(PHYSICAL CHEMISTRY) SOLID STATE

DO YOURSELF-1
1. The lattice parameters of a given crystal are 𝐚 = 𝟓. 𝟔𝟐Å, 𝐛 = 𝟕. 𝟒𝟏Å and 𝐜 = 𝟗. 𝟒𝟖Å. The three
coordinate axes are mutually perpendicular to each other. The crystal is :
(A) tetragonal (B) orthorhombic (C) monoclinic (D) trigonal.
2. In a lattice of 𝐗 and 𝐘 atoms, if 𝐗 atoms are present at corners and 𝐘 atoms at the body centre &
one 𝐗 atom is removed from a corner from each unit cell, then the formula of the compound will
be :
(A) 𝐗 𝟕 𝐘 (B) 𝐗 𝟖 𝐘𝟕 (C) 𝐗 𝟕 𝐘𝟖 (D) 𝐗 𝟕 𝐘𝟕
3. A compound alloy of gold and copper crystallises in a cubic lattice in which the gold atoms
occupy the lattice points at the corner of a cube and the copper atoms occupy the centres of each
of the cube faces. Hence compound alloy has formula:
(A) 𝐀𝐮𝐂𝐮 (B) 𝐀𝐮𝟑 𝐂𝐮 (C) 𝐀𝐮𝟐 𝐂𝐮 (D) 𝐀𝐮𝐂𝐮𝟑
4. A compound is formed by elements A and B. This crystallises in the cubic structure where the 𝐀
atoms are at the corners of the cube and 𝐁 atoms are at the body centres. The simplest formula
of the compound is :
(A) 𝐀 𝟖 𝐁𝟒 (B) 𝐀𝐁𝟔 (C) 𝐀𝐁 (D) 𝐀 𝟔 𝐁
5. Column-I and Column-II contains four entries each. Entries of Column-I are to be matched with
some entries of Column-II. One or more than one entries of Column-I may have the matching
with the same entries of Column-II.
Column-I Column-II
(Bravais Lattice(s)) [Crystal system]
(A) Primitive, face centered, body centered, end centered (p) Cubic
(B) Primitive, face centered, body centered (q) Orthorhombic
(C) Primitive, body centered (r) Hexagonal
(D) Primitive only (s) Tetragonal
6. The lattice parameters of a given crystals are a = 8.42 Å, b = 8.42 Å and c = 9.80 Å.
There coordinate axes are mutually perpendicular to each other. The crystal is:
(A) Tetragonal (B) Ortho rhombic (C) Monoclinic (D) Trigonal
7. The crystal dimensions 𝐚 = 𝐛 ≠ 𝐜; 𝛂 = 𝛃 = 𝟗𝟎∘ , 𝛄 = 𝟏𝟐𝟎º represents :
(A) Tetragonal (B) Hexagonal system
(C) Monoclinic (D) Orthorhombic system
8. Which of the following unit cells has least symmetry ?
(A) Tetragonal (B) Monoclinic (C) Triclinic (D) Cubic
9. Among the unit cells given below, which has highest symmetry ?
(A) Hexagonal (B) Orthorhombic (C) Cubic (D) Monoclinic
APNI KAKSHA 11
(PHYSICAL CHEMISTRY) SOLID STATE
DO YOURSELF-2
1. A metal crystallizes in two cubic phases i.e., FCC and BCC whose unit cell lengths are 3.5Å and
3.0 Å respectively. The ratio of their densities is :
(A) 3.12 (B) 2.04 (C) 1.26 (D) 0.72
2. In a ccp structure, the:
(A) first and third layers are repeated
(B) first and fourth layers are repeated
(C) second and fourth layers are repeated
(D) first, third and sixth layers are repeated.
3. An fcc lattice has lattice parameter a = 400 pm. Calculate the molar volume of the lattice including
all the empty space:
(A) 10.8 mL (B) 96 mL (C) 8.6 mL (D) 9.6 mL
4. The shortest distance between Ist and Vth layer of HCP arrangement is :

2 2 2 2
(A) 8r (B) 4r (C) 16r (D) 8r
3 3 3 3

5. A body centred cubic arrangement is show :

H G
E F
O
D C
A B
O is the body centre ; A, B, C, D, .........., H are the corners. What is the magnitude of the angle AOB?
(A) 120° (B) 109° 28’ (C) 104° 31’ (D) 70° 32’

6. The radius of metal atom can be expressed in terms of the length of a unit cell is :
(A) it is a/2 for simple cubic lattice

(B) it is a 3
4 for b.c.c. lattice
(C) it is a for F.C.C. lattice
2 2
(D) All of the above.

APNI KAKSHA 22
(PHYSICAL CHEMISTRY) SOLID STATE
DO YOURSELF-3
1. In the zinc blende structure, zinc ions occupy alternate tetrahedral voids and S2– ions exist as
ccp. The radii of Zn2+ and S2– ions are 0.83 Å and 1.74 Å respectively. The edge length of the ZnS
unit cell is
(A) 2.57 Å (B) 5.14 Å (C) 5.93 Å (D) 4.86 Å
2. If the distance between Na+ and Cl – ions in NaCl crystal is ‘a’ pm, what is the length of the cell
edge?

(A) 2a (B) a (C) 4a (D) a

2 4
3. Which of the following statement is incorrect about rock salt type structure ?
(A) It has FCC arrangement of Na+.
(B) Na+ & Cl– ions have co-ordination number of 6 :6.
(C) A unit cell fo NaCl consists of four NaCl units
(D) All halides of alkali metals have rock salt type structure.
4. In the zinc blende structure S2– adopt ccp arragement and Zn2+ occupy.
(A) Octahedral sites (B) Hexagonal sites
(C) Tetrahedral sites (D) None of these
5. The numbers of tetrahedral and octahedral holes in a ccp array of 100 atoms are respectively
(A) 200 and 100 (B) 100 and 200 (C) 200 and 200 (D) 100 and 100
6. In a face centred cubic arrangement of metallic atoms, what is the relative ratio of the sizes of
tetrahedral and octahedral voids?
(A) 0.543 (B) 0.732 (C) 0.414 (D) 0.637
7. CsBr has b.c.c. structure with edge length 4.3 A. The shortest inter ionic distance in between Cs+
and Br– is:
(A) 3.72 (B) 1.86 (C) 7.44 (D) 4.3
 
8. In the fluorite structure if the radius ratio is  3 – 1 , how many ions does each cation touch ?
 2 
(More than one may be correct)
(A) 4 anions (B) 12 cations (C) 8 anions (D) No cations

APNI KAKSHA 34
(PHYSICAL CHEMISTRY) SOLID STATE
DO YOURSELF-4
1. In a crystal some ions are missing from normal sites. This is an example of
(A) F-centre (B) Interstitial defect
(C) Frenkel defect (D) Schottky defect
2. When an ion leaves its correct lattice site and occupies interstitial sites in its crystal lathice,
it is called
(A) Crystal defect (B) Frenkel defect (C) Schottky defect (D) None of these
3. AgCl is crystallized from molten AgCl containing a little CdCl2. The solid obtained will have

(A) cationic vacancies equal to number of Cd2+ ions incorporated

(B) cationic vacancies equal to double the number of Cd2+ ions
(C) anionic vacancies
(D) neither cationic nor anionic vacancies
4.
A+ B+ A+ B–

B– B– A+

A+ B– B–

B– A+ B– A+
Which of the following is correct
(A) The defect is known as schottky defect.
(B) The defect is known as Frenkel defect .
(C) Density of compound in the defect increases.
(D) Stoichiometry of compound will change slightly.
5. Which of the following is incorrect
(A) The defect is known as schottky defect
(B) Density of compound in the defect decreases
(C) NaCl(s) is example which generally shows this defect
(D) Stoichoimetry of compound will change slightly.
6. Analysis show that nickel oxide consist of nickel ion with 96% ions having d 8 configuration and
4% having d7 configuration. Which amongst the following best represents the formula of the
oxide.
(A) Ni1.02O1.00 (B) Ni0.96O1.00
(C) Ni0.98O1.98 (D) Ni0.98O1.00

APNI KAKSHA 43
(PHYSICAL CHEMISTRY) SOLID STATE
7. The correct statement(s) regarding defects solids is (are) [More than one may be correct
(A) Schottky defect is usually favoured by small difference in the sizes of cation and anion.
(B) Schottky defect lowers the density of solids.
(C) Compounds having F-centres are diamagnetic.
(D) Frenkel defect is a dislocation defect.

APNI KAKSHA 44
(PHYSICAL CHEMISTRY) SOLID STATE
EXERCISE (O-I)
PROBLEMS BASED ON CLASSIFICATION OF SOLIDS
1. How many of the following are covalent network solids?
S8, Bronze, SiO2, Diamond, ZnSO4 , Si, AlN , SiC, CO2.
(A) 4 (B) 5 (C) 6 (D) 6
2. Which of the following solids substances will have same refractive index when measured in
different directions?
(A) NaCl (B) Monoclinic sulphur
(C) Rubber (D) Graphite
3. Which of the following is not a characteristic of a crystalline solid?
(A) Definite and characteristic heat of fusion.
(B) Isotropic nature.
(C) A regular periodically repeated pattern of arrangement of constituent particles in the entire
crystal.
(D) A true solid
4. Which of the following is an amorphous solid?
(A) Graphite (C) (B) Quartz glass (SiO2)
(C) Chrome alum (D) Silicon carbide (SiC)
5. Which of the following is true about the value of refractive index of quartz glass?
(A) Same in all directions (B) Different in different directions
(C) Cannot be measured (D) Always zero
6. Which of the following statement is not true about amorphous solids?
(A) On heating they may become crystalline at certain temperature.
(B) They may become crystalline on keeping for long time.
(C) Amorphous solids can be moulded by heating.
(D) They are anisotropic in nature.
7. The sharp melting point of crystalline solids is due to ___________.
(A) a regular arrangement of constituent particles observed over a short distance in the crystal
lattice.
(B) a regular arrangement of constituent particles observed over a long distance in the crystal
lattice.
(C) same arrangement of constituent particles in different directions.
(D) different arrangement of constituent particles in different directions.

APNI KAKSHA 45
(PHYSICAL CHEMISTRY) SOLID STATE
PROBLEMS BASED ON CRYSTAL SYSTEMS, UNIT CELLS
8. Which of the following are the correct axial distances and axial angles for rhombohedral
system?
(A) a = b = c,  = =   90° (B) a = b  c,  =  =  = 900
(C) a  b = c,  =  =  = 900 (D) a  b  c,       900
9. a  b  c,       900 represents
(A) tetragonal system (B) orthorhombic system
(C) monoclinic system (D) triclinic system
10. The most unsymmetrical system is:
(A) Cubic (B) Hexagonal (C) Triclinic (D) Orthorhombic
11. A match box exhibit -
(A) Cubic geometry (B) Monoclinic geometry
(C) Tetragonal geometry (D) Orthorhombic geometry
12. The crystal system of a compound with unit cell dimensions, a = 0.387 and b = 0.387 and
c = 0.504nm and  =  = 90º and  = 120º is :
(A) Cubic (B) Hexagonal (C) Orthorhombic (D) Rhombohedral
PROBLEMS BASED ON SIMPLE CUBIC AND BBC
13. Which of the following is incorrect for simple cubic metallic crystal -
(A) The coordination number of an atom is 6
(B) The atom along the edge length of the cube touches each other
(C) There is no empty space in between the atoms.
(D) An atom touches 6 other atoms.
14. What is incorrect regarding bcc unit cell -

(A) Z = 2 (B) a 3 = 4r (C) C.N. = 6 (D) Packing fraction = 0.68

15. A metal crystallizes in a body centered cubic lattice (bcc) with the edge of the unit cell 5.2Å. The
distance between the two nearest neighbours is
(A) 10.4 Å (B) 4.5 Å (C) 5.2Å (D) 9.0Å
16. Fraction of edge length covered by atoms in BCC structure is -

(A) 1 (B) 3  / 8 (C) 1/ 2 (D) 3/2

17. Iron has body centred cubic lattice structure. The edge length of the unit cell is found to be 286
pm. What is the radius of an iron atom?
(A) r = 124 pm (B) r = 128 pm
(C) r = 124 Å (D) r = 128 Å
APNI KAKSHA 46
(PHYSICAL CHEMISTRY) SOLID STATE
18. In a FCC unit cell
(A) √𝟑𝐚 = 𝟒𝐫 (B) √𝟐𝐚 = 𝟒𝐫 (C) a = 2r (D) √𝟐𝐚 = 𝟐𝐫
19. Which is incorrect for FCC lattice -
(A) a 2 = 4R (B) Co-ordination number = 12
(C) Void fraction = 0.32 (D) No of atoms per unit cell = 4
20. An element crystallizes in both fcc & bcc lattices. Then ratio of edge length of fcc unit cell to bcc
unit cell will be –
(A) 1 : 𝟐√𝟐 (B) √𝟑: √𝟐 (C) √𝟐: √𝟑 (D) √𝟔 : 1
21. Which one of the following schemes of ordering closed packed sheets of equal sized spheres
generate crystal of minimum packing fraction.
(A) ABCABC (B) ABACABAC (C) ABBAABBA (D) ABCBCABCBC
PROBLEMS BASED ON HCP UNIT CELL
22. What is not true regarding hexagonal close packing (hcp)-
(A) packing fraction is 0.74
(B) coordination number is 12
(C) ABCABC type packing
(D) No of atoms per prism =6
23. The shortest distance between Ist and Vth layer of HCP arrangement is:

2 3 2 3
(A) 8 r (B) 4 r (C) 16 r (D) 8 r
3 2 3 2
24. Volume of HCP unit cell is:

