 8 (2) 6 (3) 12 (4) 4
Sol. Answer (2)
For BCC crystallization
No. of nearest neighbouring atoms = 8
No. of next nearest neighbouring atoms = 6.
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66 The Solid State Solutions of Assignment (Set-2)
5. A binary solid has atoms B constitutes fcc lattice and atoms A occupies 25% of tetrahedral holes. The formula
of solid is
(1) AB (2) A2B (3) AB2 (4) AB4
Sol. Answer (3)
B– occupies the lattice :
1 1
B– ions = 8 6 4
8 2
Number of tetrahedral voids = 8
25
A+ becomes ×8=2
100
Formula of solid = A2B4 or AB2
6. Which of the following layering pattern will have a void fraction of 0.26?
(1) ABCCBAABC... (2) ABCABCABC... (3) ABBAABBBA... (4) ABCAABCA...
Sol. Answer (2)
ABCABCABC...........packing is similar to FCC packing
4
4 3
3 ⎛ a ⎞ = 0.74
Packing fraction = ⎜ ⎟
a3 ⎝ 2 2 ⎠
7. In a CCP structure of compound XY, atom X is present at octahedral voids. The ratio of 6th C. N. and 3rd C.N.
for an atom X located at body-centre is
1 1
(1) 3 (2) (3) 4 (4)
3 4
Sol. Answer (1)
6th co-ordination of atom X will be 24 ‘X’ atoms present at four adjacent edge-centres of each of six adjacent
units cells.
3rd co-ordination of atom X will be 8 Y atoms present at all corners of the unit cell.
Therefore,
6 th C.N. 24
3
3rd C.N. 8
8. The ratio of number of closed packed atoms to the number of tetrahedral holes in cubic closed packing is
(1) 1 : 1 (2) 1 : 2 (3) 1 : 3 (4) 2 : 1
Sol. Answer (2)
In CCP :
1 1
No. of atoms present = 8 × +6× =4
8 2
Number of tetrahedral voids = 8
4
Ratio = =1:2
8
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Solutions of Assignment (Set-2) The Solid State 67
9. In a crystalline solid, anion B are arranged in cubic close packing and cation A are equally distributed between
octahedral and tetrahedral voids. If all the octahedral voids are occupied, the formula for the solid is
(1) AB (2) AB2 (3) A2B (4) A2B3
Sol. Answer (3)
Anions ‘B’ are in CCP
1 1
Therefore no. of anions = 8 6 4
8 2
Cation A are equally distributed between octahedral and tetrahedral voids
4 O-voids are occupied
4 T-voids are occupied
Cations A are 4 + 4 = 8
Formula becomes A8B4 = A2B
11. If the total number of atoms per unit cell in an hcp structure and a bcc structure gets halved,
then ratio of percentage voids in hcp and bcc structures is
34 21 22 37
(1) (2) (3) (4)
27 22 21 34
Sol. Answer (2)
Normal occupancy of hcp = 74%
Normal occupancy of bcc = 68%
If number of atoms in both are halved percentage occupancies will be 37% and 34% respectively for hcp and
bcc, therefore
[Density]
12. An element (At. mass = 50 g/mol) having fcc structure has unit cell edge length 400 pm. The density of
element is
(1) 5.188 g/cc (2) 10.376 g/cc (3) 2.56 g/cc (4) 1.2 g/cc
Sol. Answer (1)
Given : Mw = 50 g; Z = 4; a = 400 pm
a = 400 × 10–12 × 102 cm = 4 × 10–8 cm
Z Mw 4 50
3
a NA (4 10 ) 6.023 1023
–8 3
200 10 2000
= 5.188 g/cm3.
64 6.023 64 6.023
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68 The Solid State Solutions of Assignment (Set-2)
13. The number of atoms in 100 g of a bcc crystal lattice with density = 10 g/cc and edge length = 100 pm is
(1) 4 × 1025 (2) 2 × 1025 (3) 8 × 1025 (4) 1 × 1025
Sol. Answer (2)
For a BCC unit cell, Z = 2
= 10 g/cc : a = 100 pm × 10–12 × 102
a = 1 × 10–8 cm
Z Mw
a 3 NA
M=
X=
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Solutions of Assignment (Set-2) The Solid State 69
Sol. Answer (2)
1 1
Number of X atoms/ ions per unit cell = 8 6 4
8 2
1
Number of M atoms/ions per unit cell = 1 4 2
4
Empirical formula of the compound is MX2
17. The packing efficiency of the two-dimensional square unit cell shown below is [IIT-JEE 2010]
18. In ionic solids AB and CD, radius-ratios are x and y respectively. If x + y = 0.75 and x – y = 0.25, then cations
in AB and CD are respectively in
(1) T-voids, O-voids (2) O-voids, T-voids (3) T-voids, T-voids (4) O-voids, O-voids
Sol. Answer (2)
rA rC
x y 0.75 … (i)
rB rD
rA rC
x y 0.25 … (ii)
rB rD
2x = 1 x = 0.5
That lies between 0.414 – 0.732 therefore A+ is in octahedral void and y = 0.25 that lies between 0.225 - 0.414
therefore C+ is in tetrahedral voids.
