8

Solid State

Objective Questions I (Only one correct option) 6. The radius of the largest sphere which fits properly at the
1. The ratio of number of atoms present in a simple cubic, body centre of the edge of a body centred cubic unit cell is
centered cubic and face centered cubic structure are, (Edge length is represented by ‘a’) (2019 Main, 11 Jan II)
respectively. (2019 Main, 12 April II) (a) 0.134 a (b) 0.027 a (c) 0.047 a (d) 0.067 a
(a) 8 : 1 : 6 (b) 1 : 2 : 4 7. A solid having density of 9 ´ 103 kgm -3 forms face centred
(c) 4 : 2 : 1 (d) 4 : 2 : 3 cubic crystals of edge length 200 2 pm. What is the molar
2. An element has a face-centred cubic (fcc) structure with a cell mass of the solid?
edge of a. The distance between the centres of two nearest [Avogadro constant = 6 ´ 1023 mol-1 , p = 3]
tetrahedral voids in the lattice is (2019 Main, 12 April I) (2019 Main, 11 Jan I)
-1
a 3 (a) 0.03050 kg mol (b) 0.4320 kg mol-1
(a) 2a (b) a (c) (d) a
2 2 (c) 0.0432 kg mol-1 (d) 0.0216 kg mol-1
3. Consider the bcc unit cells of the solids 1 and 2 with the 8. A compound of formula A2B3 has the hcp lattice. Which
position of atoms as shown below. The radius of atom B is atom forms the hcp lattice and what fraction of tetrahedral
twice that of atom A. The unit cell edge length is 50% more is voids is occupied by the other atoms ? (2019 Main, 10 Jan II)
solid 2 than in 1. What is the approximate packing efficiency 2
(a) hcp lattice- A, tetrahedral voids-B
in solid 2? (2019 Main, 8 April II) 3
1
A A A A (b) hcp lattice-A, tetrahedral voids-B
3
A 1
A A A (c) hcp lattice-B, tetrahedral voids-A
B 3
A 2
A A A (d) hcp lattice-B, tetrahedral voids-A
A 3
A A A A 9. Which primitive unit cell has unequal edge lengths
Solid 1 Solid 2 ( a ¹ b ¹ c ) and all axial angles different from 90°?
(2019 Main, 10 Jan I)
(a) 65% (b) 90% (a) Hexagonal (b) Monoclinic
(c) 75% (d) 45% (c) Tetragonal (d) Triclinic
4. The statement that is incorrect about the interstitial 10. At 100°C, copper (Cu) has FCC unit cell structure with cell
compounds is (2019 Main, 8 April II)
edge length of x Å. What is the approximate density of Cu (in g
(a) they are very hard
cm -3 ) at this temperature?
(b) they have metallic conductivity
[Atomic mass of Cu = 63.55 u] (2019 Main, 9 Jan II)
(c) they have high melting points
211 205
(d) they are chemically reactive (a) 3 (b) 3
x x
5. Element ‘B ’ forms ccp structure and ‘A ’ occupies half of the 105 422
octahedral voids, while oxygen atoms occupy all the (c) 3 (d) 3
x x
tetrahedral voids. The structure of bimetallic oxide is
(2019 Main, 8 April I) 11. The one that is extensively used as a piezoelectric material
(a) A2BO4 (b) AB2O4 is (2019 Main, 9 Jan I)
(c) A2B2O (d) A4B2 O (a) quartz (b) tridymite
(c) amorphous silica (d) mica
124 Solid State

12. Which type of ‘defect’ has the presence of cations in the 20. The packing efficiency of the two-dimensional square unit
interstitial sites? (2018 Main) cell shown below is (2010)
(a) Schottky defect (b) Vacancy defect
(c) Frenkel defect (d) Metal deficiency defect
13. A metal crystallises in a face centred cubic structure. If the
edge length of its unit cell is ‘a’, the closest approach between
two atoms in metallic crystal will be (2017 Main) l
(a) 2 a (b) 2 2 a (a) 39.27% (b) 68.02% (c) 74.05% (d) 78.54%
a 21. Which of the following fcc structure contains cations in
(c) 2 a (d)
2 alternate tetrahedral voids? (2005, 1M)