(A) 24 2 r3 (B) 8 2 r3 (C) 16 2 r3 (D) 24 3 r3

PROBLEMS BASED ON DENSITY
25. At 912ºC and 105 Pa, -Iron (bcc form) may be transformed into -iron (fcc form). If density of
-iron is  then what is density of -iron (assume no change in radius of iron atom )-

4 3 1.5
(A) /0.74 (B)  0.68 (C) (D)
0.74 3 1.5 4
39
26. 19 K (Specific gravity = 0.89) crystallized in bcc arrangement. What is radius of K atom (in cm)
1/3 1/3
 2 3  39   3 3  39 
(A)  2  (B)  
   0.89NA   32  0.89NA 
1/3 1/3
 4 3  39   3 3  39 
(C)  2  (D)  
   0.89NA   64  0.89NA 
APNI KAKSHA 47
(PHYSICAL CHEMISTRY) SOLID STATE
PROBLEMS BASED ON TV AND OV
27. The interstitial hole is called tetrahedral because
(A) It is formed by four spheres.
(B) Partly same and partly different.
(C) It is formed by four spheres the centres of which form a regular tetrahedron.
(D) None of the above three.
28. The size of an octahedral void formed in a closest packed lattice as compared to tetrahedral void
is
(A) Equal (B) Smaller (C) Larger (D) Not definite
29. In a lattice of X and Y atoms, if X atoms are present at corners and Y atoms at the body centre &
one X atom is removed from a corner from each unit cell, then the formula of the compound will
be :
(A) X7Y (B) X8Y7 (C) X7Y8 (D) X7Y7
30. If ‘Z’ is the number of atoms in the unit cell that represents the closest packing sequence
---ABCABC ---, the number of tetrahedral voids in the unit cell is equal to
(A) Z (B) 2Z (C) Z/2 (D) Z/4
31. If the anions (A) form hexagonal closest packing and cations (C) occupy only 2/3 octahedral
voids in it, then the general formula of the compound is
(A) CA (B) CA2 (C) C2A3 (D) C3A2
PROBLEMS BASED ON IONIC CRYSTAL
32. If x = radius of Na+ & y = radius of Cl– & a is the unit cell edge length for NaCl crystal, then which
of the given relation is correct?

(A) x + y = a (B) 2x + 2y = a (C) x + y = 2a (D) x + y = a 2

33. Edge length of M+X– (NaCl structure) is 7.2 Å. Radius of X– ion is ( rM + = 1.6 Å):

(A) 2.0 Å (B) 5.6 Å (C) 2.8 Å (D) 38 Å

34. How many unit cells are there in 1 gram of NaCl
4  NA NA NA NA
(A) (B) (C) (D)
58.5 58.5 58.5  4 58.5  8
35. A compound XY crystallizes in 8 : 8 lattice with unit cell edge length of 480 pm. If the radius of
Y– is 225 pm, then the radius of X+ is
(A) 127.5 pm (B) 190.68 pm (C) 225 pm (D) 255 pm
36. The mass of a unit cell of CsCl corresponds to
(A) 1 Cs+ and 1 Cl– (B) 1 Cs+ and 6 Cl– (C) 4 Cs+ and 4 Cl– (D) 8 Cs+ and 1 Cl–

APNI KAKSHA 48
(PHYSICAL CHEMISTRY) SOLID STATE
37. Diamond belongs to the crystal system:
(A) Cubic (B) triclinic (C) tetragonal (D) hexagonal
38. An ionic compound AB has ZnS type structure. If the radius A+ is 22.5 pm, then the ideal radius
of B– would be
(A) 54.35 pm (B) 100 pm (C) 145.16 pm (D) none of these
39. The coordination number of cation and anion in Fluorite CaF2 and CsCl are respectively
(A) 8:4 and 6:3 (B) 6:3 and 4:4 (C) 8:4 and 8:8 (D) 4:2 and 2:4
PROBLEMS BASED ON DEFECTS IN SOLIDS
40. Which of the following is the most likely to show schottky defect
(A) CaF2 (B) ZnS (C) AgCl (D) CsCl
41. In the Schottky defect, in AB type ionic solids
(A) cations are missing from the lattice sites and occupy the interstitial sites
(B) equal number of cations and anions are missing
(C) atom of tetrahedral voids displaces into octahedral voids
(D) equal number of extra cations and electrons are present in the interstitial sites
42. F–centers are
(A) the electrons trapped in anionic vacancies
(B) the electrons trapped in cation vacancies
(C) presence of cations in the interstitial sites
(D) presence of anions in the interstitial sites
43. Strongly heated ZnO crystal can conduct electricity. This is due to
(A) Movement of extra Zn2+ ions present in the interstitial sites
(B) Movement of electrons present in the interstitial sites
(C) Movement of oxide ions
(D) None of these
44. Which of the following oxides behaves as conductor or insulator depending upon temperature?
(A) TiO (B) SiO2 (C) TiO3 (D) MgO
45. Cations are present in the interstitial sites in __________.
(A) Frenkel defect (B) Schottky defect
(C) Vacancy defect (D) Metal deficiency defect
46. Schottky defect is observed in crystals when __________.
(A) some cations move from their lattice site to interstitial sites.
(B) equal number of cations and anions are missing from the lattice.
(C) some lattice sites are occupied by electrons.
(D) some impurity is present in the lattice.

APNI KAKSHA 49
(PHYSICAL CHEMISTRY) SOLID STATE
47. Which of the following defects is also known as dislocation defect?
(A) Frenkel defect (B) Schottky defect
(C) Non-stoichiometric defect (D) Simple interstitial defect
PROBLEMS BASED ON ELECTRICAL PROPERTIES
48. Which of the following oxides shows electrical properties like metals?
(A) SiO2 (B) MgO (C) SO2(s) (D) CrO2
49. The lattice site in a pure crystal cannot be occupied by _________.
(A) molecule (B) ion (C) electron (D) atom
50. Graphite cannot be classified as __________.
(A) conducting solid (B) network solid
(C) covalent solid (D) ionic solid
51. Which kind of defects are introduced by doping?
(A) Dislocation defect (B) Schottky defect
(C) Frenkel defects (D) Electronic defects
52. Silicon doped with electron-rich impurity forms ________.
(A) p-type semiconductor (B) n-type semiconductor
(C) intrinsic semiconductor (D) insulator
PROBLEMS BASED ON MAGNETIC PROPERTIES
53. Which of the following arrangements shows schematic alignment of magnetic moments of
antiferromagnetic substances?

(A)

(B)

(C)

(D)

54. Which of the following statements is not true?

(A) Paramagnetic substances are weakly attracted by magnetic field.
(B) Ferromagnetic substances cannot be magnetised permanently.
(C) The domains in antiferromagnetic substances are oppositely oriented with respect to each
other.
(D) Pairing of electrons cancels their magnetic moment in the diamagnetic substances.

APNI KAKSHA 50
(PHYSICAL CHEMISTRY) SOLID STATE
55. A ferromagnetic substance becomes a permanent magnet when it is placed in a magnetic field
because ________.
(A) all the domains get oriented in the direction of magnetic field.
(B) all the domains get oriented in the direction opposite to the direction of magnetic field.
(C) domains get oriented randomly.
(D) domains are not affected by magnetic field.
56. The value of magnetic moment is zero in the case of antiferromagnetic substances because the
domains ________.
(A) get oriented in the direction of the applied magnetic field.
(B) get oriented opposite to the direction of the applied magnetic field.
(C) are oppositely oriented with respect to each other without the application of magnetic field.
(D) cancel out each other’s magnetic moment.
57. Which of the following statements are correct?
(A) Ferrimagnetic substances lose ferrimagnetism on heating and become paramagnetic.
(B) Ferrimagnetic substances do not lose ferrimagnetism on heating and remain ferrimagnetic.
(C) Antiferromagnetic substances have domain structures similar to ferromagnetic substances
and their magnetic moments are not cancelled by each other.
(D) In ferromagnetic substances all the domains get oriented in the direction of magnetic field
and remain as such even after removing magnetic field.

APNI KAKSHA 51
(PHYSICAL CHEMISTRY) SOLID STATE
EXERCISE (S-I)
PROBLEMS BASED ON CLASSIFICATION OF SOLIDS
1. Classify each of the following solids.
(a) Tetra phosphorus decaoxide (P4O10) (b) Graphite
(c) Brass (d) Ammonium phosphate [(NH4)3 PO4 ]
(e) SiC (f) Rb
(g) 2 (h) LiBr
(i) P4 (j) Si
(k) Plastic.
PROBLEMS BASED ON CRYSTAL SYSTEMS, UNIT CELLS
2. How many Bravais lattices are possible in 3D ?
3. What are the crystallographic parameters of hexagonal, monoclinic and triclinic unit cell
respectively.
PROBLEMS BASED ON 2D ARRANGEMENT
4. Given below are two dimensions lattices with nicely shaded regions. You just have to find the
contributions (in fractions) of particles marked to the shaded regions and the total number of
particles in the regions.
(a) (b) (a) (b) (a) (b)
(iv) (a)

(a)

(b)
(i) (ii) (iii) (v)

5. What is the coordination number in a square close packed structure in two dimensions?
PROBLEMS BASED ON SC, BBC AND FCC
6. A metal crystallises in bcc. Find the % fraction of edge length not covered and also % fraction of
edge length covered by atom is:
7. A closed packed structure of uniform spheres has the edge length of 534 pm. Calculate the radius
of sphere, if it exists in
(a) Simple cubic lattice (b) BCC lattice (c) FCC lattice
8. Xenon crystallises in the face-centred cubic lattice and the edge of the unit cell is 620 pm. What
is the nearest neighbour distance and what is the radius of xenon atom?

APNI KAKSHA 52
(PHYSICAL CHEMISTRY) SOLID STATE
9. Following figure shows an FCC unit cell with atoms of radius r marked 1(corner),
2(face center), 3(face center). A quadrilateral is also shown by joining the centers of 4 face
centered atoms.
Find: (i) The distances between atoms 1 & 2, 2 & 3 and 1 & 3.
(ii) The shape and dimensions of the quadrilateral.
3

2
1
PROBLEMS BASED ON DENSITY
10. The effective radius of the iron atom is 1.42 Å. It has FCC structure. Calculate its density
(Fe = 56 amu)
11. Gold crystallizes in a face centered cubic lattice. If the length of the edge of the unit cell is
407 pm, calculate the density of gold as well as its atomic radius assuming it to be spherical.
Atomic mass of gold = 197 amu.
12. An element crystallizes in a structure having FCC unit cell of an edge 200 pm. Calculate the
density, if 200 g of this element contains 24×1023 atoms.
13. Iron crystallizes in several modifications. At about 910°C, the body-centered cubic ‘ ’ form
undergoes a transition to the face-centered cubic ‘𝛄’ form. Calculate the ratio of the density of
iron to that of  iron at the transition temperature.
14. Iron occurs as bcc as well as fcc unit cell. If the effective radius of an atom of iron is
124 pm. Compute the density of iron in both these structures.
PROBLEMS BASED ON RADIUS RATIO
15. The two ions A+ and B– have radii 88 and 200 pm respectively. In the closed packed crystal of
compound AB, predict the co-ordination number of A+.
16. If the radius of Mg2+ ion, Cs+ ion, O2– ion, S2– ion and Cl– ion are 0.65 Å , 1.69 Å, 1.40 Å, 1.84 Å, and
1.81 Å respectively. Calculate the co-ordination numbers of the cations in the crystals of MgS,
MgO and CsCl.
PROBLEMS BASED ON TV AND OV
17. What is the number and closest distance between octahedral voids and tetrahedral voids in fcc
unit cell?
18. In a compound, oxide ions are arranged in cubic close packing arrangement. Cations
A occupy one-sixth of the tetrahedral voids and cations B occupy one-third of the octahedral
voids. The formula of the compound is AxByOz, then find the value of x + y + z.
APNI KAKSHA 53
(PHYSICAL CHEMISTRY) SOLID STATE
19. A cubic solid is made up of two elements A and B. Atoms B are at the corners of the cube and A
at the body centre. What is the formula of compound?
20. A cubic solid is made by atoms A forming close pack arrangement, B occupying
one-fourth of tetrahedral void and C occupying half of the octahedral voids. What is the formula
of compound?
21. Spinel is a important class of oxides consisting of two types of metal ions with the oxide ions
arranged in CCP pattern. The normal spinel has one-eight of the tetrahedral holes occupied by
one type of metal ion and one half of the octahedral hole occupied by another type of metal ion.
Such a spinel is formed by Zn2+, Al3+ and O2–, with Zn2+ in the tetrahedral holes. Give the formulae
of spinel.
PROBLEMS BASED ON NaCl STRUCTURE
22. KF crystallizes in the NaCl type structure. If the radius of K+ ions 132 pm and that of
F– ion is 135 pm, what is the shortest K–F distance? What is the edge length of the unit cell? What
is the closet K–K distance?
23. The density of KBr is 2.75 g cm–3. The length of the edge of the unit cell is 654 pm.
Find the number of formula unit of KBr present in the single unit cell.
(N = 6.023 ×1023 mol–1, Atomic mass : K = 39, Br = 80)
24. A crystal of lead (II) sulphide has NaCl structure. In this crystal the shortest distance between
Pb+2 ion and S2– ion is 297 pm. What is the length of the edge of the unit cell in lead sulphide?
Also calculate the unit cell volume.
r+ 1
25. Percentage of void space in AB solid having rock salt structure if = having cation anion
r– 2
contact.
Given  = 3.15.
PROBLEMS BASED ON ZnS, CsCl STRUCTURE
26. CsCl has the bcc arrangement and its unit cell edge length is 400 pm. Calculate the inter ionic
distance in CsCl.
27. If the length of the body diagonal for CsCl which crystallises into a cubic structure with Cl – ions
at the corners and Cs+ ions at the centre of the unit cells is 7 Å and the radius of the Cs+ ion is
1.69 Å, what is the radius of Cl– ion?
28. Rbl crystallizes in CsCl structure in which each Rb+ is surrounded by eight iodide ions each of
radius 2.17 Å. Find the length of one side of RbI unit cell.