19. The arrangement of X– ions around A+ ion in solid AX is given in the figure (not drawn to scale). If the radius
of X– is 250 pm, then the radius of A+ is [JEE(Advanced)-2013]
X–
A+
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70 The Solid State Solutions of Assignment (Set-2)
20. In a compound XY2O4 oxide ions are arranged in ccp structure. Cation X are present in octahedral voids and
cation Y are equally distributed between octahedral and tetrahedral voids. The fraction of the octahedral voids
occupied is
1 1 1 1
(1) (2) (3) (4)
4 2 8 6
Sol. Answer (2)
1 1
O2– occupies ccp O2– is equal to 8 6 4
8 2
‘X’ is present in O Voids
‘Y’ is present in T Voids as well as O Voids
1
Therefore, 2 atoms are present in O voids. So, fraction of octahedral voids occupied is equal to =
2
21. The ionic radii of Rb+ and I– are 1.46 and 2.16 Å. The most probable type of structure exhibited by Rbl is
(1) CsCl type (2) NaCl type
(3) ZnS type (4) CaF2 type
Sol. Answer (2)
The radius ratio for the given below values
R 1.46
Rb
0.67
R– 2.16
I
The radius ratio lies within the range 0.414 to 0.732 hence it becomes NaCl type.
23. An ionic solid crystallizes as rock salt structure (NaCl) and the edge length of fcc unit cell having rock salt
structure is 508 pm. If the radius of cation is 110 pm, then radius of the anion is
(1) 144 pm (2) 288 pm (3) 398 pm (4) 618 pm
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Solutions of Assignment (Set-2) The Solid State 71
Sol. Answer (1)
a (FCC) = 508 pm ; Rc = 110 pm
R(anion) = ?
We can say
2(Rc + Ra) = a
a 508
Rc + Ra = = 254 pm
2 2
Ra = 254 – 110 = 144 pm
24. Which of the following has highest number of formula units per unit cell?
(1) NaCl type structure (2) Na2O type structure
(3) CaF2 type structure (4) All have same number of formula unit
Sol. Answer (4)
All have the four formula units.
25. In Zinc blende structure, Zn+2 ions are present in alternate tetrahedral voids and S–2 in ccp. The coordination
number of Zn+2 and S–2 are respectively
(1) 8, 8 (2) 4, 4 (3) 4, 8 (4) 8, 4
Sol. Answer (2)
Since S2– occupies ccp.
1 1
Number of S2– = 8 × +6× =4
8 2
Zn2+ occupies alternate tetrahedral voids
1
Zn2+ = 8 × =4
2
Coordination number becomes 4 : 4.
26. Metallic gold crystallises in fcc lattice with edge length 4.070 Å. The closet distance between gold atoms is
(1) 2.878 Å (2) 8.140 Å
(3) 2.035 Å (4) 1.357 Å
Sol. Answer (1)
For FCC lattice
Edge length a = 4.070 Å
a 4.070
d= 2.878 Å
2 1.414
27. Zinc sulphide exists in two different structural forms as zinc blende (FCC) and Wurtzite (HCP). What will be
the coordination number of cation and anion in both the structures?
(1) 6 : 6 for both (2) 4 : 4 for both
(3) 4 : 4 and 6 : 6 respectively (4) 6 : 6 and 4 : 4 respectively
Sol. Answer (2)
In fcc and hcp for Zinc blende and Wurtzite, Zn2+ is surrounded by 4 S2– ions and vice versa. Therefore, the
coordination number is 4 : 4.
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72 The Solid State Solutions of Assignment (Set-2)
28. CsBr has cubic structure with edge length 4.3 Å. The shortest interionic distance between Cs+ and Br– is
a = 4.3 Å
Body diagonal = 3a
3a 1
Interionic distance = (body diagonal)
2 2
3a 3 4.3
3.72 Å
2 2
29. In diamond, carbon atom occupy FCC lattice points as well as alternate tetrahedral voids. If edge length of
the unit cell is 3.56 pm, then radius of carbon atom is
3a
In FCC tetra void touch the lattice point at
4
3a
2r r = Radius of carbon atom
4
3 356 pm
r 77.07 pm
8
30. NH4Cl crystallizes in a body-centered cubic type lattice with a unit cell edge length of 387 pm. The distance
between the oppositely charged ions in the lattice is
3a
For BCC opp charged ions touch at
2
a = 387 pm
3a
335.1 pm
2
31. In diamond, the C.N. of carbon and number of carbon atoms per unit cell respectively are
(1) 4, 8 (2) 4, 6 (3) 6, 4 (4) 6, 6
Sol. Answer (1)
In diamond C forms ccp in which alternate tetrahedral voids are occupied.