14. Sodium metal crystallises in a body centred cubic lattice with (a) NaCl (b) ZnS (c) Na 2 O (d) CaF2
a unit cell edge of 4.29Å. The radius of sodium atom is 22. A substance Ax B y crystallises in a face centred cubic (fcc)
approximately (2015 Main) lattice in which atoms A occupy each corner of the cube and
(a) 1.86Å (b) 3.22Å atoms B occupy the centres of each face of the cube. Identify
(c) 5.72Å (d) 0.93Å the correct composition of the substance Ax B y (2002, 1M)
15. CsCl crystallises in body centred cubic lattice. If ‘a’ its edge (a) AB3
length, then which of the following expressions is correct? (b) A4 B3
(2014 Main) (c) A3 B
3a
(a) r + rCl - = 3a (b) r + rCl - = (d) composition cannot be specified
Cs + Cs + 2
23. In a solid AB having the NaCl structure, A atoms occupy the
3 corners of the cubic unit cell. If all the face centred atoms
(c) r + + rCl - = a (d) r + + rCl - = 3a
Cs 2 Cs
along one of the axes are removed, then the resultant
16. The arrangement of X ions around A + ion in solid AX is
-
stoichiometry of the solid is (2001, S, 1M)
given in the figure (not drawn to scale). If the radius of X - is (a) AB2 (b) A2 B (c) A4 B3 (d) A3 B4
250 pm, the radius of A + is (2013 Adv.) 24. The coordination number of a metal crystallising in a
–
hexagonal close-packed structure is (1999, 2M)
X (a) 12 (b) 4 (c) 8 (d) 6
A+

Objective Questions II
(One or more than one correct option)
(a) 104 pm (b) 125 pm 25. The correct statement(s) for cubic close packed (ccp) three
(c) 183 pm (d) 57 pm dimensional structure is (are) (2016 Adv.)
17. Experimentally it was found that a metal oxide has formula (a) The number of the nearest neighbours of an atom present
M 0.98O. Metal M, present as M 2+ and M 3 + in its oxide. in the topmost layer is 12
Fraction of the metal which exists as M 3+ would be (b) The packing efficiency of atom is 74%
(a) 7.01% (b) 4.08% (2013 Main) (c) The number of octahedral and tetrahedral voids per atom
(c) 6.05% (d) 5.08% are 1 and 2, respectively
18. Which of the following exists as covalent crystals in the solid (d) The unit cell edge length is 2 2 times the radius of the atom
state? (2013 Main) 26. If the unit cell of a mineral has cubic close packed (ccp) array
(a) Iodine (b) Silicon of oxygen atoms with m fraction of octahedral holes
(c) Sulphur (d) Phosphorus occupied by aluminium ions and n fraction of tetrahedral
holes occupied by magnesium ions, m and n respectively, are
19. A compound M p X q has cubic close packing (ccp) (2015 Adv.)
arrangement of X . Its unit cell structure is shown below. The 1 1 1 1 1 1 1
(a) , (b) 1 , (c) , (d) ,
empirical formula of the compound, is (2012) 2 8 4 2 2 4 8
27. The correct statement(s) regarding defects in solids is/are
(a) Frenkel defect is usually favoured by a very small
M
difference in the sizes of cation and anion (1999)
X
(b) Frenkel defect is a dislocation defect
(c) Trapping of an electron in the lattice leads to the formation
of F-centre
(a) MX (b) MX 2 (c) M 2 X (d) M 5 X 14 (d) Schottky defects have no effect on the physical properties
of solids
 Solid State 125