APNI KAKSHA 54
(PHYSICAL CHEMISTRY) SOLID STATE
PROBLEMS BASED ON DEFECTS IN SOLIDS
29. The composition of a sample of wustite is Fe0.93O1.0. What percentage of iron is present in the
form of Fe(III)?
30. If NaCl is dopped with 10–3 mol % SrCl2, what is the numbers of cation vacancies per mole of
NaCl?
31. A non-stoichiometric compound Fe7S8 consist of iron in both Fe+2 and Fe+3 form and sulphur is
present as sulphide ions. Calculate cation vacancies as a percentage of total cation in the sample.

APNI KAKSHA 55
(PHYSICAL CHEMISTRY) SOLID STATE
EXERCISE (O-II)
1. Identical 4 spheres are taken and are arranged in a layer of square packing touching each other
as shown

The percentage of vacant space is

 3   
(A) 100 1 − (B) 100 1 −  (C) 100 − 3 (D) 
 8   6 8 6
2. A crystal is made of particles A and B. A forms FCC packing and B occupies all the octahedral
voids. If all the particles along the plane as shown in figure are removed, then, the formula of the
crystal would be :

(A) AB (B) A5B7 (C) A7B5 (D) None of these

3. In a solid, S2– ions are packed in fcc lattice. Zn2+ occupies half of the tetrahedral voids in an
alternating arrangement. Now if a plane is cut (as shown) then the cross-section would be:

Zn2+
S2–

(A) (B) (C) (D)

4. The density of CaF2 (fluorite structure) is 3.18 g/cm3. The length of the side of the unit cell is
(A) 253 pm (B) 344 pm (C) 546 pm (D) 273 pm
5. Correct statement(s) for the packing of identical disc in two dimensions is/are:
(A) For square close packing, coordination number is 4.
(B) For hexagonal close packing, coordination number is 6.
(C) There is only one void per atom in both, square and hexagonal close packing.
(D) Hexagonal close packing is more efficiently packed than square close packing.
6. Choose the correct option/options-
APNI KAKSHA 56
(PHYSICAL CHEMISTRY) SOLID STATE
(A) Two adjacent face centre atoms present on a horizontal plane doesn't touch each other in fcc
unit cell
(B) If the radius of cations and anions are 0.2 Å and 0.95 Å then coordination number of cation
in the crystal is 4.
(C) Minimum distance between two cubical voids in simple cube unit cell lattice will be a where
a is length of edge of unit cell
(D) NaCl is a ‘AB’ crystal lattice that can be interpreted to be made up of two individual fcc unit
cells of A+ and B– fused together in such a manner that the corner of one unit cell becomes
the edge centre of the other.
7. Which of the following statement(s) is/are correct –
(A) In a face centred cubic unit cell, the edge centre is an octahedral void.
(B) In a face centred cubic unit cell, the body centre is an octahedral void.
(C) In FCC unit cell, octahedral and tetrahedral voids are equal in number.
(D) Coordination number of FCC unit cell is 12
8. Which of the following statements is/are correct?
(A) In an anti-fluorite structure anions form FCC lattice and cations occupy all tetrahedral voids.
(B) Number of nearest Na+ ions of another Na+ in Na2O crystal will be 8.
(C) Each sphere is surrounded by six voids in two dimensional hexagonal close packed layers
(D) 8 Cs+ ions occupy the second nearest neighbour locations of a Cs+ ion
9. Which of the following are true -
(A) Ratio of nearest neighbours in simple cubic cell to next nearest neighbours in FCC is 1
(B) Packing efficiency of a unit cell in which atoms are present at each corner and each edge
centre is 26 % in metallic crystal.
(C) Ratio of nearest neighbours in simple cubic cell to next nearest neighbours in BCC 1
(D) If number of unit cell along one edge are 'x' then total number of unit cell in cube = x3
10. Which statements is correct about HCP and CCP lattice
(A) Number of tetrahedral voids are twice of octahedral holes
(B) 2 tetrahedral and 1 octahedral voids are present in HCP unit cell per atom.
(C) Tetrahedral voids = 2 × octahedral voids, is valid for ccp and hcp.
(D) Distance between two hexagonal planes in CCP or HCP arrangement is same for a metal exist
in both forms.
11. Correct statement for ccp is:
(A) Each octahedral void is surrounded by 6 spheres and each sphere is surrounded by 4
octahedral voids

APNI KAKSHA 57
(PHYSICAL CHEMISTRY) SOLID STATE
(B) Each octahedral void is surrounded by 6 spheres and each sphere is surrounded by 6
octahedral voids
(C) Each octahedral void is surrounded by 6 spheres and each sphere is surrounded by 8
octahedral voids
(D) Each octahedral void is surrounded by 6 spheres and each sphere is surrounded by 12
octahedral voids
12. Which of the following statements is correct in the rock-salt structure of ionic compounds?
(A) coordination number of cation is four whereas that of anion is six.
(B) coordination number of cation is six whereas that of anion is four.
(C) coordination number of each cation and anion is four.
(D) coordination number of each cation and anion is six.
13. Select correct statement(s)
(A) Density of crystal always increases due to substitutional impurity defect.
(B) An atom/ion is transferred from a lattice site to an interstitial position in Frenkel defect.
(C) In AgCl, the silver ion is displaced from its lattice position to an interstitial position. Such a
defect is called a Frenkel defect
(D) By defects in solids density of solids either remains constant or decreases but it can never
increase.
14. Select the correct statement (s) :
(A) CsCl mainly shows Schottky defect
(B) ZnS mainly shows Frenkel defect
(C) NaCl unit cell contain 4Na+ and 4Cl—
(D) In NaCl one Na+ is surrounded by 6 Cl— then 12 Na+ and then 8 Cl— .
Comprehension: (Q. 15 & 16)
Solid balls of radius 17.32 cm crystallises in bcc pattern, during one such crystallisation some
oxygen gas is trapped. This trapped oxygen at 640K creates pressure of 5 atm.
Assume:
(i) BCC arrangement is not disturbed due to trapping of gas.
(ii) Gas is uniformly distributed inside unit cell

[Take R = 0.08 atm-litre/mole-K, NA = 6 × 1023, Mass of a solid ball = 64 g]

15. Calculate number of oxygen molecules present in a unit cell

(A) 24 × 1023 (B) 12 × 1023 (C) 6 × 1023 (D) 3 × 1023
16. Calculate percentage increase in density due to trapping of gas
(A) 16.67 % (B) 33.33 % (C) 100% (D) 50%
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(PHYSICAL CHEMISTRY) SOLID STATE
Comprehension: (Q. 17 to 19)
Calcium crystallizes in a cubic unit cell with density 3.2 g/cc. Edge-length of the unit cell is 437
pm
17. The type of unit cell is:
(A) Simple cubic (B) BCC (C) FCC (D) Edge-centred
18. The nearest neighbour distance is:
(A) 154.5 pm (B) 309 pm (C) 218.5 pm (D) 260 pm
19. The number of nearest neighbours of a Ca atom are:
(A) 4 (B) 6 (C) 8 (D) 12
20. If the metal is melted, density of the molten metal was found to be 3 g/cc. What will be the
percentage of empty space in the liquid metal?
(A) 31% (B) 36% (C) 28% (D) 49%
Comprehension: (Q. 21 & 22)
There is large variety of non-stoichiometric inorganic solids which contain an excess or
deficiency of one of the elements. Such solids showing deviations from the ideal stoichiometric
composition form an important group of solids. For example in the vanadium oxide, VOx, x can
be anywhere between 0.6 and 1.3. There are solids which are difficult to prepare in the
stoichiometric composition. Thus, the ideal composition in compounds such as FeO is difficult to
obtain (normally we get a composition of Fe0.95 O but it may range from Fe0.93 O to Fe0.96O). Non-
stoichiometric behaviour is most commonly found for transition metal compounds though are
also known for some lanthanides and actinides.
Zinc oxide loses oxygen reversibly at high temperatures and turns yellow in colour.
The excess metal is accommodated interstitially, giving rise to electrons trapped in the
neighborhoods. The enhanced electrical conductivity of the non-stoichiometric ZnO arises from
these electrons.
Anion vacancies in alkali halides are produced by heating the alkali halide crystals in an
atmosphere of the alkali metal vapour. When the metal atoms deposit on the surface they diffuse
into the crystal and after ionisation the alkali metal ion occupies cationic vacancy whereas
electron occupies anionic vacancy. Electrons trapped in anion vacancies are referred to as F-
centers (from Farbe the German word for colour) that gives rise to interesting colour in alkali
halides. Thus, the excess of potassium in KCl makes the crystal appear violet and the excess of
lithium ions LiCl makes it pink.
21. When LiCI is heated into the vapour of lithium, the crystal acquires pink colour. This is due to
(A) Schottky defects (B) Frenkel defects
(C) Metal excess defect leading to F-centers (D) Electronic defect

APNI KAKSHA 59
(PHYSICAL CHEMISTRY) SOLID STATE
22. AgCl is crystallized from molten AgCl containing a little CdCl2. The solid obtained will have
(A) cationic vacancies equal to number of Cd2+ ions incorporated
(B) cationic vacancies equal to double the number of Cd2+ ions
(C) anionic vacancies
(D) neither cationic nor anionic vacancies
MATCH THE COLUMN
23. Match the column
Column I Column II
(A) Tetragonal and Hexagonal (P) are two crystal systems
(B) Cubic and Rhombohedral (Q) a = b  c
(C) Monoclinic and Triclinic (R) a  b  c
(D) Cubic and Hexagonal (S) a = b = c
24. Match the column:
Column I Column II
(A) Rock salt structure (P) Co-ordination number of cation is 4
3a
(B) Zinc Blend structure (Q) = r+ + r–
4
(C) Fluorite structure (R) Co-ordination number of cation and anion are same
a
(S) Distance between two nearest anion is
2

MATCHING LIST TYPE

25. Match the column
Column I Column II
(Arrangement of the atoms/ions) (Planes in fcc lattice)

(P) (1)

(Q) (2)

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(PHYSICAL CHEMISTRY) SOLID STATE

(R) (3)

(S) (4)

Code:
P Q R S P Q R S
(A) 4 3 1 2 (B) 4 3 2 1
(C) 3 2 1 4 (D) 1 2 4 3
26. Column I Column II
[Distance in terms of edge length of cube (a)]
(P) 0.866 a (1) Shortest distance between cation & anion in CsCl structure.
(Q) 0.707 a (2) Shortest distance between two cation in CaF2 structure.
(R) 0.433 a (3) Shortest distance between carbon atoms in diamond.
(S) 1.414 a (4) the distance at which second nearest neighbour is present in
simple cubic unit cell
Code :
P Q R S P Q R S
(A) 4 3 1 2 (C) 3 2 1 4
(B) 1 2 3 4 (D) 1 2 4 3

APNI KAKSHA 61
(PHYSICAL CHEMISTRY) SOLID STATE
EXERCISE (S-II)
1. How many spherical balls of radii 2 cm can be placed completely inside a cubical box of edge = 8
cm?

2. Calculate the density of diamond from the fact that it has face centered cubic structure with two
atoms per lattice point and unit cell edge length of 3.569 Å.
3. An element crystallizes into a structure which may be described by a cubic type of unit cell
having one atom on each corner of the cube and two atoms on one of its body diagonals. If the
volume of this unit cell is 24×10–24 cm3 and density of element is 7.2 g cm–3, calculate the number
of atoms present in 200 g of element.
4. What is the percent by mass of titanium in rutile, a mineral that contain Titanium and oxygen, if
structure can be described as a closet packed array of oxide ions, with titanium in one half of the
octahedral holes. What is the oxidation number of titanium? (Ti = 48)
5. A solid A+ and B– had NaCl type closed packed structure. If the anion has a radius of
250 pm, what should be the ideal radius of the cation? Can a cation C+ having a radius of
180 pm be slipped into the tetrahedral site of the crystal of A+B–, without disturbing the crystal?
Give reasons for your answer.
6. What will be packing fraction of solid in which atoms are present at corners and cubic void is
occupied? The insertion of the sphere into void does not disturb simple cubic lattice.
7. For ABCABC packing distance between two successive tetrahedral void is X and distance

y 2
between two successive octahedral void is y in a unit cell, then is.
X
8. Calculate the perimeter of given plane in HCP unit cell (Given that radius of atoms = R Å).