1 1
Therefore, C.N. of carbon = 4 and number of C atoms/unit cell = 4 6 8 8
2
8
(THV )
ccp
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Solutions of Assignment (Set-2) The Solid State 73
[Defect and Properties of Solid]
32. If a cation leaves a site in solid lattice, and is located at an interstitial position. The lattice defect is
(1) Interstitial defect (2) Schottky defect (3) Valency defect (4) Frenkel defect
Sol. Answer (4)
It is a Frenkel’s defect where a cation leaves the site and occupies an interstitial position.
nNi3 (0.98 x)
3x + 2(0.98 – x) = 2
0.04
Percentage of Ni3+ = 100 4.08
0.98
= Cation
–
e
= Anion
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74 The Solid State Solutions of Assignment (Set-2)
37. Anti-ferromagnetism is in
(1) (2) (3) (4)
Sol. Answer (4)
Anti Ferromagnetic has a compensatory wavy form
38. Tetrahedral void is surrounded by four atoms. Which atoms in the given figure are around the tetrahedral void?
4
3
5
2
1
SECTION - B
2. What will be the distance between two nearest neighbours in primitive, fcc and bcc unit cell?
(1) For primitive, d = a (2) For fcc, d = 0.707a
(3) For bcc, d = 1.732a (4) For bcc, d = 1.414a
Sol. Answer (1, 2)
Distance between the neighbouring atoms
⎛ a⎞
For primitive ⎜ d ⎟
⎝ 2⎠
⎛ a ⎞
For FCC ⎜ d ⎟
⎝ 2⎠
⎛ 3 a⎞
For BCC ⎜ d ⎟
⎝ 2 ⎠
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Solutions of Assignment (Set-2) The Solid State 75
Sol. Answer (2, 3, 4)
Manner of aggregation of layers in ccp can be represented as ABCA……..
So fourth layer repeats.
1
No. of effective atoms = 8 1
8
8. CsCl has bcc structure. If atomic mass of Cs and Cl atom is 133 and 35.5 amu respectively, what would be
correct about its unit cell?
(1) Number of formula unit (z) = 1 (2) Number of formula unit (z) = 2
(3) Mass of unit cell = 370 g mol–1 (4) Mass of unit cell = 168.5 g mol–1
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76 The Solid State Solutions of Assignment (Set-2)
9. Which of the following statements is/are correct for fluorite structure (CaF2)?
(1) Ca2+ ions are in ccp with fcc unit cell and F– ions occupy all the tetrahedral voids
(2) Ca2+ ion is surrounded by 4F– ions
(3) Mass of one unit cell = mass of 4Ca2+ + Mass of 4F–
(4) C.N. of F– = 4, C.No. Ca2+ = 8
Sol. Answer (1, 4)
In CaF2 : Ca2+ occupies FCC (or ccp) and FÈ are present in tetrahedral voids
1 1
No. of Ca2+ = 8 6 4
8 2
FÈ = 1 × 8 = 8
Formula becomes Ca4F8 CaF2
Coordination no. of FÈ = 4
Coordination no. of Ca2+ = 8
4 corners ⎫ 4 2
⎬ ⇒ Cl removed
2 face centres ⎭ 8 2
2 edge centres ⎫ 2
⎬ ⇒ Na removed 1
& 1body centre ⎭ 4
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Solutions of Assignment (Set-2) The Solid State 77
Thus same number of Na+ and Cl– are removed
Rectangular plane touches :
4
4 face-centres Cl– removed =
2
4 edge centres ⎫ 4
⎬ ⇒ Na removed 1
1body centre ⎭ 4
2
2 face centres ⇒ Cl
2
2
2 corners Cl– removed =
8
12. In an oxide, oxide ions are packed with FCC unit cell in which B3+ ion occupy x% of octahedral void and A2+
ion occupy y% of tetrahedral void, then what is correct about the unit cell?
(1) Formula is A3B2O6 in which x = 50% and y = 12.5%
(2) Formula is A2B4O6 in which x = 50% and y = 50%
(3) Formula is AB2O4 in which x = 50% and y = 12.5%
(4) Formula is AB2O4 in which x = 12.5% and y = 50%
Sol. Answer (3)
In AB2O4
O2– present as ccp
1 1
No. of O2– = 8 6 4
8 2
4O2– are present
8 T-voids and 4 O-voids are present in FCC unit cell
B3+ occupy x% of O-voids are occupied, since 2B atoms are present,
we can conclude 50% O-voids are occupied
X = 50%
A 2+ ions occupy tetrahedral voids and y% are occupied. Since only one ion is present it means
1
× (T-voids) are present
8
y = 12.5%
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78 The Solid State Solutions of Assignment (Set-2)
14. The density of KBr is 2.75 g/cm3 and edge length of unit cell is 654 pm (K = 39, Br = 80) then what are the
features of this unit cell?