28. Which of the following statement(s) is/are correct? 31. The number of atoms in one of this hcp unit cell is
(a) The coordination number of each type of ion in CsCl crystal (2008, 3 ´ 4M = 12M)
is 8 (1998, 2M) (a) 4 (b) 6 (c) 12 (d) 17
(b) A metal that crystallises in bcc structure has a coordination 32. The volume of this hcp unit cell is
number of 12 64 r3
(a) 24 2 r3 (b) 16 2 r3 (c) 12 2 r3 (d)
(c) A unit cell of an ionic crystal shares some of its ions with 3 3
other unit cells 33. The empty space in this hcp unit cell is
(d) The length of the unit cell in NaCl is 552 pm. (a) 74 % (b) 47.6 % (c) 32 % (d) 26 %
(rNa + = 95 pm; rCl - =181 pm)
Match the Columns
Numerical Value 34. Match the crystal system / unit cells mentioned in Column I
29. Consider an ionic solid MX with NaCl structure. Construct a with their characteristic features mentioned in Column II.
new structure (Z) whose unit cell is constructed from the unit (2007, 6M)
cell of MX following the sequential instruction given below. Column I Column II
Neglect the charge balance. (2018 Adv.) A. Simple cubic and face p. have these cell
(a) Remove all the anions (X ) except the central one centred cubic parameters a = b = c
(b) Replace all the face centered cations (M ) by anions (X ) and a = b = g = 90°
(c) Remove all the corner cations (M ) B. Cubic and q. are two crystal
(d) Replace the central anion (X ) with cation (M ) rhombohedral systems
æ Number of anions ö C. Cubic and tetragonal r. have only two
The value of ç ÷ in Z is ___
è Number of cations ø crystallographic
angles of 90°
Assertion and Reason D. Hexagonal and s. belong to same crystal
monoclinic system
Read the following questions and answer as per the direction
given below :
(a) Statement I is correct Statement II is correct Statement II is
Integer Answer Type Questions
the correct explanation of Statement I 35. A crystalline solid of a pure substance has a face-centred
(b) Statement I is correct Statement II is correct Statement II is cubic structure with a cell edge of 400 pm. If the density of
not the correct explanation of Statement I the substance in the crystal is 8 g cm -3 , then the number of
(c) Statement I is correct Statement II is incorrect atoms present in 256 g of the crystal is N ´ 1024 . The value of
(d) Statement I is incorrect Statement II is correct N is (2017 Adv.)
30. Statement I In any ionic soid (MX ) with Schottky defects, 36. The number of hexagonal faces that are present in a truncated
the number of positive and negative ions are same. octahedron is (2011)

Statement II Equal numbers of cation and anion vacancies 37. Silver (atomic weight = 108 g mol -1 ) has a density of
are present. 10.5 g cm-3 . The number of silver atoms on a surface of area
(2001, 1M)
10-12 m2 can be expressed in scientific notation as y ´ 10 x.
The value of x is (2010)
Passage Based Questions
Subjective Questions
Passage
38. The edge length of unit cell of a metal having molecular
In hexagonal systems of crystals, a frequently encountered
weight 75 g/mol is 5 Å which crystallises in cubic lattice. If
arrangement of atoms is described as a hexagonal prism. Here, the
the density is 2 g/cc then find the radius of metal atom.
top and bottom of the cell are regular hexagons and three atoms are
(N A = 6 ´ 1023 ). Give the answer in pm. (2006, 3M)
sandwiched in between them. A space-filling model of this
structure, called hexagonal close-packed (hcp), is constituted of a 39. An element crystallises in fcc lattice having edge length
sphere on a flat surface surrounded in the same plane by six 400 pm. Calculate the maximum diameter of atom which can
identical spheres as closely as possible. Three spheres are then be placed in interstitial site without distorting the structure.
placed over the first layer so that they touch each other and (2005, 2M)
represent the second layer. Each one of these three spheres touches 40. The crystal AB (rock salt structure) has molecular weight
three spheres of the bottom layer. 6.023 y u. Where, y is an arbitrary number in u. If the
Finally, the second layer is covered with a third layer that is minimum distance betweeen cation and anion is y1 / 3 nm and
identical to the bottom layer in relative position. Assume radius of the observed density is 20 kg / m3 . Find the (i) density in
every sphere to be ‘r ’. kg / m3 and (ii) type of defect. (2004, 2M)
126 Solid State

41. (i) Marbles of diameter 10 mm are to be put in a square area 43. A metal crystallises into two cubic phases, face centred cubic
of side 40 mm so that their centres are within this area. (fcc) and body centred cubic (bcc), whose unit cell lengths
(ii) Find the maximum number of marbles per unit area and are 3.5 and 3.0 Å, respectively. Calculate the ratio of
deduce an expression for calculating it. (2003, 4M)
densities of fcc and bcc. (1999, 3M)
44. Chromium metal crystallises with a body centred cubic
42. The figures given below show the location of atoms in three
lattice. The length of the unit edge is found to be 287 pm.
crystallographic planes in a fcc lattice. Draw the unit cell for Calculate the atomic radius . What would be the density of
the corresponding structures and identify these planes in chromium in g/cm 3 ? (1997, 3M)
your diagram. (2000)
45. A metallic element crystallises into a lattice containing a
sequence of layers of ABABAB…… Any packing of layers
leaves out voids in the lattice. What percentage of this lattice
is empty space? (1996, 3M)
46. Sodium crystallises in a bcc cubic lattice with the cell edge,
a = 4.29 Å. What is the radius of sodium atom? (1994, 2M)