APNI KAKSHA 62
(PHYSICAL CHEMISTRY) SOLID STATE
2
9. An element 'M' crystallizes in ABAB....type packing if adjacent layer A & B are 10 pm apart,
3
then calculate radius of largest sphere which can be fitted in the void. (in pm) without disturbing

the lattice arrangement (Given: 2 = 1.414 )

Fill your answer as sum of digits (excluding decimal places) till you get the single digit answer.
10. Find packing fraction of unit cell of AAAAA.......type hypothetical arrangement in which hexagonal
packing is taken in layer.
11. A cubic unit cell contains manganese ions at the corners and fluoride ions at the center of each
edge.
(a) What is the empirical formula of the compound?
(b) What is the co-ordination number of the Mn ion?
(c) Calculate the edge length of the unit cell, if the radius of Mn ion is 0.65 Å and that of F– ion is
1.36 Å.
12. Potassium crystallizes in a body-centered cubic lattice with edge length, a = 5.2 Å.
(a) What is the distance between nearest neighbours?
(b) What is the distance between next-nearest neighbours?
(c) How many nearest neighbours does each K atom have?
(d) How many next-nearest neighbours does each K atom have?
13. AgCl has the same structure as that of NaCl. The edge length of unit cell of AgCl is found to be 555
pm and the density of AgCl is 5.561 g cm–3. Find the percentage of sites that are unoccupied.
rNa+ rNa+
14. KCl crystallizes in the same type of lattice as does NaCl. Given that = 0.5 and = 0.7
rCl− rK+

Calculate:
(a) The ratio of the sides of unit cell for KCl to that for NaCl and
(b) The ratio of densities of NaCl to that for KCl.
15. Prove that void space in fluorite structure per unit volume of unit cell is 0.374.
16. Ice crystallizes in a hexagonal lattice. At the low temperature at which the structure was
determined, the lattice constants where a = 4.53 Å, and b = 7.60 Å How many molecules are
contained in a given unit cell?
[density (ice) = 0.92 gm/cm3)]

APNI KAKSHA 63
(PHYSICAL CHEMISTRY) SOLID STATE
17. The olivine series of minerals consists of crystals in which Fe and Mg ions may substitute for
each other causing substitutional impurity defect without changing the volume of the unit cell.
In olivine series of minerals, oxide ion exist as FCC with Si4+ occupying 1/4th of octahedral voids
and divalent ions occupying 1/4th of tetrahedral voids. The density of forsterite (magnesium
silicate) is 3.21 g/cc and that of fayalite (ferrous silicate) is 4.34 g/cc. Find the formula of
forsterite and fayalite minerals and the percentage of fayalite in an olivine with a density of 3.88
g/cc.
18. In the 1980’s a class of ceramic materials was discovered that exhibits superconductivity at the
unusually high temperature of 90 K. One such material contains yttrium, barium, copper and
oxygen and is called “YBCO”. It has a nominal composition of YBa2Cu3O7, but its actual
composition is variable according to the formula YBa2Cu3O7- (0 <  < 0.5).
(a) One unit cell of the idealized crystal structure of YBCO is shown below. Identify which circles
correspond to which elements in the structure.

c
b
x
a

The true structure is actually orthorhombic (a  b  c), but it is approximately tetragonal,

with a  b  (c/3).
(b) Estimate the density of this sample of YBCO (with  = 0.25) in g cm–3. Use a = 500 pm and
c = 1500 pm. Ba (137.33), Y (88.91), Cu (63.5), O (16).

APNI KAKSHA 64
(PHYSICAL CHEMISTRY) SOLID STATE
EXERCISE (JEE-MAIN)
1. In a solid AB. A atoms are in ccp arrangement and B atoms occupy all the octahedral sites. If two
atoms from the opposite faces are removed, then the resultant stoichiometry of the compound
is AxBy. The value of x is_______. [nearest integer] [JEE Main, June 2022]
2. Metal deficiency defect is shown by Fe0.93O. In the crystal, some Fe2+ cations are missing and loss
of positive charge is compensated by the presence of Fe3+ ions. The percentage of Fe2+ ions in the
Fe0.93O crystals is _________ . (Nearest integer) [JEE Main, June 2022]
3. Select the correct statements. [JEE Main, July 2021]
(A) Crystalline solids have long range order.
(B) Crystalline solids are isotropic.
(C) Amorphous solid are sometimes called pseudo solids.
(D) Amorphous solids soften over a range of temperatures.
(E) Amorphous solids have a definite heat of fusion.
Choose the most appropriate answer from the options given below.
(A) (A), (B), (E) only (B) (B), (D) only
(C) (C), (D) only (D) (A), (C), (D) only
4. The parameters of the unit cell of a substance are [JEE Main, July 2021]
a = 2.5, b = 3.0, c = 4.0,  =90°,  =120°,  =90°.
The crystal system of the substance is :
(A) Hexagonal (B) Orthorhombic
(C) Monoclinic (D) Triclinic
5. In a binary compound, atoms of element A form a hcp structure and those of element M occupy
2/3 of the tetrahedral voids of the hcp structure. The formula of the binary compound
is: [JEE Main, March 2021]
(A) M2A3 (B) M4A3 (C) M4A (D) MA3
6. Given below are two statements.
Statement I: Frenkel defects are vacancy as well as interstitial defects. [JEE Main, Aug. 2021]
Statement II: Frenkel defect leads to colour in ionic solids due to presence of F-centres.
Choose the most appropriate answer for the statements from the options given below:
(A) Statement I is false but Statement II is true
(B) Both Statement I and Statement II are true
(C) Statement I is true but Statement II is false
(D) Both Statement I and Statement II are false

APNI KAKSHA 65
(PHYSICAL CHEMISTRY) SOLID STATE
7. A hard substance melts at high temperature and is an insulator in both solid and in molten
state.
This solid is most likely to be a / an : [JEE Main, Mar. 2021]
(A) Ionic solid (B) Molecular solid
(C) Metallic solid (D) Covalent solid
8. Match items of List–I with those of List–II : [JEE Main, Aug. 2021]
List–I List–II
(Property) (Example)
(a) Diamagnetism (i) MnO
(b) Ferrimagnetism (ii) O2
(c) Paramagnetism (iii) NaCl
(d) Antiferromagnetism (iv) Fe3O4
Choose the most appropriate answer from the options given below:
(A) (a)–(ii), (b)–(i), (c)–(iii), (d)–(iv)
(B) (a)–(i), (b)–(iii), (c)–(iv), (d)–(ii)
(C) (a)–(iii), (b)–(iv), (c)–(ii), (d)–(i)
(D) (a)–(iv), (b)–(ii), (c)–(i), (d)–(iii)
9. A diatomic molecule X2 has a body-centred cubic (bcc) structure with a cell edge of 300 pm. The
density of the molecule is 6.17 g cm–3. The number of molecules present in 200 g of X2 is:
(Avogadro constant (NA) = 6 × 1023 mol–1) [Jee Main, 2020]
(A) 8 NA (B) 2 NA (C) 4 NA (D) 40 NA
10. An element with molar mass 2.7 × 10–2 kg mol–1 forms a cubic unit cell with edge length 405 pm.
It its density is 2.7 × 103 kg m–3, the radius of the element is approximately ___×10–12 m (to the
nearest integer). [Jee Main, 2020]
11. An element crystallizes in a face-centred cubic (fcc) unit cell with cell edge a. The distance
between the centres of two nearest octahedral voids in the crystal lattice is: [Jee Main, 2020]
a
(A) (B) a (C) a (D) 2a
2 2
12. The radius of the largest sphere which fits properly at the centre of the edge of body centred
cubic unit cell is : (Edge length is represented by 'a') : [Jee Main, Jan 2019]
(A) 0.047 a (B) 0.027 a (C) 0.067 a (D) 0.134 a
13. Consider the bcc unit cells of the solids 1 and 2 with the position of atoms as shown below. The
radius of atom B is twice that of atom A. The unit cell edge length is 50% more in solid 2 then in
1. What is the approximate packing efficiency in solid 2 ? [Jee Main, April 2019]

APNI KAKSHA 66
(PHYSICAL CHEMISTRY) SOLID STATE
A A A A
A A A A
B
A
A A A A
A A A A
Solid 1 Solid 2

(A) 90% (B) 45% (C) 75% (D) 65%

14. Element ‘B’ forms ccp structure and ‘A’ occupies half of the octahedral voids, while oxygen atoms
occupy all the tetrahedral voids. The structure of bimetallic oxide is : [Jee Main, April 2019]
(A) AB2O4 (B) A4B2O (C) A4BO4 (D) A2B2O
15. An element has a face-centred cubic (fcc) structure with a cell edge of a. The distance between
the centres of two nearest tetrahedral voids in the lattice is: [Jee Main, April 2019]

(A) 2a (B) a (C) a (D) 3 a

2 2
16. Which type of 'defect' has the presence of cations in the interstitial sites? [Jee Main, 2018]
(A) Metal deficiency defect (B) Schottky defect
(C) Vacancy defect (D) Frenkel defect
17. All of the following share the same crystal structure except :- [Jee Main, 2018]
(A) RbCl (B) CsCl (C) LiCl (D) NaCl
18. 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 [Jee-Main (offline)-17]
a
(A) 2 a (B) (C) 2a (D) 2 2a
2
19. Which of the following compounds is metallic and ferromagnetic?
[Jee-Main (offline)-16]
(A) CrO2 (B) VO2 (C) MnO2 (D) TiO2
20. Sodium metal crystallizes in a body centred cubic lattice with a unit cell edge of 4.29Å. The radius
of sodium atom is approximately: [Jee-Main (offline)-15]
(A) 5.72Å (B) 0.93Å (C) 1.86Å (D) 3.022Å
21. CsCl crystallises in body centred cubic lattice. If 'a' is its edge length then which of the following
expression is correct : [Jee-Main (offline)-14]

3
(A) rCs+ + rCl− = a (B) rCs+ + rCl− = 3a
2
3a
(C) rCs+ + rCl− = 3a (D) rCs+ + rCI− =
2
APNI KAKSHA 67
(PHYSICAL CHEMISTRY) SOLID STATE
22. In a face centered cubic lattice atoms A are at the corner points and atoms B at the face centered
points. If atom B is missing from one of the face centered points, the formula of the ionic
compound is: [AIEEE-2011, Jee-Main (online)-14]
(A) AB2 (B) A2B3 (C) A5B2 (D) A2B5
23. The appearance of colour in solid alkali metal halides is generally due to:
(A) Frenkel defect (B) F-centres (C) Schottky defect (D) Interstitial position
24. In a monoclinic unit cell, the relation of sides and angles are respectively
[Jee-Main (online)-14]
(A) a  b  c and       90º
(B) a  b  c and  =  = 90º  
(C) a = b  c and  =  =  = 90º
(D) a  b  c and  =  =  = 90º
25. The total number of octahedral void(s) per atom present in a cubic close packed structure is :-
[Jee-Main (online)-14]
(A) 1 (B) 2 (C) 3 (D) 4
26. Experimentally it was found that a metal oxide has formula M0.98O. Metal M, is present as M2+
and M3+ in its oxide. Fraction of the metal which exists as M3+ would be:
[Jee-Main (offline)-13]
(A) 7.01% (B) 4.08% (C) 6.05% (D) 5.08
27. An element having an atomic radius of 0.14 nm crystallizes in an fcc unit cell. What is the length
of a side of the cell? [Jee-Main (online)-13]
(A) 0.96 nm (B) 0.4 nm (C) 0.24 nm (D) 0.56 nm
28. Which one of the following statements about packing in solids is incorrect?
(A) Void space in ccp mode of packing is 26% [Jee-Main (online)-13]
(B) Coordination number in hcp mode of packing is 12
(C) Void space in hcp mode of packing is 32%
(D) Coordination number in bcc mode of packing is 8
29. In a face centred cubic lattice, atoms of A form the corner points and atoms of B form the face
centred points. If two atoms of A are missing from the corner points, the formula of the ionic
compound is [Jee-Main (online)-13]
(A) AB2 (B) AB3 (C) AB4 (D) A2B5
30. Copper crystallises in fcc with a unit length of 361pm. What is the radius of copper atom?
[AIEEE-2011, Jee-Main (online)-13]
(A) 181pm (B) 128pm (C) 157pm (D) 108pm

APNI KAKSHA 68
(PHYSICAL CHEMISTRY) SOLID STATE
31. Lithium forms body centred cubic structure. The length of the side of its unit cell is 351 pm.
Atomic radius of the lithium will be: [AIEEE-12]
(A) 152 pm (B) 75 pm (C) 300 pm (D) 240 pm
32. Among the following the incorrect statement is: [Jee-Main (online)-12]
(A) Density of crystals remains unaffected due to Frenkel defect
(B) In BCC unit cell the void space is 32%
(C) Electrical conductivity of semiconductors and metals increases with increase in temperature
(D) Density of crystals decreases due to Schottky defect
33. A solid has 'bcc' structure. If the distance of nearest approach between two atoms is
1.73 Å, the edge length of the cell is: [Jee-Main (online)-12]
(A) 314.20 pm (B) 216 pm (C) 200 pm (D) 1.41 pm
34. Ammonium chloride crystallizes in a body centred cubic lattice with edge length of unit cell of
390 pm. If the size of chloride ion is180 pm, the size of ammonium ion would be:
[Jee-Main (online)-12]
(A) 158 pm (B) 174 pm (C) 142 pm (D) 126 pm
35. The radius of a calcium ion is 94 pm and of the oxide ion is 146 pm. The possible crystal structure
of calcium oxide will be [Jee-Main (online)-12]
(A) Octahedral (B) Tetrahedral (C) Pyramidal (D) Trigonal
36. Percentages of free space in cubic close packed structure and in body centered packed structure
are respectively [AIEEE-10]
(A) 48% and 26% (B) 30% and 26% (C) 26% and 32% (D) 32% and 48%
37. The edge length of a face centered cubic cell of an ionic substance is 508 pm. If the radius of the
cation is 110 pm, the radius of the anion is: [AIEEE-10]
(A) 144 pm (B) 288 pm (C) 398 pm (D) 618 pm
38. In a compound, atoms of element Y form ccp lattice and those of element X occupy 2/3rd of
tetrahedral voids. The formula of the compound will be: [AIEEE-08]
(A) X4Y3 (B) X2Y3 (C) X2Y (D) X3Y4
39. Total volume of atoms present in a face-centred cubic unit cell of a metal is (r is atomic radius):
[AIEEE-06]
24 3 12 3 16 3 20 3
(A) r (B) r (C) r (D) r
3 3 3 3
40. Lattice energy of an ionic compound depends upon: [AIEEE-05]
(A) Size of the ion only (B) Charge on the ion only
(C) Charge on the ion and size of the ion (D) Packing of ions only