(1) Unit cell is fcc type (2) Number of formula units = 4
(3) Solid has bcc type (4) Number of formula units = 2
Sol. Answer (1, 2)
(KBr) = 2.75 g/cm3.
a (edge length) = 654 pm
We can apply the equation
Z Mw 2.75 (6.54 108 )3 (6.023 1023 )
= 3 Z
a NA 119
(6.54)3 6.023 101
Z = (2.75) 4
119
It is FCC lattice (unit cell) and no. of formula unit = 4
15. Fe3O4 has inverse spinel structure. What is not true about this solid?
(1) Fe3+ ions are equally distributed between octahedral and tetrahedral voids
(2) Tetrahedral voids are equally distributed between Fe2+ and Fe3+ ions
(3) No. of O–2 > Fe+3 > Fe+2
(4) Coordination no. of Fe3+ = 8 through out the unit cell
Sol. Answer (2, 4)
Fe3O4 has inverse spinel structure
O2– ions forms FCC unit cell
1
Fe3+ occupies (TV) = one Fe3+
8
1
Fe2+ occupies (OV) = one Fe2+
4
1
Fe3+ occupies (OV) = one Fe3+
4
Formula ratio of Fe2+, Fe3+, O2– = 1 : 2 : 4
16. CsCl structure is interchanged into NaCl structure. This can be done because
(1) Temperature is increased (2) Pressure is decreased
(3) Temperature is decreased (4) Presure is increased
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Solutions of Assignment (Set-2) The Solid State 79
Sol. Answer (1, 2)
In CsCl co-ordination number is 8, this can be converted into NaCl structure (CN = 6) by release in packing
that can be achieved either by increase of temperature or by decrease in pressure.
21. The correct statement(s) regarding defects in solids is(are) [IIT-JEE 2009]
(1) Frenkel defect is usually favoured by a very small difference in the sizes of cation and anion
(2) Frenkel defect is a dislocation defect
(3) Trapping of an electron in the lattice leads to the formation of F-center
(4) Schottky defects have no effect on the physical properties of solids
Sol. Answer (2, 3)
A Schottky defect are favoured by small difference in sizes of cation and anion.
B In Frenkel defect cations are dislocated therefore. (True)
C Electron trapped in lattice are called F-centre. (True)
D Schottky defect decrease density.
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80 The Solid State Solutions of Assignment (Set-2)
22. If the unit cell of a mineral has cubic close packed (ccp) array of oxygen atoms with m fraction of octahedral
holes occupied by aluminium ions and n fraction of tetrahedral holes occupied by magnesium ions, m and n,
respectively, are [JEE(Advanced)-2015]
1 1 1 1 1 1 1
(1) , (2) 1, (3) , (4) ,
2 8 4 2 2 4 8
Sol. Answer (1)
The formula will be MgAl2O4
Total tetrahedral voids = 8
Total octahedral voids = 4
1
as only one Mg atom is present hence, n =
8
2 1
as there are two Al atoms are present hence, m = =
4 2
1 1
m, n = ,
2 8
23. The CORRECT statements(s) for cubic closed packed (ccp) three dimensional structure is(are)
[JEE(Advanced)-2016]
(1) The number of the nearest neighbours of an atom present in the topmost layer is 12
(2) The efficiency of atom packing is 74%
(3) The number of octahedral and tetrahedral voids per atom are 1 and 2, respectively
(4) The unit of cell edge length is 2 2 times the radius of the atom
Sol. Answer (2, 3, 4)
In CCP, the coordination number for atom in top-most layer is 9.
SECTION - C
Linked Comprehension Type Questions
Comprehension-I
NaCl is a AB type of solid. Its crystalline structure is known as rock salt structure in which rNa+ and rCl– are
95 and 181 pm respectively, where Cl– is present at the lattice point of face centered cubic unit cell Na+ ions
are located in void and those compounds which have same crystalline structure also have same coordination
system in which Na+ and Cl– ions are surrounded by certain number of opposite ions respectively. Under high
pressure coordination number changes to 8 : 8 type from 6 : 6 type.
2. LiCl adopts rock salt crystalline structure in which edge length is 5.40 Å. What would be the radii of Li+?
(1) 0.89 Å (2) 2.7 Å (3) 1.78 Å (4) 0.98 Å
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Solutions of Assignment (Set-2) The Solid State 81
Sol. Answer (1)
Since it is a FCC lattice and cations occupy the octahedral voids.
2 (R R ) = a [Edge length]
Li Cl–
1.78
R = = 0.89 Å
Li
2
3. In rock salt type structure of AB solid, what would be the maximum radius of X+ that can displace A+ if radius
of B– is 100 pm?
(1) 41.4 pm (2) 73.2 Å (3) 41.4 Å (4) 73.2 pm
Sol. Answer (4)
R
A
= 0.732 R = (0.732) (100) = 73.2 pm
R A
B–
4. If the atomic mass of Li and Cl are 7 and 35.5 amu respectively, then what would be number of LiCl molecule
in cube of LiCl with length × height × breadth = 1 × 1 × 1 = 1 cm3?
(1) Nearly 2.5 × 1022 (2) Nearly 4 × 1020
(3) Nearly 12 × 1030 (4) Nearly 14 × 1023
Sol. Answer (1)
In volume (a3) number of LiCl molecules = 4
(5.40 × 10–8)3 cm3 = 4
4
1 cm3 =
(5.40)3 10 –24
Comprehension-II
Magnesium and Titanium form a crystalline oxide in which Mg appears at the eight corners, oxygen appears
at face centres and titanium appears at the centre of cube. The atomic mass of magnesium, titanium and
oxygen is 24, 45.9 and 16 amu respectively. A similar compound is formed by calcium with titanium and oxygen.
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82 The Solid State Solutions of Assignment (Set-2)
Comprehension-III
Atoms A, B, C and D are located at corners, face-centres, T-voids and O-voids respectively.