Answers
1. (b) 2. (c) 3. (b) 4. (d) 5. (b) 6. (d) 7. (a) 8. (c) 9. (d)
10. (d) 11. (a) 12. (c) 13. (d) 14. (a) 15. (c) 16. (a) 17. (b) 18. (b)
19. (b) 20. (d) 21. (b) 22. (a) 23. (d) 24. (a) 25. (b,c,d) 26. (a) 27. (b,c)
28. (a,c,d) 29. (3) 30. (a) 31. (b) 32. (a) 33. (d) 34. A ® p, s; B ® q; C ® q; D ® q, r
35. (2) 36. (8) 37. (7) 38. (217 pm) 39. (117 pm) 43. (1.26) 44. (7.3 g/cm 3)
45. (0.74) 46. (1.86 Å)

Hints & Solutions

1. The ratio of number of atoms present in simple cubic, body é aù a a
these two is ê a - ú - = .
centred cubic and face centered cubic structure are 1 : 2 : 4 ë 4 û 4 2
respectively.
2. In fcc unit cell, two tetrahedral voids are formed on each of the 3. Key Idea Packing efficiency
four non-parallel body diagonals of the cube at a distance of
Volume occupied by sphere
3a / 4 from every corner along the body diagonal. = ´ 100
Volume of cube
One of the body diagonal
of cubic unit cell Given,
A
rB = 2rA
1
— AB 50
4
Ö3 a Position of 2 TVs a2 = a1 + a1 = 15
. a1
— A¢ 1 on one of the 100
4 —(AB)
2 body diagonal For bcc lattice
of the unit cell
4 rA = 3 a1
B¢ 1
—(AB) 3 a1
4 rA =
B 4
Ö3 a 4 rA
—
4 a1 =
3
The angle between body diagonal and an edge is cos-1 (1/ 3 ). æ 4r ö
\ . ç A÷
a2 = 15
So, the projection of the line on an edge is a/ 4. Similarly, other è 3ø
tetrahedral void also will be a/4 away. So, the distance between 3 æ 4 rA ö
= ç ÷
2 è 3ø
 Solid State 127