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(PHYSICAL CHEMISTRY) SOLID STATE
41. An ionic compound has a unit cell consisting of A ions at the corners of a cube and B ions on the
centres of the faces of the cube. The empirical formula of this compound would be–
[AIEEE-05]
(A) A2B (B) AB (C) A3B (D) AB3
42. What type of crystal defect is indicated in the diagram below? [AIEEE-04]
Na+ Cl– Na+ Cl– Na+ Cl–
Cl– Cl– Na+ Na+
Na+ Cl– Cl– Na+ Cl–
Cl– Na +Cl– Na+ Na+
(A) Frenkel defect (B) Schottky defect
(C) Interstitial defect (D) Frenkel and Schottky defects
43. How many unit cells are present in a cube-shaped ideal crystal of NaCl of mass 1.00g ?
(A) 1.28 × 1021 unit cells (B) 1.71 × 1021 unit cells [AIEEE-03]
(C) 2.57 × 1021 unit cells (D) 5.14 × 1021 unit cells
44. The no. of atoms per unit cell in B.C.C. & F.C.C. is respectively: [AIEEE-02]
(A) 8, 10 (B) 2, 4 (C) 1, 2 (D) 1, 3

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(PHYSICAL CHEMISTRY) SOLID STATE
EXERCISE (JEE-ADVANCED)

1. Atoms of metals 𝒙, 𝒚, and 𝒛 form face-centred cubic (fcc) unit cell of edge length 𝐋𝒙 , body-centred
cubic (bcc) unit cell of edge length 𝐋𝒚 , and simple cubic unit cell of edge length 𝐋𝒛 , respectively.
√𝟑 𝟖 𝟑
If 𝒓𝒛 = 𝒓 ;𝒓
𝟐 𝒚 𝒚
= 𝒓 ; 𝑴𝒛 = 𝟐 𝑴𝒚 and 𝑴𝒛 = 𝟑𝑴𝒙 , then the correct statement (s) is (are)
√𝟑 𝒙

[Given : 𝑴𝒙 , 𝑴𝒚 , and 𝑴𝒛 are molar masses of metals 𝒙, 𝒚, and 𝒛, respectively.

𝐫𝐱 , 𝐫𝐲 , and 𝐫𝐳 are atomic radii of metals 𝒙, 𝒚, and 𝒛, respectively.] [JEE Adv. 2023]

(A) Packing efficiency of unit cell of 𝒙 > Packing efficiency of unit cell of 𝒚 > Packing efficiency of
unit cell of 𝒛
(B)𝐋𝐲 > 𝐋𝐳
(C)𝐋𝐱 > 𝐋𝐲
(D) Density of 𝒙 > Density of 𝒚

2. Atom X occupies the fcc lattice sites as well as alternate tetrahedral voids of the same lattice. The
packing efficiency (in %) of the resultant solid is closest to
(A) 25 (B) 35 (C) 55 (D) 75 [JEE Adv. 2022]
3. For the given close packed structure of a salt made of cation X and anion Y shown below (ions of
only one face are shown for clarity), the packing fraction is approximately

(packing fraction Packing efficiency ) [JEE-2021]

100

(A) 0.74 (B) 0.63 (C) 0.52 (D) 0.48

4. The cubic unit cell structure of a compound containing cation M and anion X is shown below.

When compared to the anion, the cation has smaller ionic radius. Choose the correct
statement(s). [JEE-2020]
(A) The empirical formula of the compound is MX.

APNI KAKSHA 71
(PHYSICAL CHEMISTRY) SOLID STATE
(B) The cation M and anion X have different coordination geometries.
(C) The ratio of M-X bond length to the cubic unit cell edge length is 0.866.
(D) The ratio of the ionic radii of cation M to anion X is 0.414.
5. Consider an ionic solid MX with NaCl structure. Construct a new structure (Z) whose unit cell is
constructed from the unit cell of MX following the sequential instructions given below. Neglect
the charge balance. [JEE-2018]
(i) Remove all the anions (X) except the central one
(ii) Replace all the face centered cations (M) by anions (X)
(iii) Remove all the corner cations (M)
(iv) Replace the central anion (X) with cation (M)
 number of anions 
The value of   in Z is _____.
 number of cations 
6. A crystalline solid of a pure substance has a face-centred cubic structure with a cell edge of 400
pm. If the density of the substance in the crystal is 8 g cm-3, then the number of atoms present in
256 g of the crystal is N × 1024. The value of N is [JEE-2017]
7. The CORRECT statement(s) for cubic close packed (ccp) three dimensional structure is (are)
[JEE-2016]
(A) The number of the nearest neighbours of an atom present in the topmost layer is 12
(B) The efficiency of atom packing is 74%
(C) The number of octahedral and tetrahedral voids per atom are 1 and 2, respectively

(D) The unit cell edge length is 2 2 times the radius of the atom
8. If the unit cell of a mineral has cubic close packed (ccp) array of oxygen atoms with m fraction of
octahedral holes occupied by aluminum ions and n fraction of tetrahedral holes occupied by
magnesium ions m and n respectively, are – [JEE-2015]
1 1 1 1 1 1 1
(A) , (B) 1, (C) , (D) ,
2 8 4 2 2 4 8
9. 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, the radius of A+ is - [JEE-2013]

X-

A+

(A) 104 pm (B) 125 pm (C) 183 pm (D) 57 pm

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(PHYSICAL CHEMISTRY) SOLID STATE
10. A compound MpXq has cubic close packing (ccp) arrangement of X. Its unit cell structure is shown
below. The empirical formula of the compound is: [JEE-2012]

M=
M=

(A) MX (B) MX2 (C) M2X (D) M5X14

11. The number of hexagonal faces that present in a truncated octahedron is. [JEE-2011]
12. Silver (atomic weight = 108 g mol–1) has a density of 10.5 g cm–3. The number of silver atoms on
a surface of area 10–12 m2 can be expressed in scientific notation as y ´ 10x. The value of x is
[JEE 2010]
13. The packing efficiency of the two-dimensional square unit cell shown below is
[JEE-2010]

(A) 39.27% (B) 68.02% (C) 74.05% (D) 78.54%

14. The correct statement(s) regarding defects in solid is (are) [JEE 2009]
(A) Frenkel defect is usually favoured by a very small difference in the sizes of cation and anion.
(B) Frenkel defect is a dislocation defect
(C) Trapping of an electron in the lattice leads to the formation of F-center.
(D) Schottky defects have no effect on the physical properties of solids.
Paragraph for Question No. 15 to 17
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

APNI KAKSHA 73
(PHYSICAL CHEMISTRY) SOLID STATE
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’.
15. The number of atoms in this HCP unit cells is [JEE 2008]
(A) 4 (B) 6 (C) 12 (D) 17
16. The volume of this HCP unit cell is [JEE 2008]

(A) 24 2r3 (B) 16 2r3 (C) 12 2r3 (D) 64 r3

3 3

17. The empty space in this HCP unit cell is [JEE 2008]
(A) 74% (B) 47.6 % (C) 32% (D) 26%
18. Match the crystal system / unit cells mentioned in Column I with their characteristic features
mentioned in Column II. Indicate your answer by darkening the appropriate bubbles of the 4 ×
4 matrix given in the ORS. [JEE 2007]
Column I Column II
(A) simple cubic and face-centred cubic (P) have these cell parameters a = b = c and
==
(B) cubic and rhombohedral (Q) are two crystal systems
(C) cubic and tetragonal (R) have only two crystallographic angles of 90°
(D) hexagonal and monoclinic (S) belong to same crystal system.
19. The edge length of unit cell of a metal having atomic weight 75 g/mol is 5 Å which crystallizes in
cubic lattice. If the density is 2 g/cc then find the radius of metal atom. (N A = 6 × 1023). Give the
answer in pm. [JEE 2006]
20. An element crystallises in FCC lattice having edge length 400 pm. Calculate the maximum
diameter which can be placed in interstitial sites without disturbing the structure.
[JEE 2005]
21. Which of the following FCC structure contains cations in alternate tetrahedral voids?
[JEE 2005]
(A) NaCl (B) ZnS (C) Na2O (D) CaF2
22. (i) AB crystallizes in a rock salt structure with A : B = 1 : 1. The shortest distance between A
and B is Y1/3 nm. The formula mass of AB is 6.023 Y amu where Y is any arbitrary constant.
Find the density in kg m–3. [JEE–2004]
(ii) If measured density is 20 kg m-3. Identify the type of point defect.
23. Marbles of diameter 10 mm each are to be arranged on a flat surface so that their centres lie
within the area enclosed by four lines of length each 40 mm. Sketch the arrangement that will

APNI KAKSHA 74
(PHYSICAL CHEMISTRY) SOLID STATE
give the maximum number of marbles per unit area, that can be enclosed in this manner and
deduce the expression to calculate it. [JEE 2003]
24. A substance AxBy crystallises in a FCC lattice in which atoms “A” occupy each corner of the cube
and atoms “B” occupy the centres of each face of the cube. Identify the correct composition of the
substance AxBy. [JEE-2002]
(A) AB3 (B) A4B3
(C) A3B (D) composition cannot be specified
25. The figures given below show the location of atoms in three crystallographic planes in FCC
lattice. Draw the unit cell for the corresponding structure and identify these planes in your
diagram. [JEE-2000]

26. In a solid “AB” having NaCl structure “A” atoms occupy the corners of the cubic unit cell. If all the
face-centred atoms along one of the axes are removed, then the resultant stoichiometry of the
solid is [JEE-2000]
(A) AB2 (B) A2B (C) A4B3 (D) A3B4
27. In any ionic solid [MX] with schottky defects, the number of positive and negative ions are same.
[T/F] [JEE-2000]
28. The coordination number of a metal crystallising in a hcp structure is [JEE-2000]
(A) 12 (B) 4 (C) 8 (D) 6
29. A metal crystallises into two cubic phases, FCC and BCC whose unit cell lengths are 3.5 and 3.0 Å
respectively. Calculate the ratio of densities of FCC and BCC. [JEE-1999]

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(PHYSICAL CHEMISTRY) SOLID STATE
ANSWER KEY
EXERCISE (O-I)
1. (B) 2. (C) 3. (B) 4. (B) 5. (A) 6. (D) 7. (B)
8. (A) 9. (D) 10. (C) 11. (D) 12. (B) 13. (C) 14. (C)
15. (B) 16. (D) 17. (A) 18. (B) 19. (C) 20. (B) 21. (C)
22. (C) 23. (A) 24. (A) 25. (C) 26. (B) 27. (C) 28. (C)
29. (C) 30. (B) 31. (C) 32. (B) 33. (A) 34. (C) 35. (B)
36. (A) 37. (A) 38. (B) 39. (C) 40. (D) 41. (B) 42. (A)
43. (B) 44. (C) 45. (A) 46. (B) 47. (A) 48. (D) 49. (C)
50. (D) 51. (D) 52. (B) 53. (D) 54. (B) 55. (A) 56. (C & D)
57. (A & D)
EXERCISE (S-I)

1. Ionic – LiBr , (NH4)3PO4 ; Metallic – Brass, Rb; Molecular – P4O10 , I2 , P4

Network – SiC, Graphite, Si, Amorphous – Plastic
2. 14
3.

Crystal System Features Unit cell found Examples

𝐚≠𝐛≠𝐜
Monoclinic sulphur, 𝐏𝐛𝐂𝐫𝐎𝟒
Monoclinic 𝛂 = 𝛄 = 𝟗𝟎∘ 𝐒, 𝐄𝐂
𝐍𝐚𝟐 𝐒𝐎𝟒 ⋅ 𝟏𝟎𝐇𝟐 𝐎, 𝐍𝐚𝟐 𝐁𝟒 𝐎𝟕 ⋅ 𝟏𝟎𝐇𝟐 𝐎
𝛃 ≠ 𝟏𝟐𝟎∘ , ≠ 𝟗𝟎∘ , ≠ 𝟔𝟎∘

𝐚=𝐛≠𝐜
Hexagonal 𝐒 Graphite, 𝐙𝐧𝐎, 𝐂𝐝𝐒, 𝐌𝐠, 𝐏𝐛𝐈𝟐 , 𝐒𝐢𝐂
𝛂 = 𝛃 = 𝟗𝟎∘ , 𝛄 = 𝟏𝟐𝟎∘

𝐚≠𝐛≠𝐜
Triclinic 𝐒 𝐊 𝟐 𝐂𝐫𝟐 𝐎𝟕 , 𝐂𝐮𝐒𝐎𝟒 . 𝟓𝐇𝟐 𝐎, 𝐇𝟑 𝐁𝐎𝟑 .
𝛂 ≠ 𝛃 ≠ 𝛄 ≠ 𝟗𝟎∘

4. (a) (b) Total particles

(i) 1/4 1 2
(ii) 1/2 1/4 2
(iii) 1/6 1/2 2
(iv) 1/6 – 1/2
(v) 1/3 1/6 1
5. 4 6. 86.6%
7. (a) 267 pm, (b) 231.2 pm, (c) 188.8 pm