1. It atoms touching one of the body-diagonal plane of symmetry are removed, then formula of compound is
(1) AB2C4D7 (2) AB4C8D7 (3) AB2C4D5 (4) AB4C8D5
Sol. Answer (4)
Body diagonal plane touches :
4
4 corners removed A =
8
2
2 face-centres removed B =
2
4THVs removed C = 4
⎧2 edge centres ⎫ 2
&⎨ ⎬ ⇒ removed D 1
⎩1body centre ⎭ 4
Therefore, compared will become
A 1 B3 1 C8 4 D 3 AB4 C8D5
1 4
2 2
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Solutions of Assignment (Set-2) The Solid State 83
2. If atoms touching each of one of the 2-fold, 3-fold and 4-fold axis of symmetry are removed, then formula of
compound is
(1) A3B4C12D10 (2) A3B2C6D5 (3) A3B8C24D10 (4) A3B6D3D5
Sol. Answer (3)
Two fold axis is along diagonally opposite edge centres so
A removed = 0
2
D removed = 1
4
2
3-fold axis is along body diagonal so A removed =
8
2
3-fold axis passes through opposite face centres, so B removed =
2
Therefore, overall the compound will be
A 1 B3 1 C8 D 3 A 3 B2 C8 D 5
1 4
4 2 4 2
A3B8C21D10
3. If the body-centre is the origin and atoms present in (or touching) first octant are removed, then formula of the
compound is
(1) A7B12C56D18 (2) A7B12C28D20 (3) A16B7C28D20 (4) A7B16C56D18
Sol. Answer (1)
A removed = 1/8
B removed = 3/2
C removed = 1
D removed = 7/4
4. If the minimum distances of atoms B, C and D from atom A are x, y and z respectively, then x : y : z is equal to
ratio 2 2 : 3 : 2
Comprehension-IV
In hexagonal systems of crystals, a frequently encountered arrangement of atoms is described as a hexagonal
prism. Here, the top and bottom of the cell are regular hexagons and three atoms are sandwiched in between
them. A space-filling model of this structure, called hexagonal close-packed (HCP), is constituted of a sphere
on a flat surface surrounded in the same plane by six identical spheres as closely as possible. Three spheres
are then placed over the first layer so that they touch each other and represent the second layer. Each one
of these three spheres touches three spheres of the bottom layer. Finally, the second layer is covered with a
third layer that is identical to the bottom layer in relative position. Assume radius of every sphere to be ‘r’.
[IIT-JEE 2008]
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84 The Solid State Solutions of Assignment (Set-2)
1 1
= 12 2 3 1
6 2 ⎛ no. of atoms in ⎞
corner Face
Centre
⎜ hexagonal primitive ⎟
⎜
⎝ unit cell ⎟
⎠
= 6
64
(1) 24 2 r 3 (2) 16 2 r 3 (3) 12 2 r 3 (4) r3
3 3
⎛ 3 2⎞ ⎛ 2⎞
= ⎜⎜ 6 4 a ⎟⎟ 4r ⎜ 3 ⎟
⎝ ⎠ ⎝ ⎠
3 ⎛ 2⎞
2r ⎜⎜ 4r
2
= 6 ⎟
4 ⎝ 3 ⎟⎠
= 24 2 r 3
4 3
r 6
3
Packing fraction =
Base area Height
4 3
6
r
3
=
⎛ 3 2⎞ 2
⎜⎜ 6 a ⎟⎟ 4r
⎝ 4 ⎠ 3
= 0.74
% of empty space = (1 – 0.74) × 100
= 26%
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Solutions of Assignment (Set-2) The Solid State 85
SECTION - D
Assertion-Reason Type Questions
1. STATEMENT-1 : Schottky type of defect is shown by crystals with high co-ordination numbers.
and
STATEMENT-2 : In Schottky defect, equal number of cations and anions are missing from their lattice sites.
Sol. Answer (2)
In Schottky defect, equal number of positive and negative ions are missing but it does not explain that this
defect is shown by crystal’s with high coordination number.
2. STATEMENT-1 : Na2O adopts structure similar to that of CaF2 but positions of positive and negative ions are
reversed.
and
STATEMENT-2 : The structure of Na2O is also known as antifluorite structure.
Sol. Answer (2)
Statement-1 is correct as both Na2O and CaF2 structures are same. Only positive and negative ions are
interchanged.
Statement-2 is correct but not the correct explanation.
4. STATEMENT-1 : Molecular solids have higher melting point than covalent solids.
and
STATEMENT-2 : In molecular solids, the lattice points are occupied by molecules.
Sol. Answer (4)
The covalent forces are stronger than the molecular forces i.e. Melting Point of covalent solids is higher than
that of molecular solid.
Statement-2 is correct as lattice points are occupied by molecules.
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86 The Solid State Solutions of Assignment (Set-2)
6. STATEMENT-1 : In NaCl structure, Na+ ions occupy octahedral holes and Cl– ions show ccp like packing.
and
a
STATEMENT-2 : The distance of the nearest neighbours in NaCl structure is where a is the edge length
2
of the cube.