a2 = 2 3 rA a 3 2a - 3a
r= - a=
4 3 4 2 4 4
prA ´ zA + prB3 ´ zB
3 3 a(2 - 3 )
Packing efficiency = r=
a23 4
1 r = 0.067a
[As the atoms A are present at the edges only zA = ´ 8 = 1,
8 7. Density of a crystal
atom B is present only at the body centre zB = 1 ]
M ´Z d ´ N A ´ a3
æ4 3 ö æ4 3 ö d= 3
ÞM =
ç prA ´ 1÷ + ç prB ´ 1÷ NA ´a Z
3 ø è3
\ PE 2 = è ø
Given, d = 9 ´ 103 kg m -3
a23
M = Molar mass of the solid
4 3 4 4 3
prA + p (2rA )3 prA ´ 9 Z = 4 (for fcc crystal)
3 3 3 p
= 3
= 3
= N A = Avogadro’s constant = 6 ´ 1023 mol -1
(2 3 rA ) 8 ´ 3 3 rA 2 3
a = Edge length of the unit cell
= 90.72% » 90% = 200 2 pm = 200 2 ´ 10-12 m
4. Interstitial compounds are formed when a neutral atom with a On substituting all the given values, we get
small radius occupies in an interstitial hole (tetrahedral or
(9 ´ 103 ) kg m -3 ´ (6 ´ 1023 ) mol -1 ´ (200 2 ´ 10-12 )3 m 3
octahedral voids) in a transition metal’s hcp or ccp lattices =
(host lattice). Examples of small atoms (guest atom) are H, B, C 4
and N. = 0.0305 kg mol -1
Interstitial compounds are non-stoichiometric (Birtholide) in
composition. They are very hard with very high melting points.
8. Total effective number of atoms in hcp unit lattice = Number of
octahedral voids in hcp = 6
The electrical conductivity of interstitial compounds are
comparable to that of the pure metal. These are chemically \Number of tetrahedral voids (TV) in hcp
unreactive in nature. = 2 ´ Number of atoms in hcp lattice
5. The number of element ‘B ’ in the crystal structure = 4 N = 2 ´ 6 = 12
As, formula of the lattice is A2 B3 .
Number of tetrahedral voids = 2N
Suppose, A B
Number of octahedral voids = N
æ1 ö
N 4 ç ´ TV ÷ (hcp)
\Number of ‘A’ in the crystal = = =2 è3 ø
2 2
1
Number of oxygen (O) atoms = 2N = 2 ´ 4 = 8 Þ ´ 12 6
3
\The structure of bimetallic oxide = A2 B4 O8 = AB2 O4
2
Þ 1
6. For body centred cubic bcc structure, 3
3 Þ 2 3
radius (R ) = a ...(i)
4 1
So, A = tetrahedral voids, B = hcp lattice
Where, a = edge length 3
According to question, the structure of cubic unit cell can be 9. Triclinic primitive unit cell has dimensions as, a ¹ b ¹ c and
shown as follows:
a ¹ b ¹ g ¹ 90° .
R 2r R
Among the seven basic or primitive crystalline systems, the
triclinic system is most unsymmetrical. In other cases, edge
length and axial angles are given as follows :
Hexagonal : a = b ¹ c and a = b = 90°, g = 120°
Monoclinic : a ¹ b ¹ c and a = g = 90°, b ¹ 90°
Tetragonal : a ¹ b ¹ c and a = b = g = 90°

10. For fcc, rank of the unit cell (Z ) = 4

a Mass of one Cu-atom, M = 63.55 u
Avogadro’s number, N A = 6.023 ´ 1023 atom
\ a = 2(R + r) ...(ii)
On substituting the value of R from Eq. (i) to Eq. (ii), we get Edge length, a = x Å = x ´ 10-8 cm
a 3 Z ´M
= a+ r density (d ) =
2 4 N A ´ a3
128 Solid State

4 ´ 63.55 422.048 16.

= = g cm-3 PLAN Given arrangement represents octahedral void and for this
6.023 ´ 1023 ´ (x ´ 10-8 )3 x3 r+ (cation)
= 0.414
r- (anion)
11. Piezoelectric materials are those materials that produce an
r( A + )
electric current when they are placed under mechanical stress. = 0.414
Crystalline solids can be used as piezoelectric material hence, r( X - )
quartz is a correct answer. r( A + ) = 0.414 ´ r( X - ) = 0.414 ´ 250pm
12. It is the ‘‘Frenkel defect’’ in which cations leave their original = 103.5 pm » 104 pm
site and occupy interstitial site as shown below.
17. From the valency of M 2+ and M 3+ , it is clear that three
+ – + – + – + – Original M 2+ ions will be replaced by M 3+ causing a loss of one
– + – + – + – + vacant site
+ – + – + – + – of cation M 3+ ion. Total loss of them from one molecule of
– + – – + – + MO = 1 - 0.98 = 0.02
Cation in
+ – + – + – + –
– + –
+
+ – + – +
interstitial site Total M 3+ present in one molecule of
+ – + – + – + – MO = 2 ´ 0.02 = 0.04
– + – + – + – + That M 2+ and M 3+ = 0.98
0.04 ´ 100
13. For fcc arrangement, 4 r = 2a Thus, % of M 3+ = = 4.08%
0.98
where, r = radius and a = edge length
18. Silicon exists as covalent crystal in solid state. (Network like
2a a structure, as seen in diamond).
\ Closest distance = 2 r = =
2 2 19. Contribution of atom from the edge centre is 1/4. Therefore,
number of
14. For bcc unit cell, 3 a = 4a 1
M = ´ 4 (from edge centre) + 1 (from body centre) = 2
3 4
r= a 1 1
4 Number of X = ´ 8 (from corners) + ´ 6
8 2
3
= ´ 4.29Å = 1.85Å (from face centre) = 4
4 Þ Empirical formula = M 2 X 4 = MX 2
r = 1.85Å » 1.86Å 1
20. Contribution of circle from corner of square =
15. In CsCl, Cl - lies at corners of simple cube and Cs+ at the body 4
centre. Hence, along the body diagonal, Cs+ and Cl - touch each Þ Effective number of circle per square
1
other so rCs+ + rCl - = 2r = ´ 4 + 1 (at centre) = 2
4
Calculation of r
Þ Area occupied by circle = 2pr2, r = radius.
In DEDF,
Also, diagonal of square 4 r = 2 L, where L = side of square.
G B Area occupied by circles
Þ Packing fraction =
H r A Area of square
2pr2 2pr2 p
2r