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(PHYSICAL CHEMISTRY) SOLID STATE
8. 438.5 pm, 219.25 pm 9. (i) 2r, 2r, 2 3 r , (ii) Square
10. 5.74 g cm–3 11. 19.4g/cm3, 143.9 pm
12. 41.67 g cm–3 13. 1.09 14. 7.922 g/cc , 8.625 g/c

a a
15. (6) 16. 4, 6, 8 17. 4, 8, , 18. 5 (ABO3)
2 2
19. A, B 20. A2BC 21. ZnAl2O4 22. 267 pm, 534 pm, 378 pm
23. 4 24. a =5.94×10–8cm, V=2.096 × 10–22 cm–3 25. 30%
26. = 346· 4 pm 27. 1.81Å 28. 4.34 Å
29. 15.05 30. 6.02 × 1018 31. 12.5

EXERCISE (O-II)
1. (B) 2. (A) 3. (D) 4. (C) 5. (ABD) 6. (ACD)
7. (ABD) 8. (AC) 9. (ABCD) 10. (ABCD) 11. (B)
12. (D) 13. (BC) 14. (ABCD)
Comprehension: (Q. 15 & 16)
15. (B) 16. (D)
Comprehension: (Q. 17 to 20)
17. (C) 18. (B) 19. (D) 20. (A)
Comprehension: (Q. 20 & 21)
21. (C) 22. (A)
23. A → P, Q ; B → P,S ; C → P,R ; D → P
24. A → R,S ; B → P,Q,R,S ; C → Q
25. (A) 26. (B)

EXERCISE (S-II)
1. 8 2. 3.5 g cm–3 3. 3.48 × 1024 atoms 4. 60%, +4
5. 103.4 pm, No 6. 0.7285 7. 2 8. 14.53 R 9. 2.07
10. 0.605
11. (a) MnF3, (b) 6, (c) 4.02Å
12. (a) 4.5 Å, (b) 5.2 Å, (c) 8, (d) 6, (e) 0.92 g/cm3
13. 0.24 14. (a) 1.143, (b) 1.172 15. Not Available
16. 4 molecules of H2O 17. Mg2SiO4, Fe2SiO4, 66.32%
18. (a)

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(PHYSICAL CHEMISTRY) SOLID STATE

= Cu

=O

= Ba

=Y

c
b
a

(b) density = 5.90 g cm–3

EXERCISE (JEE-MAIN)
1. (3) 2. (85) 3. (D) 4. (C) 5. (B) 6. (C) 7. (D)
8. (C) 9. (C) 10. (143) 11. (A) 12. (C) 13. (A) 14. (A)
15. (C) 16. (D) 17. (B) 18. (B) 19. (A) 20. (C) 21. (A)
22. (D) 23. (B) 24. (B) 25. (A) 26. (B) 27. (B) 28. (C)
29. (C) 30. (B) 31. (A) 32. (C) 33. (C) 34. (A) 35. (A)
36. (C) 37. (A) 38. (A) 39. (C) 40. (C) 41. (D) 42. (B)
43. (C) 44. (B)
EXERCISE (JEE-ADVANCED)
1. ABD 2. (B) 3. (B) 4. (A,C) 5. (3) 6. (2) 7. (BCD) 8. (A)
9. (A) 10. (B)

11. 8 ⎯⎯→

12. (7) 13. (D) 14. (BC)

Paragraph for Question No. 15 to 17
15. (B) 16. (A) 17. (D)
18. A → P, S ; B → P,Q ; C → Q ; D → Q,R

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(PHYSICAL CHEMISTRY) SOLID STATE
19. 216.5 pm 20. 117.1 pm 21. (B)
22. (i) = 5 kg m–3
(ii) There is huge difference in theoretically calculated density and observed density. It is only
possible if some foreign species occupies interstitial space i.e. substitution defect.
23. 18
24. (A)

fcc plan

25.
26. (D) 27. True 28. (A) 29. 1.259

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(PHYSICAL CHEMISTRY) SOLID STATE
SOLUTION
EXERXISE (O-I)
1. Covalent network solids are → [SiO2, Diamond, Si, AlN & SiC]
2. (C)
7. Factual
8. Factual
9. For triclinic system
abc &      = 90°,
Hence most unsymmetrical.
10. In match box
abc &  =  =  = 90°,
Hence orthorhombic geometry
11. For hexagonal crystal system
a=bc &  =  = 90° &  = 120°

3a
14. The distance between 2 nearest neighbor in B.C.C. is
2
3  5.2
i.e.
2
i.e. 4.5Å
15. In BCC

3 a = 4r

Fraction of edge occupied by atoms = 2r

a
𝟐𝒓 √𝟑
= 𝟒 =
𝒓 𝟐
√𝟑

16. For B.C.C.

3a 3  286
r= = i.e. r = 124 pm
4 4
20. Factual
22. The shortest distance between 1st & Vth layer of HCP arrangement is 2C
 
i.e. 2   2  4r 
 
 3 

2
i.e. 8 r
3

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(PHYSICAL CHEMISTRY) SOLID STATE
23. Volume of HCP unit CsCl = (Area of Base × height)

 
i.e.  6  3  a 2   2 2 a a
 
 4  3

6 3 2
i.e.  (2r)2 + 2  (2r) (As a = 2r)
4 3
3
= 24 2 r .

fcc,Fe  / 3 2
24. =
bcc,Fe 3 / 8
25. Volume occupied by atoms in an bcc unit cell is -
𝐌
𝟒 𝟑 𝟐×𝐍 √𝟑𝛑
𝐀
𝟐 × 𝛑𝐫 = [ ]×
𝟑 𝛒 𝟖

26. It is formed by 4 spheres the centres of which form a regular tetrahedron

27. For tetrahedral voids
r = 0.225 R
& for octahedral voids
r = 0.414 R
 Size of an octahedral void formed in a closed packed lattice is larger as compared to
tetrahedral void.
1
28. Number of atom X = 7
8
Number of atom y = 1
Formula of compound will be (X7 Y8)
29. For -----ABCABC----- closed packing sequence, it forms, it forms C.C.P / F.C.C.
Number of tetrahedral voids is twice the number of atoms in the unit cell.
Number of tetrahedral void = 2 × Z
Number of octahedral void = Z
30. Number of atom A = 6
2
Number of atom C =  6 i.e. 4
3
Formula of compounds is (A3C2)
31. For NaCl

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(PHYSICAL CHEMISTRY) SOLID STATE
𝟐(𝐫𝐍𝐚+ + 𝐫𝐂𝐥− ) = a
 2x + 2y = a
32. (
For F.C.C. of M+ X– 2 rM+ + rX− = 7.2 )
 2 × 1.6 + 2rx− = 7.2  rx − = 2Å

NA
33. 1 mole i.e. 58.5 g NaCl contains unit cells
4
 NA 
 1 gm cubic crystal of NaCl contains   unit cells
 58.5  4 
34. For compounds (XY) for which crystallizes in 8 : 8 lattice.

3
 rX+ + rY− a
2
 3 
 rX+   480 − 225 
 2 

 rX + = 190.68 pm

1
35. Number of Cs+ → 8 i.e 1
8
Number of Cl– → 1
36. Factual

 rZn+2 
37. For ZnS type structure  .402  it is a 4 : 4 coordination number compound.
 
 rS−2 
rA +
 = 0.225
rB−

22.5
 = 0.225
rB−

 rB− = 100 pm
38. For CaF2 → Coordination number of cation & Anion is 8 : 4
& For CsCl → coordination number of cation & Anion is 8 : 8
39. Schottky defect is shown by ionic substances in which the cation & Anion are of almost similar
sizes.
40. Schottky defect is basically a vacancy defect in ionic solids. In order to maintain electrical
neutrality, the number of missing cation & anions are equal.
41. Factual
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(PHYSICAL CHEMISTRY) SOLID STATE
1
42. ZnO ⎯⎯⎯
heating
→ Zn+2 + O2 + 2l−
2
So, strongly heated ZnO crystal can conduct electricity, this is due to movement of electrons in
the anion vacancies.
EXERXISE (S-I)
1. Molecular solid → P4O10, I2, P4

Ionic solid → (NH4)3PO4, LiBr

Metallic solid → Brass, Rb

Network/covalent solid → Graphite, Sic, Si
Amorphous solid → Plastic
2. There are 14 Bravais lattices possible in 3-D.
3.

Crystal system Features Unit cell found Examples

𝐚≠𝐛≠𝐜 Monolinic sulphur, 𝐏𝐛𝐜𝐫𝐨𝟒 ,

Monoclinic 𝜶 = 𝐲 = 𝟗𝟎∘ 𝐒, 𝐄𝐜 𝐍𝐚𝟐 𝐒𝐎𝟒 ⋅ 𝟏𝟎𝐇𝟐 𝐎,
𝜷 ≠ 𝟏𝟐𝟎∘ , ≠ 𝟗𝟎∘ , ≠ 𝟔𝟎∘ 𝐍𝐚𝟐 𝐁𝟒 𝐎𝟕 ⋅ 𝟏𝟎𝐇𝟐 𝐎

𝐚=𝐛≠𝐜
Graphite, 𝐙𝐧𝐨, 𝐜𝐝𝐬, 𝐌𝐠,
Hexagonal 𝜶 = 𝜷 = 𝟗𝟎∘ 𝐒
𝐏𝐛𝐈𝟐 , 𝐬𝐢𝐜
𝜸 = 𝟏𝟐𝟎∘

𝐚≠𝐛≠𝐜 𝐊 𝟐 𝐂𝐫𝟐 𝐎𝟕 , 𝐂𝐮𝐒𝐎𝟒 ⋅ 𝟓𝐇𝟐 𝐎,

Triclinic 𝐒
𝜶 ≠ 𝜷 ≠ 𝜸 ≠ 𝟗𝟎∘ 𝐇𝟑 𝐁𝐎𝟑 .

4.

Contributions of particles Contributions of particles

Total no. of
Ques. No. marked to theshaded marked to theshaded
Particles
region(a) region ( b)

𝟏 𝟏
(i) 1 (𝟒 × 𝟒 + 𝟏) i.e. 2
𝟒

𝟏 𝟏 𝟏 𝟏
(ii) (𝟐 × 𝟐 + 𝟒 × 𝟒) i.e. 2
𝟐 𝟒

𝟏 𝟏 𝟏 𝟏
(iii) (𝟔 × 𝟑 + 𝟐 × 𝟑) i.e. 2
𝟔 𝟐

𝟏 𝟏 𝟏
(iv) − (𝟔 × 𝟑) i.e. 𝟐
𝟔

𝟏 𝟏 𝟏 𝟏
(v) (𝟑 × 𝟐 + 𝟔 × 𝟐) i.e. 1
𝟑 𝟔

APNI KAKSHA 83
(PHYSICAL CHEMISTRY) SOLID STATE
3a
5. IN B.C.C, r=
4
also, edge length of unit cell = a
radius of atom = r
∴ Edge length not covered by atom = a – 2r

3a 2 − 3 
or a– = a 
2 2
2 − 3 
a 
∴ Percentage fraction not covered =  2 
100
a
i.e. 13.4 %
∴ Percentage fraction of Edge length covered is (100 – 13.4)
i.e. 86.6 %

6. Edge length (a) = 534 pm

a 534
(a) simple cubic lattice : a = 2r  r = r=
2 2
i.e. r = 267 pm

3a 3  534
(b) BCC lattice : r =  r=
4 4
i.e. r = 231.2 pm
a 534
(c) FCC lattice : r =  r=
2 2 2 2
i.e. r = 188.8 pm
7. Edge length (a) → 620 pm
a 620
(i) Nearest neighbour distance for F. C. C = =
2 2
i.e. 438.5 pm
a 620
(ii) For F. C. C, radius i.e. r = =
2 2 2 2
i.e. r = 219.2 pm

8. For F.C.C, a = 2 2 r

APNI KAKSHA 84
(PHYSICAL CHEMISTRY) SOLID STATE
 a  2 2r
(i) Distance between atoms 1 and 2 : =  = i. e. 2r
 2 2
2 2
Distance between atoms 2 & 3: a a
 2 + 2
   

a 2 2r
= = i.e. 2r
2 2

(2 2r )
2
Distance between 1 and 3: + (2r)2

= 12r 2

= 2 3r
(ii) Shape = square
Length of square = 2r.

9. For F.C.C a = 2 2 r
a = 2 2 × 142 Å
i.e. a = 2 2 × 1.42 × 10–8 cm.
Z M 4  56
density = =
a  NA ( )
3 3
2 2 1.42 10–8  6.022 1023

i.e. density = 5.74 g cm–3

Z M
10. (i) density =
a 3  NA

= 4 197
( 407 10 )  6.022 10
–10 3 23

density = 19.4 g cm–3

(ii) For F.C.C, a= 2 2r

a 407
r= =
2 2 2 2
i.e. r = 143.9 pm
11. 200 gm of this element contains 24×1023 atom.
 200 
 molar mass =  NA  g
 24 10 
23

Z M
Now, density =
a 3  NA

APNI KAKSHA 85
(PHYSICAL CHEMISTRY) SOLID STATE
= 4  200NA = density = 41.67 g cm–3
( 200 10 ) –10 3
 24 10 NA 23

4
12. For B.C.C, a = r & Z=2
3
For F.C.C, a = 2 2r & Z=4
3
 4r 
(density)  4  56    NA
 
3
= = = 1.09
(density) 
( 2  56
)
3
2 2 r  NA

4r
13. For B.C.C, a =
3
Z M
density =
a 3  NA
2  56
= 3
 4 124 10 –10

  6.022 10
23

 3 
= 7.92 g cm–3.