Sol. Answer (2)
a
Statement (1) is correct & the distance of the nearest neighbours in NaCl structure is .
2
So, both statements are correct.
7. STATEMENT-1 : For NaCl structure, Cl– ions occupy corners and face centre and Na+ ions occupy edge
centres and body centre.
and
STATEMENT-2 : The radius ratio of NaCl structure varies from 0.414 to 0.732.
Sol. Answer (3)
Statement (1) is correct as Cl– occupies corners and face centers and Na+ occupies octahedral voids but
radius ratio of NaCl structure is fixed, and not varies from 0.414 to 0.732.
3
8. STATEMENT-1 : For a CsCl unit-cell, r +r a where a is edge-length.
Cs+ Cl– 2
and
STATEMENT-2 : CsCl structure has FCC type unit-cell.
Sol. Answer (3)
CsCl is bcc type unit cell.
10. STATEMENT-1 : p-type semiconductors are formed due to metal excess defect.
and
STATEMENT-2 : F-centres are created due to metal excess defect.
Sol. Answer (4)
p-type are formed by metal deficient defect.
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Solutions of Assignment (Set-2) The Solid State 87
SECTION - E
Matrix-Match Type Questions
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88 The Solid State Solutions of Assignment (Set-2)
5. Match the crystal system/unit cells mentioned in Column I with their characteristic features mentioned in
Column II. [IIT-JEE-2007]
Column I Column II
(A) Simple cubic and face-centred cubic (p) Have these cell parameters a = b = c and
==
(C) Cubic and tetragonal (r) Have only two crystallographic angles of 90°
SECTION - F
Fact.
2. How many aluminium ions are present per unit cell of corundum (Al2O3)?
2
Al3+ ions occupy rd octahedral holes.
3
2
Hence, n = ×6=4
3
3. Calculate the number of formula units of NaCl per unit cell of NaCl.
Given :
N0 Vuc
Z ⇒Z4
M
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Solutions of Assignment (Set-2) The Solid State 89
4. Solid spheres of diameter 10 cm are arranged in a square packing, with side of the square as
50 cm. If ‘n’ is the number of spheres whose centre either lie inside or on the side of the square, then find
the value of n .
Total no. of spheres whose centre either lie inside or on the side of the square are 36.
So, n =6
5. In a B.C.C. unit-cell of compound AB, A is located at cubical void. Calculate the ratio of 4th C.N. and 3rd C.N.
of A.
ratio = 2
6. Atoms A, B, C and D are present at corners, face centres, body-centre and edge-centres respectively. If atoms
touching one of the 2-fold axis, 3-fold axis and 4-fold axis are removed, then total number of atoms remaining
1
per unit cell is x + . Find x.
4
2
C removed = (1) and D removed =
4
2
A removed =
8
2
So, B removed =
2
3 5 (3 8 10) 21 ⎛ 1⎞
Remaining atoms = 20 ⎜5 ⎟
4 2 4 4 ⎝ 4⎠
x=5
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90 The Solid State Solutions of Assignment (Set-2)
7. In following unit cell find out the difference of number of axis of rotation to the number of planes of symmetry
8. The number of hexagonal faces that are present in truncated octahedron is [IIT-JEE 2011]
d = 8 g cm–3 (density)
ZM
d M = molecular mass (g/mol)
NA a3
SECTION - G
r
1. STATEMENT-1 : In fluorite structure, 1.
r
STATEMENT-2 : Effectively there are 4 unoccupied octahedral voids in a unit cell of CaF2 .
STATEMENT-3 : Effectively there are 4 unoccupied tetrahedral voids in a unit cell of CaF2 .
(1) T F F (2) TFT (3) FFF (4) TTF
Sol. Answer (4)
See description of fluorite structure.
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Solutions of Assignment (Set-2) The Solid State 91
2. STATEMENT-1 : There are 6 atoms of Mg for unit cell of its crystal.
STATEMENT-2 : Mg forms HCP lattice.
Factual
STATEMENT-3 : If the radius of cation is nearly equal to radius of anion, then most favourable arrangement
is BCC.
SECTION - H
Aakash Challengers Questions
1. Potassium crystallizes in bcc unit cell with distance between nearest neighbours of 4.52 Å, if its atomic
mass = 39 amu.
(c) How many nearest neighbouring atoms does each potassium atom has?
a 3
Sol. In bcc nearest distance
2
= 4.52
⎛ 4.52 2 ⎞
(a) a ⎜ ⎟ Å 5.22 Å
⎝ 3 ⎠
2 39
(b) d 0.919 g/cc
6.022 1023 (5.22 1010 )3
(c) 8
2. An element occurs in BCC with edge length 300 pm. The density of solid is 7.2 g cm–3. Find out
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92 The Solid State Solutions of Assignment (Set-2)
2M
Sol. d 7.2
6.022 10 (300 10 10 )3
23
⎛ 27 1 7.2 ⎞
(a) Number of atoms = ⎜ 24 ⎟
⎝ 58.5 1.66 10 ⎠
= 2 × 1024
2
(b) Number of unit cells in the foil = 1024
2
3. Calculate the ratio of minimum distances between two T-voids and two alternate T-voids in a cubic unit-cell.
a
Sol. Minimum distance between two THVs =
2
a 2
Distance between alternate THVs =
2
1
Ratio =
2
4. KF crystallizes in the rock salt type structure. If the radius of K+ ion is 132 pm and that of F– ion is 135 pm,
(i) What is the shortest distance between K+ and F– ions? (ii) What is the edge length of the unit cell ?