c a = 2 = = = 0.785
r L 8r2 4
F C
b Þ % packing efficiency = 78.5%.
a
E a D 21. In ZnS, S2- (sulphide ions) are present at fcc positions giving
four sulphide ions per unit cell. To comply with 1 : 1
Body centred cubic unit cell stoichiometry, four Zn 2+ ions must be present in four alternate
tetrahedral voids out of eight tetrahedral voids present.
FD = b = a2 + a2 = 2 a
In NaCl, Na + ions are present in octahedral voids while in Na 2O,
In DAFD, Na + ions are present in all its tetrahedral voids giving the desired
c2 = a2 + b2 = a2 + ( 2 a)2 = a2 + 2 a2 2 : 1 stoichiometry. In CaF2 , Ca 2+ ions occupies fcc positions
c2 = 3 a2 Þ c = 3 a and all the tetrahedral voids are occupied by fluoride ions.
As D AFD is an equilateral triangle. 1
22. In cubic system, a corner contribute th part of atom to one unit
8
\ 3a = 4r [QC = 3r + r + r]
1
cell and a face centre contribute part of atom to one unit cell.
3a 2
Þ r=
4 Therefore,
3 3 1
Hence, rCs + + rCl- = 2 r = 2 ´ a= a Number of A per unit cell = ´ 8 = 1
4 2 8
 Solid State 129

1 æ4 ö
Number of B per unit cell = ´6= 3 4 ç pr3 ÷
2 Volume of 4 spheres è 3 ø ´ 100
= =
Þ Formula = AB3 Volume of unit cell [ 2( 2r)]3
23. In NaCl, Na + occupies body centre and edge centres while Cl - ~ 74%
= 74.05% -
occupies corners and face centres, giving four Na + and four Cl - 26. Oxide ions are at ccp positions, hence 4O2– ions. Also, there
per unit cell. In the present case A represent Cl - and B represents are four octahedral voids and eight tetrahedral voids. Since ‘m’
Na + . Two face centres lies on one axis. fraction of octahedral voids contain Al 3+ and ‘n’ fraction of
1
Þ Number of A removed = 2 ´ = 1 tetrahedral voids contain Mg2+ ions, to maintain
2
Number of B is removed because it is not present on face centres. etectroneutrality 2(2Al 3+ = + 6charge) and
Þ A remaining = 4 - 1 = 3, B remaining = 4, (Mg2+ = + 2charge), will make unit cell neutral
Formula = A3 B4 2 1 1
Hence: m = = , n=
4 2 8
24. Three consecutive layers of atoms in hexagonal close packed
lattice is shown below: 27. (a) Wrong statement. A small difference in sizes of cation and
anion favour Schottky defect while Frenkel defect is
A favoured by large difference in sizes of cation and anion.
(b) Correct statement. In Frenkel defect the smaller atom or ion
gets dislocated from its normal lattice positions and occupies
the interstitial space.
(c) Correct Statement In F-centre defect, some anions leave
X B
the lattice and the vacant sites hold the electrons trapped in it
maintaining the overall electroneutrality of solid.
(d) Wrong statement : In Schottky defect, some of the atoms or
ions remaining absent from their normal lattice points
A
without distorting the original unit cell dimension. This
lowers the density of solid.
Atom X is in contact of 12 like atoms, 6 from layer B and 3 from 28. (a) The unit cell of CsCl has bcc arrangement of ions in which
top and bottom layers A each. each ion has eight oppositely charged ions around it in the
25. (a) Nearest neighbour in the topmost layer of ccp structure is 9 nearest neighbours as shown below :
thus, incorrect.
(b) Packing efficiency is 74% thus, correct.
(c) Tetrahedral voids = 2 Cs+
Octahedral voids = 1 per atom thus, correct. Cl–
4
(d) Edge length, a = r = 2 2r
2 Unit cell of CsCl
A
thus, correct (b) In bcc, coordination number of atom is 8.
Explanation Edge length = a (c) In an unit cell, a corner is shared in eight unit cells and a face
a centre is shared between two adjacent unit cells.
Radius = r
(d) In NaCl unit cell; 2(rNa+ + rCl - ) = a
AC 2 = AB 2 + BC 2
a C Þ a = 2 (95 + 181) = 552 pm
(4 r)2 = a2 + a2 = 2a2 B
Hence, a, c, d are correct.
4 r = 2a 29. The unit cell of initial structure of ionic solid MX looks like
2 a Cl– (at face centre)
Þ r= a= Þ a=2 2 r
4 2 2
Cl– (at corner)
In ccp structure, number of spheres is 4.
æ4 ö Na+ (at face)
Hence, volume of 4 spheres = 4 ç pr3 ÷
è3 ø
Total volume of unit cell = a3 = (2 2r)3 Na+ (at corner edge)
% of packing efficiency
In NaCl type of solids cations (Na + ) occupy the octahedral
voids while anions (Cl - ) occupy the face centre positions.
130 Solid State