For F.C.C, a = 2 2 r

Z M 4  56
density = = = 8.625 g cm–3.
a  NA ( )
3 3
2 2 124 10 –10
 6.022 1023

𝐫𝐀+ 𝟖𝟖
14. = = 0·440
𝐫𝐁 − 𝟐𝟎𝟎

 r+ 
So, by radius ratio rule is lies in the range i.e.  0·444  −  0.732 
 r 
So, C. N. of A  is 6.

rMg+2 0.65
15. For MgS : = = 0.353
rs−2 1.84
So, by radius ratio rule, C. N = 4
rMg+2 0.65
for MgO : = = 0.464
rO−2 1.40
So, by radius ratio rule, C. N. = 6
rcs+ 1.69
for CsCl : = = 0.933
rcl− 1.81
So, by radius ratio rule, C. N. = 8
16. For F.C.C.
APNI KAKSHA 86
(PHYSICAL CHEMISTRY) SOLID STATE
Number of octahedral voids = 4
Number of tetrahedral voids = 8
2 2
Distance between 2 octahedral voids = a a
 2 + 2
   

 a 
i.e.  
 2
a a a
Distance between 2 tetrahedral voids = a – − =
4 4  2 
17. Number of oxide ions = 4
1 4
Number of A particles = 8 i.e.
6 3
1 4
Number of B particles = 4 i.e.
3 3
So formula is A 4 B4 O4 or ABO3
3 3

x+y+z=5
18. Number of atom A = 1
1
Number of atom B = 8 i.e. 1
8
Formula of compound is (AB)
19. Number of atom A = 4
1
Number of atom B = 8 i.e. 2
4
1
Number of atom C =  4 i.e. 2
2
So, formula of compound is (A2BC).
20. Number of O–2 = 4
Number of Zn+2 = 1
Number of Al+3 = 2
So, formula of spinel is (ZnAl2O4)

21. rk + = 132 pm

rf − = 135 pm
(i) Shortest K–F distance is (132 + 135)

APNI KAKSHA 87
(PHYSICAL CHEMISTRY) SOLID STATE
i.e. 267 pm
(ii) Edge length = 2 rk+ + rf − ( )
= 2 × 267
= 534 pm

(iii) Closest k–k distance = (267)2 + (267)2 = 368 pm

 a 3  NA
22. Z=
M
2.75 (654 10–10 )3  6.0231023
= =4
119
 Number of formula units of KBr present in single unit cell = 4
r− a
Also, r+ = =
2 3 2
a
i.e. r+ =
6
4   ( r+3 + r−3 )
4
Packing fraction = 3 100
a3

4  a   a  
3 3

4   +   
3   6   3  
= 100 = 70 %
a3
 percentage of void space in AB is 30 %
23. (i) (
Edge length i.e. a = 2 rPb+2 + rS−2 )
= 2 (297)
= 594 pm or 5.94 × 10–8 cm
(ii) Volume of unit cell= a3
= (5.94×10–8)3
= 2.096 × 10–22 cm3
a r 1
24. r+ + r– = , given + =
2 r− 2
r− a
 + r− =
2 2
3r− a a
 = r– =
2 2 3
APNI KAKSHA 88
(PHYSICAL CHEMISTRY) SOLID STATE
3a
25. Inter–ionic distance in CsCl is
2
3
=  400
2
= 346· 4 pm c

26. For CsCl : 3a = 2 ( rCs + rCl

+ − )
7 = 2 × 1.69 + 2rCl−

3.62
 rCl− =
2
i.e. rCl− = 1.81 Å

r+
27. By radius ratio rule = − = 0.732 for cubical void
r
rRb+
 = 0.732  rRb + = (0.732 × 2.17) = 1.59 Å
rI−

(r )
3
Now, Rb + + rI− = a
2
2  (1.59 + 2.17)
 a=  a = 4.34 Å
3
28. Fe0.93 O1.0
Consider 1 mole of oxide
mole of Fe = 0.93 & mole of O–2 = 1
Let mole of Fe+2 be x & mole of Fe+2 be (0.93 – x)
by charge balancing, 2x + 3 (0.93 – x) = 2 × 1 x = 0.79
mole of Fe+2 = 0.79
0.14
mole of Fe+3 = 0.14 % of Fe+3 = 100 = 15.05 %
0.93
29. Number of Se+2 ions present = number of cationic vacancies

10−3
Number of cation vacancies per mole of NaCl =  NA
100
i.e. 6.022 × 1018.
1
30. Cation vacancies as a percentage of Fe+2 initially present in sample is   x 100
8

APNI KAKSHA 89
(PHYSICAL CHEMISTRY) SOLID STATE
EXERCISE (O-II)
2. m-(1)
1 1 5
Number of atom A → 4 + 4 i.e.
8 2 2
1 5
Number of atom B → 10  i.e.
4 2
Formula of compounds is AB.
m-(2)

1 1  1 1 
In new arrangement, A particles =   8 +  6  −   4 +  2 
8 2  8 2 
5
i.e.
2
1   1  5
& B particle =  12 + 1 − 1 +  2  =
4   4  2
So, formula is (AB).
3. S–2 ions for F.C.C. lattice & Zn+2 ions occupy alternate tetrahedral voids.
4. For CaF2 Ca+2 occupy C.C.P & occupy all tetrahedral voids
Z M
Density =
a 3  NA
4  73
a3 =
6.022 1023  3.18
a = 546 pm
5. (A) For square close packing , coordination number is 4 is a true statement.
(B) For hexagonal closed packing, coordination number is 6 is a true statement.
(C) There is only one void per atom in square close packing but 2 in hexagonal close packing is
wrong statement.
(D) P.F. in Hexagonal close packing is 90.65 %
P.F. in square close packing is = 78.5 %
Hexagonal close packing is more Efficiently packed then square closed packing.
6. Factual
7. Number of tetrahedral voids = 2 × Z
Number of octahedral voids = Z
For F.C.C, body centre is occupied by octahedral void
Correct options are (A), (B) & (D).
APNI KAKSHA 90
(PHYSICAL CHEMISTRY) SOLID STATE
8. Factual
11. F.C.C octahedral voids are present at each edge centre & at the body centre
Each octahedral void is surrounded by 6 spheres & Each sphere is surrounded by
6 octahedral voids.
12. for Rock-Salt structure, coordination number of each cation & Anion is six.
13. Factual
14. Correct option are (A), (B), (C) and (D)
CsCl mainly shows Schottky defect due to comparable size of cation & Anion.
ZnS mainly shows frenkel defect due to variation in size of cation & Anion
For NaCl,
(i) Unit cell contains 4Na+ & 4Cl–
a a
(ii) One Na+ is surrounded by 6Cl– then 12 Na+ & then 8Cl– at a distance , & a respectively.
2 2
Comprehension: (Q. 15 & 16)
3
 4 17.32 
15. Volume occupied by O2 =    0.32 = 20.5 litres
 3 
Using, PV = nRT
P.V 5  20.5
n O2 = = =2
RT 0.08  640
number of oxygen molecules present in unit cell = 2 × NA = 2 × 6 × 1023 = 12× 1023
Correct option is (B)

16. Total density = 2  (64 + 64) = 6.6 × 10–27.

3
 4 17.22 
  6 10
23

 3 

 6.6 − 3.3 
% increase in density =   100 = 50 %
 6.6 
Correct option is (D).
Comprehension: (Q. 17 to 19)
Calcium crystallizes in a cubic unit cell with density 3.2 g/cc. Edge-length of the unit cell is 437
pm
Z M
17. d=
a 3  NA

3.2  (437 10–10 )3  6.022 1023

Z= Z=4
40

APNI KAKSHA 91
(PHYSICAL CHEMISTRY) SOLID STATE
F.C.C.
Correct option is (C)
𝐚 𝟒𝟑𝟕
18. Nearest neighbour distance = = = 𝟑𝟎𝟗 𝐏𝐦
√𝟐 √𝟐

Correct option is (B)

𝒂
19. Nearest neighbours are at a distance and the number is 12
√𝟐

Correct option is (D).

20. Density of molten metal is 3 g cm–3.

3 (437 10–10 )3  6.022 1023

Z=
40
Z = 3.76
Now, If Z = 4 the % occupancy 74%
74
For Z = 3.76 the % occupancy =  3.76 = 69 %
4
% Empty space = 31%
Comprehension: (Q. 21 & 22)
21. This is due to metal Excess defect
 Correct option is (C)
22. This is impurity defect  Correct option is (A)
MATCH THE COLUMN
For tetragonal&Hexagonal
23. (A)
(P) are twocrystalsystems
(Q) a = b  c
For cubic&R hom bohedral
(B)
(P) are twocrystalsystems
(S) a = b = c
For monoclinic&Triclinic
(C)
(P) are twocrystalsystems
(R) a  b  c

For cubic&Hexagonal
(D)
(P)are twocrystalsystems
24. (A) Rock salt structure :
(R) Coordination number of cation & anion are 6. i.e. same
a
(S) Distance between 2 nearest anion is
2

APNI KAKSHA 92
(PHYSICAL CHEMISTRY) SOLID STATE
(B) Zinc blend structure :
(P) Coordination number of cation is 4.

3a
(Q) = r+ + r–
4
(R) Coordination number of cation & anion are smae
a
(S) Distance between two nearest anion is
2
(C) Fluorite structure

3a
(Q) = r+ + r–
4

MATCHING LIST TYPE

25. Correct option is (A)
26. Correct option is (B)

EXERCISE (S-II)
1. a = 2 × (diameter of ball)
→ Number of spherical balls of radii 2 cm that can be placed completely inside a cubical box
of edge = 8 cm is 8.
2. Ans. = 3.5g/cm3
Z M (4  2) 12
Density = = = 3.5 g/cm3
a  NA
3
6.022 1023  (3.569 10–8 )3
1
3. Z= 8 + 2 z = 3
8
Z M  a 3  NA
density i.e. r= M=
a 3  NA z
7.2  24 10–24  6.022 1023
→ M= → M = 34.56 gm
3
As, 34.56 gm of element contains 6×1023 atoms
→ 200 gm of an element contains
i.e. 3.48 × 1024 atoms
4. Number of O–2 = 4
Number of Ti+n = 2

APNI KAKSHA 93
(PHYSICAL CHEMISTRY) SOLID STATE
→ By charge balancing, 2 × n = 8
n=4
 Ti should be present in +4 0.S & the compound should be (TiO2)
48
Also, % be mass of Ti = 100 i.e. = 60%
80
r+
5. = 0.414
r−
 r+ = 0.414 × 250
r+ = 103.5 pm
Cation C+, having a radius 180 pm cannot be slipped into the tetrahedral site of the crystal of A +
B–, without disturbing the crystal.
4 4
1 r+3 + 1 r−3
6. P.F. = 3 3 3 3
8(r+ + r− )3

4 4
1 r+3 + 1 r−3
3 3 3 3
8(r+ + r− )3

4
 (r+ + r− )3
= 3  3 3 = 0.7285
8(r+ + r− )3

a
7. X ⎯→
2
a
y ⎯→
2
y 2 a 2 2
= =2
X 2 a
8. Perimeter of plane is = (2c + 8R)

2
=2× × 4R + 8R
3
= 6.53 R + 8R
= 14.53 R

2
9. × 2r = 10 43
3
r = 5 pm.

APNI KAKSHA 94
(PHYSICAL CHEMISTRY) SOLID STATE
Radius of largest sphere which can be fitted in the void = 5 × 0.414 = 2.07 pm
 1 1 4 3
12  6 + 2  2   3 r
10. Packing fraction =   = 0.605
3
6   (2r)2  2r
4
1
11. (a) Number of Mn+3 ion = 8 i.e. 1
8
1
Number of F ion = 12  i.e. 3
4
Empirical formula of compounds is MnF3.
 1 3 8 
(b) Coordination number = 6  
 4 
(c) ( )
Edge length (a) = 2 rMn+3 + rF− = 2 (0.65 + 1.36) i.e. 4.02 Å

3a
12. (a) Distance between nearest neighbor =
2
3  5.2
i.e. = 4.5 Å
2
(b) Distance between next nearest neighbor = a i.e. 5.2 Å
(c) Nearest neighbor for K atom = 8
(d) Next nearest neighbour for K atom = 6

 a 3  NA 5.561 (555 10–10 )3  6.0231023

13. For AgCl, z= = = 3.9902
M 143.5
Percentage of sites that are unoccupied is
𝟏𝟎𝟎
= (𝟏𝟎𝟎 − × 𝟑. 𝟗𝟗𝟎𝟐) = 0.24 i.e. 0.24%
𝟒

rNa+ rNa+ rK+

14. (a) = 0.5 & = NaCl & KCl has octahedral structure. = 0.714
rCl− rK− rCl−

In octahedral Edge length = rcation + ranion. Let a = Edge length of KCl octahedron

a = rK+ + rCl− & b = Edge length of NaCl octahedron

b = rNa + + rCl−

rNa + + rCl−
Now, = 1.5 .....(1)
rCl−

rK+ + rCl−
& = 1.714 .....(2)
rCl−

APNI KAKSHA 95
(PHYSICAL CHEMISTRY) SOLID STATE
a 1.714
=
b 1.5
a
i.e. = 1.143.
b
dNaCl  M   a3   58.5 
(b) =  3    =   (1.143)3 = 1.172
dKCl  a NaCl  M KCl  74.5 
r+
15. Let = 0.732
r−

 r +  3 
4 4  3  −  + 2
4  r+3 + 8  r+3  r  
P.F = 3 3  3 3 = = 62.6 %
64(r+ + r− )
3
 r+ 
3

4  − + 1
r 
Void space in favorite structure per unit cell = 0.374
Z M
16. d=
a 3  NA
Z 18
0.92 = Z=4
 3 
6  (4.53)  7.4110   6.022 10
2 –24 23