(iii) What is closest K-K distance?
Sol. Shortest distance = r+ + r– = 132 + 135 = 267 pm
Edge length = 2(r+ + r–) = 534 pm
a 534
K–K distance = 377.6 pm
2 1.414
5. AB crystallizes in a rock salt structure. The nearest distance between A and B is Y1/3 nm, where Y is a
constant. The molecular mass of AB is 6.023 Y g/mol–1. Determine the density in kgm–3.
1
a
Sol. Nearest distance = y3
2
1
a 2y 3
M = 6.023 y
4 6.023y 40
d 3
10 24 5 kgm3
⎛ 1
⎞ 8
⎜ 2y ⎟ 6.023 10
3 23
⎝ ⎠
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Solutions of Assignment (Set-2) The Solid State 93
6. Four solids W, X, Y and Z are given. All have a metallic lustre. The solids could be gold, lead sulphide, mica
(which is quartz or SiO2) and iodine. The results of the investigation are:
(a) W is a good electrical conductor; X, Y and Z are poor electrical conductors.
(b) When the solids are hit with a hammer, W flattens out, X shatters into many pieces, Y is smashed into
a powder and Z is not affected.
(c) When the solids are heated with a Bunsen burner, Y melts with some sublimation, but X, W and Z do
not melt.
(d) In treatment with 7M HNO3, X dissolves and there is no effect on W, Y or Z.
On the basis of these test results, identify the solids.
Sol. (a) W is gold because metal is good conductor of electricity.
(b) W(gold) is ductile and malleable, X(PbS) is shatters to many pieces, Y(I2) is smashed and Z(SiO2)
which is very hard is not affected.
(c) I2 melts and sublimes, Au, SiO2 and PbS do not melt.
(d) PbS reacts with HNO3, gold has no effect.
7. Tungsten has a body centred cubic lattice and each lattice point is occupied by one atom. Calculate the radius
of metallic tungsten if density of tungsten is 19.30 gcm–3 and atomic weight is 183.9.
zm z 183.9
Sol. d ⇒ 19.30
a3 NA ⎛ 4R ⎞
3
⎟ 6.023 10
23
⎜
⎝ 3⎠
R = 1.37 Å.
8. KCl crystallizes in the same type of lattice as does NaCl.
r r
Na+ Na+
Given that, 0.5 and 0.7
r r
Cl– K+
Calculate :
(a) The ratio of the side of unit cell for KCl to that the NaCl
(b) The ratio of density of NaCl to that for KCl.
Sol. Let radius of Na+ is x
x x
rK rCl
aKCl 0.7 0.5 3.428
1.143
aNaCl rNa rCl x 3
x
0.5
(b) KCl = 1.175
3
dNaCl MNaCl ⎛ aKCl ⎞
⎜ ⎟ 1.17
dKCl MKCl ⎝ aNaCl ⎠
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94 The Solid State Solutions of Assignment (Set-2)
9. Potassium crystallizes in a body centred cubic lattice. What is the approximate number of unit cells in 4.0
gm of potassium? (Atomic mass of potassium = 39)
Sol. Mass of one unit cell = 2 × 39 = 78 amu = 78 × 1.67 × 10–24 g
4 4 6.023 1023
Number of unit cells = 3.09 1022
78 1.67 1024 78
10. An element A (Atomic weight = 100) having b.c.c. structure has unit cell edge length 400 pm. Calculate the
density of A, number of unit cells and number of atoms in 10 g of A.
2 100
Sol. d 1030 5.188 g/cm3
(400)3 6.023 1023
10
Number of unit cells = 3.011 1022
2 100 1.67 10 24
11. What would be the edge length of that fcc unit cell in which an atom with maximum diameter 117.1 pm can
be placed in between its interstitial sites without changing its structure?
⎛ r ⎞ ⎛ r ⎞
⎜
Sol. Either octahedral voids ⎜ – 0.414 ⎟ or tetrahedral voids ⎜⎜ – 0.225 ⎟⎟ are occupied by interstitial sites in
⎟
⎝r ⎠ ⎝r ⎠
FCC where r+ is the radius of atom in interstitial sites and r– is the radius of atom forming the cubic lattice.
2 0.414 2
Diameter of interstitial site = 117.1 = a
4
a = 400 pm
12. For a unit cell of edge length 10 Å, atomic mass of that element is 150 amu and density is 1 g cm–3. Find
out the atomic radius.
Sol. Edge length (a) = 10 Å = 10 × 10–10 m = 1.0–9 m = 10–9 × 102 cm = 10–7 cm
Mw = 150 amu
= 1 g/cm3
We can use the equation
ZM
=
a3 NA
Z=4
FCC unit cell is having the radius as
a 10 –7
r= =
2 2 2 2
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Solutions of Assignment (Set-2) The Solid State 95
13. In an oxide of iron, oxygen forms hcp and iron occupies two out of every three octahedral voids. Find out the
formula of unit cell and formula of compound.