However, as per the demand of problem the position of cations = 24 2 r3

and anions are swapped.
Volume occupied by atoms
We also know that (for 1 unit cell) 33. Packing fraction =
Volume of unit cell
(A) Total number of atoms at FCC = 4 4 1
(B) Total number of octahedral voids = 4 = 6 ´ pr3 ´ = 0.74
3 24 2 r3
(as no. of atoms at FCC = No. of octahedral voids)
Þ Fraction of empty space = 1 - 0.74 = 0.26 = 26%
Now taking the conditions one by one
(i) If we remove all the anions except the central one than
number of left anions. 34. A. Simple cubic and face centred cubic both have cell
= 4 -3 = 1 parameters a = b = c and a = b = g = 90°. Also both of them
belongs to same, cubic, crystal system.
(ii) If we replace all the face centred cations by anions than
B. The cubic and rhombohedral crystal system belongs to
effective number of cations will be = 4 - 3 = 1
different crystal system.
Likewise effective number of anions will be = 1+ 3 = 4
C. Cubic and tetragonal are two different types of crystal
(iii) If we remove all the corner cations then effective number of
systems having different cell parameters.
cations will be 1- 1= 0
D. Hexagonal and monoclinic are two different crystal system
(iv) If we replace central anion with cation then effective
number of cations will be 0 + 1= 1 and both have two of their crystallographic angles of 90°.
Likewise effective number of anions will be 4 - 1= 3 4 ´M
35. Density (r) = 8 =
Thus, as the final outcome, total number of cations present in N A (4 ´ 10-8 cm )3
Z after fulfilling all the four sequential instructions = 1 256
Þ M = 128 ´ 10-24 N A Þ No of atoms = ´NA
Likewise, total number of anions = 3 M
Number of anions 3 256
Hence, the value of = =3 = ´ N A = 2 ´ 1024
Number of cations 1 128 ´ 10-24 N A
30. In ionic solid MX (1 : 1 solid) same number of M n+ and X n- ions 36. The truncated octahedron is the 14-faced Archimedean solid,
are lost in Schottky defect to maintain electroneutrality of solid. with 14 total faces : 6 squares and 8 regular hexagons.
The truncated octahedron is formed by removing the six right
square pyramids one from each point of a regular octahedron as :
A