Sol. Since oxygen forms hcp.
Six O2– ion are present:
Number of octahedral voids = Number of O2– ion
2 2
of octahedral voids means × 6 = 4 atoms of Fe
3 3
14. Iron adopts two different crystalline allotropic forms, one at 1183 K and other one below 1183 K, which differ
in structural units as bcc and fcc and known as and forms. What would be the ratio of densities of these
two forms ( and )? Assume inter atomic distance remains same.
Sol. In bcc structure
Body diagonal, 4r = 3a
4r
a=
3
2 56
ZM 3
d ( form) = = ⎛ 4r ⎞ 6.023 1023
a3NA ⎜ ⎟
⎝ 3⎠
In fcc structure,
Face diagonal = 4r = 2 a’
a’ = 2 2
3
⎛ 4r ⎞
2⎜ ⎟
density ratio of form to form = ⎝ 3⎠ = 1.0887
(2 2 r )3
15. Chromium metal crystallizes with a body centred cubic lattice. The length of the unit edge is found to be
287 pm. Calculate the atomic radius. What would be the density of chromium in g/cm3?
3a
Sol. r
4
3 287
r 124.3 pm
4
3
2 52 ⎛ 1 ⎞ 3
d ⎜ ⎟ 7.3 g/cm
6.023 1023 ⎝ 2.87 108 ⎠
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96 The Solid State Solutions of Assignment (Set-2)
16. Lithium borohydride crystallizes in orthorhombic unit cell with 4 molecules per unit cell with a = 6.8 Å, b = 4.4 Å
and c = 7.2 Å. Find the density of solid if molar mass of LiBH4 = 21.76 g mol–1.
Sol. According to the problem,
Z = 4, Molecular weight of LiBH4
= 21.76, Volume (a3) = abc
ZM 4 21.76
= =
3
a NA (6.8 4.4 7.2 10 –30 106 ) 6.023 1023
= 0.67 g/cm3.
17. The density of KCl is 1.9892 g cm–3. If atomic mass of K and Cl are 39 and 35.5 amu respectively, find the
inter ionic distance of KCl.
ZM
Sol. d =
a3NA
4 74.5
1.9892 =
a3 6.023 1023
298
a3 =
1.9892 6.023 1023
= 2.48 × 10–22
a = 6.28 × 10–8 cm = 6.28 Å
Interionic distance in KCl
a 3 6.28 3
= = Å
2 2
6.28 1.732
= Å
2
= 5.43848 Å
= 3.14 Å
18. With the help of given values of ionic radii answer the following questions :
Cations Li+ Na+ K+ Cs+ Mg2+ Ca2+
Ionic radii (pm) 60 95 133 160 65 99
Anions F– Cl– Br– I– O2– S2–
Ionic radii (pm) 135 181 195 216 140 184
(a) What would be coordination number of Mg in MgO?
(b) What type of unit cell is given by CsBr?
(c) Can we substitute Cl– from NaCl by Br – and I– ions without changing the coordination system?
(d) What type of voids are present in Na2S?
(e) What would be the maximum radii of that ion which can fit into site occupied by F– in KF such that K+
just fit without distorting lattice?
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Solutions of Assignment (Set-2) The Solid State 97
Sol. (a) For calculating the coordination number of MgO we calculate the ‘Radius Ratio’ for MgO.
r r 2
Mg 65
For MgO; r = r = = 0.464
– O 2– 140
Since it lies between 0.414 and 0.732 it shows octahedral void and coordination number of Mg is 6.
(b) For CsBr
r 160
Cs
Radius ratio = r = = 0.82
Br – 195
r
Cs
r = 0.82 > 0.732 hence it will form BCC unit cell.
Br –
r
Na
(c) For NaBr; Radius ratio = r
–
Br
95
= 0.487 …(i)
195
r 95
Na
For NaI; = = 0.439 …(ii)
rI– 216
Both the above values of radius ratio lies between 0.414 and 0.732 hence we can substitute these anions.
(d) For Na2S Radius ratio
r 95
Na
= = 0.516
r 184
S2–
Hence we can conclude that octahedral and tetrahedral voids both are present.
r
K
(e) = 0.414 (for maximum radii)
r
F–
133
= 0.414
r–
F
Radius of anion
133
r– = = 321 pm
(0.414)
19. Calculate the closest distance between two gold atoms (edge length = 1.414 Å) in a face-centred cubic lattice
of gold.
Sol. Answer (1)
a 2 a 1.414
In fcc nearest neighbours will be the points at face-centre and corner = = 1Å
2 2 1.414
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98 The Solid State Solutions of Assignment (Set-2)
20. In a BCC lattice of a metal, edge-length is 300 pm and its molar mass is 50 g/mol, calculate the density of
metal lattice.
Sol. Answer (6.2)
2 50
d
6.022 10 (300 1010 )3
23
= 0.00615 × 103
= 6.15 g/cc 6.2 g/cc
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