31. B
Q

C M
P
R S N
Truncated octahedron
A hcp unit cell
Contribution of atoms from corner = 1/ 6 Truncated octahedron unfolded in two-dimension
Contribution from face centre = 1 / 2 37. Ag crystallises in fcc unit cell with 4 atoms per unit cell.
1 1
Þ Total number of atoms per unit cell = 12 ´ + 2 ´ + 3= 6 4 ´ 108
6 2 r= = 10.5 g cm -3.
6.023 ´ 1023 ´ a3
32. In close packed arrangement, side of the base = 2r
Þ a3 (Volume of unit cell) = 6.83 ´ 10-23 cm 3
Þ RS = r
Also MNR is equilateral triangle, Ð PRS = 30° Þ a = 4 ´ 10-8 cm = 4 ´ 10-10 m
RS 3
In triangle PRS , cos 30° = = Þ Surface area of unit cell = a2 = 1.6 ´ 10-19 m 2
PR 2
2 2 Þ Number of unit cells on 10-12 m 2 surface
Þ PR = RS = r
3 3 10-12
= = 6.25 ´ 106
2 1.6 ´ 10-19
In right angle triangle PQR : PQ = QR 2 - PR 2 = 2 r
3
Q There are two atoms (effectively) on one face of unit cell
2
Þ Height of hexagon = 2PQ = 4 r Number of atoms on 10-12 m 2 surface = 2 ´ number of unit cell
3
3 2 = 1.25 ´ 107 . [Q y ´10x ]
Þ Volume = Area of base ´ height = 6 (2r)2 ´ 4 r
4 3 Þ x = 7 Þ y = 125
.
 Solid State 131

38. From the given information, the number of atoms per unit cell centres within the square = 5 (shown in diagram)
and therefore, type of unit cell can be known as Maximum number of marbles per unit area = 5 ´ 5 = 25
NM (ii) If x mm is the side of square and d is diameter of marble then
r=
NA a3 maximum number of marbles on square area with centres
within square area can be known by the following general
r N A a3 2 ´ 6 ´ 1023 ´ (5 ´ 10-8 cm )3
Þ N = = = 2 ( bcc) formula :
M 75 2
æx ö
Þ In bcc, 4 r = 3a N = ç + 1÷
èd ø
3 3
Þ r= a= ´ 5 ´ 10-10 m
4 4
= 2.17 ´ 10-10 m = 217 pm

39. In a cubic crystal system, there are two types of voids known as 42.
octahedral and tetrahedral voids. If r1 is the radius of void and r2
is the radius of atom creating these voids then
æ r1 ö ær ö N
çç ÷÷ = 0.414 and çç 1 ÷÷ = 0.225 43. Density µ
a3
è r2 ø octa è r2 ø tetra 3 3
d1 N 1 æ a2 ö 4 3 ö
The above radius ratio values indicate that octahedral void has Þ = çç ÷÷ = æç ÷ = 1.26
larger radius, hence for maximum diameter of atom to be present d2 N 2 è a1 ø 2 è 3.5 ø
in interstitial space :
44. In bcc unit cell, 4 r = 3a
r1 = 0.414 r2
3a 3
Also in fcc, 4 r2 = 2a Þ r (Cr) = = ´ 287 pm = 124.3 pm
4 4
Þ Diameter required (2r1 ) = (2r2 ) ´ 0.414 NM
a Density of solid =
= ´ 0.414 N A × a3
2
400 ´ 0.414 N = Number of atoms per unit cell, M = Molar mass
= = 117 pm
2 a3 = Volume of cubic unit cell, N A = Avogadro’s number
3
40. (i) In rock salt like crystal AB, there are four AB units per unit 2 ´ 52 g æ 1 ö
cell. Therefore, density (d ) is = ´ç ÷ = 7.3 g / cm 3
6.023 ´ 1023 çè 2.87 ´ 10-8 cm ÷ø
4 ´ 6.023 y
d=
6.023 ´ 1023 ´ 8 y ´ 10-27 45. The given arrangement : ABABAB...... represents hexagonal
1/ 3 1/ 3 -9 close-packed unit cell in which there are six atoms per unit cell.
[Q a = 2 y nm = 2 y ´ 10 m ]
Also, volume of unit cell = 24 2r3.
= 5 ´ 103 g/m 3 = 5 kg/m 3
Volume occupied by atoms
(ii) Since, observed density is greater than expected, theoretical Þ Packing fraction =
Volume of unit cell
density, there must be some excess metal occupying 4 1
interstitial spaces. This type of defect is known as metal = 6 ´ pr3 ´ = 0.74
3 24 2 r3
excess defect.
Þ Percent empty space = 100 (1 - 0.74) = 26%

41. (i) Side of square = 40 mm 10 mm 46. In bcc arrangement of atoms : 4 r = 3a, atoms on body
Diameter of marble = 10 mm diagonal remain in contact
Number of marble spheres along 3a 3 ´ 4.29
Þ r= = = 1.86 Å
an edge of square with their 4 4

40 mm

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