 4 
1 Si
17. Formula of forsterite = Mg  8 1  4 O4 i.e. Mg2SiO4
4 4
m1 m2 mT
As, + =
d1 d2 d
x 100 − x 100
+ = x = 66.3 %
4.34 3.21 3.88
% of fayalite in an olivine is 66.3%

APNI KAKSHA 96
(PHYSICAL CHEMISTRY) SOLID STATE
EXERCISE (JEE-MAIN)

 1
1. A → 4 –  2  = 3
 2
1
B → 12 × +1×1=4
4
So, Compound is A3B4
The value of x is 3.
2. In Fe0.93O for every 93 Fe ions 14 are Fe+3 and (93– 14) = 79 are Fe+2 ions
79
F+2 = 100 = 84.9%
93
 nearest integer = 85%
6. Theory based.
Z M
9. Density =
NA  a 3
2 M
6.17 =
6 10  (300 10–10 )3
23

M = 50
 Number of molecules in 200 gm. = 200  NA = 4 NA
50
Z M
10.  Density =
NA  a 3
Z  2.7 10–2
2.7 × 103 =
6.02 1023  (405 10–12 )3
Z=4
 Structure is FCC.
So, a = 2 2R
405 10–12
R= m
2 2
= 143 × 10–12 m
a
11. min distance between two octahedral voids in fcc =
2
(Distance between edge centre and body centre)
12. The radius of largest sphere which fits properly at the centre of edge of a body centred
a – 2r
cubic unit cell =
2
2 3a
a–
= 4
2
APNI KAKSHA 97
(PHYSICAL CHEMISTRY) SOLID STATE
= 0.067 a
13. Length of body diagonal = 3a
= 2rA + 2rB
= 2rA + 4rA [rB = 2rA]

= 6rA

 a = 2 3rA
4 3 4
Volume of Particle 3 rA + 3 (2rA )
3

P·F = =
Volume of unit cell a3
4
(9rA3 )
= 3
(2 3 rA )3
= 906 i.e. 90%
14.  B forms CCP structure So its effective number in a unit cell = 4
 A occupies half of the octahedral holes
So, it effective number in a unit cell = 2
 Oxygen atoms occupy all the tetrahedral holes
So, its effective number in a unit cell = 8
 Simplest ratio of A, B and oxygen atom = 1 : 2 : 4
15. Let AE be the Edge length = a.
BD be the nearest distance b/w 2 tetrahedral voids.
3a 3a A a E
AC = & CD =
2 4 B D
 by properties of triangle,
C
AE BD
=
AC BC
a  2 BD  4 F G

3a = 3a
a
 BD =
2
16. In Frenkel defect, smaller ion displaces from its actual lattice site into the interstitial sites.
a
18. The closest approach between 2 atoms in metallic crystal in F.C.C. structure is
2
19. CrO2 is magnetic & ferromagnetic both

3a 3  4.29
20. For B.C.C. r=  r=
4 4
APNI KAKSHA 98
(PHYSICAL CHEMISTRY) SOLID STATE
i.e. r = 1.86 Å

3
21. For CsCl rcs+ + rcl− = a
2
1
22. Number of atom A = 8 i.e. 1
8
1
Number of atom B = 5
2
 Formula compounds is (AB5/2) i.e. A2B5
23. The appearance of colour in solid–alkali metal halide is generally due to F–centers.
24. For monoclinic unit cell :
abc &  =  = 90°  
25. The total number of octahedral void per atom present in cubic close packed structure is 1.
26. M0.98O1
Consider 1 role of oxide
mole of M = 0.98, mole of 0–2 = 1
Let moles of M+3 = x
& moles of M+2 = (0.98 – x)
 By charge bereaving (0.98 – x) 2+ 3x – 2 = 0.
0.04
 x = 0.04  % of M+3 = 100 i.e. 4.08 %
0.98
27. For F.C.C
a= 2 2r  a = 2 2 × 0.14
i.e. a = 0.4 mm
28. The only incorrect statement is (3) i.e.. void space in hcp mode of packing is 32%
1 3
29. Number of atom A = 6 i.e.
8 4
1
Number of atom B = 6 i.e. 3  Formula of compound is AB4
2
30. For F.C.C.
a 361
r= = i.e. r = 128 pm
2 2 2 2
31. For B.C.C.

APNI KAKSHA 99
(PHYSICAL CHEMISTRY) SOLID STATE
3a 3  351
r= = i.e. r = 152 pm
4 4
32. The only incorrect statement is (3) i.e. electrical conductivity of semiconductors & metals
increases with Increases in temperature.
33. For B.C.C

3a
The distance of Nearest Approach between atom is equal to
2
3a
= 1.73
2
a = 2Å or 200 pm
34. For NH4Cl in B.C.C lattice:

3a
(rNH4 + )
+ rCl− =
2
3  390
 rNH + + 180 =
4
2
3  390
 rNH + = – 180
4
2
 rNH + = 158 pm
4

rCa+2 94
35. For Cao : = = 0.643
rO−2 146
 By radius radio rule it should be octahedral.
36. For C.C.P.
% Of free space = 26 %
For B.C.C.
% Of free space = 32 %
a
37. (r+ + r–) =
2
508
110 + r– =
2
508
 r– = – 110
2
 r– = 144 pm

APNI KAKSHA 100

(PHYSICAL CHEMISTRY) SOLID STATE
2
38. Number of Atom X = 8
3
Number of Atom Y = 4
X16
 Formula of compound is Y4 or X4 Y3
3
4
39. Total volume of atoms present in a face. centred unit cell of metal is 4  r3
3
16 3
i.e. r
3
40. Lattice energy of an ionic compounds depends on → (3)
i.e. charge on the ion & size of the ion.
1
41. Number of Atom A = 4 i.e. 1
8
1
Number of Atom B = 6 i.e. 3
2
Formula of compound is AB3
42. Schottky defect

6.022 1023
43. 58.5 gm of Nacl contains unit cells
4
6.022 1023 1
 1 gm of Nacl should contain i.e. 2.57 × 1021 unit cells
58.5 4
44. 2,4

APNI KAKSHA 101

(PHYSICAL CHEMISTRY) SOLID STATE
EXERCISE (JEE-ADVANCED)
1.

Element 𝐗 𝐘 𝐙

Packing 𝐅𝐂𝐂 𝐁𝐂𝐂 Primitive

Edge 𝐋𝐱 𝐋𝐲 𝐋𝐳

𝟒
Relation between edge length and radius 𝐋𝐱 = 𝟐√𝟐𝐫𝐱 𝐋𝐲 = 𝐫𝐲 𝐋𝐳 = 𝟐𝐫𝐳
√𝟑

𝝅 √𝟑𝝅 𝝅
Packing fraction
𝟑√𝟐 𝟖 𝟔

𝟖 √𝟑 √𝟑 𝟖
Now, 𝐫𝐲 = 𝐫 &𝐫𝐳 =𝐫 = 𝟐 × 𝐫𝐱 ⇒ 𝐫𝐳 = 𝟒𝐫𝐱
√𝟑 𝐱 𝟐 𝐲 √𝟑
𝟒 𝟖
So, 𝑳𝒙 = 𝟐√𝟐𝒓𝒙 , 𝑳𝒚 = × 𝒓𝒙 , 𝑳𝒛 = 𝟖𝒓𝒙
√𝟑 √𝟑

𝟑𝟐
𝑳𝒙 = 𝟐√𝟐𝒓𝒙 , 𝑳𝒚 = 𝒓 , 𝑳 = 𝟖𝒓𝒙
𝟑 𝒙 𝒛

So 𝐋𝐲 > 𝐋𝐳 > 𝐋𝐱
𝟒𝑴𝒙 𝟐×𝑴𝒚
Density 𝑳𝟑𝒙
, 𝑳𝟑
𝒚
𝟑𝐌 𝐲
Now, 𝟑𝐌𝐱 = 𝟐 or 𝐌𝐱 × 𝟐 = 𝐌𝐲
𝟑𝟐 𝟑
𝐝𝐞𝐧𝐬𝐢𝐭𝐲 (𝒙) 𝟒𝑴𝒙 𝑳𝟑𝒚 𝟒𝑴𝒙 ( )
= × = × 𝟑
𝐝𝐞𝐧𝐬𝐢𝐭𝐲 (𝒚) 𝟐𝑴𝒚 𝑳𝟑𝒙 𝟒𝑴𝒙 (𝟐√𝟐)𝟑

2. No. of atoms per unit cell :

𝟏 𝟏
𝒁 = 𝟖 [corner] + 𝟔 [Face] + 𝟒 [Alternate TV]
𝟖 𝟐

𝒁 =𝟏+𝟑+𝟒

𝒁=𝟖

It is diamond like structure in which

√𝟑𝒂
𝟐𝒓 =
𝟒
𝟖𝒓
⇒𝒂=( )
√𝟑

APNI KAKSHA 102

(PHYSICAL CHEMISTRY) SOLID STATE
Packing efficiency = (𝒁 × Volume of single lattice point × 𝟏𝟎𝟎)/ volume of the unit cell
𝟒
𝟖× 𝝅𝒓𝟑
Packing efficiency = 𝟑
𝟖𝒓 𝟑
× 𝟏𝟎𝟎 = 𝟑𝟓% (roughly)
[ ]
√𝟑

4 4
1 r−3 + 3  r+3
3. Packing fraction (P.E.) = 3 3
a3
r+
= 0.414 (Square planar void), a = 2r_
r–
We get,
4 3
(r– + 3r+3 )
P.F. = 3
8r–3

 
=  (1 + 3(0.414)3 ) = 0.63
6 
4. The given compound has CsCl type structure in which anion x form simple cubic unit cell and M+
cation is present in cubic void.

a 3
rM+ + rX− =
2
rM+ + rX− 3
= = 0.866
a 2
Coordination no. of M+ = 8
Coordination no. of X– = 8
rM+
And 0.732  1  Correct Ans. (A), (C)
rX–

5. 𝐗 − are present in Octahedral void

𝐌+ are present in FCC lattice point
Number of cations and anions left after each sequence are
𝑴+ 𝑿−
(i) 𝟒 𝟒−𝟑 = 𝟏
𝟏 𝟏
(ii) 𝟒 − 𝟔 × 𝟐 𝟏+𝟔×𝟐

(iii) 𝟏 − 𝟏 𝟑+𝟏=𝟒
(iv) 𝟎 + 𝟏 𝟒−𝟏=𝟑
So, total number of 𝑿− in a unit cell = 𝟑
total number of 𝐌 + in a unit cell = 𝟏

APNI KAKSHA 103

(PHYSICAL CHEMISTRY) SOLID STATE
anion 𝟑
Hence =𝟏=𝟑
cation

zm
6. For F.C.C : Density (r) =
a 3  NA

 a 3  NA 8  (4 10−8 )3  NA
m= = = 128 × 10–24 NA
z 4

 NA = 256 –24
256 NA
Number of Atoms = = 2×1024 N=2
m 128 10 NA
7. (a) Nearest neighbor in the top most layer of CCP structure is 9 thus incorrect.
4
4  r3
(b) Packing efficiency is 74% thus correct. % of packing efficiency = 3 100
a3
4
4  r3
= 3 100 i.e. 74 %
(2 2 r)3
(c) Number of tetrahedral void per atom = 2
Number of octahedral void per atom = 1
this correct
(d) In DABC A
r
AC2 = AB2 + BC2 r
 (4r)2 = a2 + a2 a r
r
 4r = 2 a B C
a
a= 2 2r
8. In CCP, O–2 ions are 4
Hence total negative charge = – 8
Let number of Al+3 ions be x
& number of Mg+2 ion be y
 Total position charge = 3x + 2y
 3x + 2y = 8
This relation is satisfied only by x = 2 & y = 1
Hence number of Al+3 = 2
& number of Mg+2 = 1
2 1
 m i.e. fraction of octahedral holes occupied by Al+3 ions = i.e.
4 2

APNI KAKSHA 104

(PHYSICAL CHEMISTRY) SOLID STATE
1
and n i.e. fraction of tetrahedral holes occupied by Mg+2 ions =
8
9. The given arrangement is octahedral void arrangement.
rA +
³ 0.414  rA + ³ 0.414 × 250
rX −

i.e. rA + ³ 103.5 pm

rA +
< 0.732  rA + < 183 pm.
rX −

So, the radius of A+ is 104 pm.

1
10. No. of M atoms =  4 +1 = 2
4
1 1
Number of X atoms =  6 + 8 = 3 + 1 = 4
2 8
So, empirical formula of compound is (MX2).
11. Fig → copy from solution given of back.
Explanation : The truncated octahedron is the 14-faced Archimedean solid with 14 total faces :
6 square & 8 regular hexagons.
The truncated octahedron is formed by removing the six right square pyramids one from each
point of regular octahedron.
Truncated octahedron unfolded in two dimensions.

12. Ag crystallises in FCC unit cell with 4 atoms per unit cell.

𝟒 × 𝟏𝟎𝟖
𝝆=
𝟔. 𝟎𝟐𝟑 × 𝟏𝟎𝟐𝟑 × 𝐚𝟑

= 𝟏𝟎. 𝟓 𝐠 𝐜𝐦−𝟑

⇒ 𝐚𝟑 ( Volume of unit cell)

= 𝟔. 𝟖𝟑 × 𝟏𝟎−𝟐𝟑 𝐜𝐦𝟑

⇒ 𝐚 = 𝟒 × 𝟏𝟎−𝟖 𝐜𝐦

= 𝟒 × 𝟏𝟎−𝟏𝟎 𝐦
⇒ Surface area of unit cell

= 𝐚𝟐 = 𝟏. 𝟔 × 𝟏𝟎−𝟏𝟗 𝐦𝟐

APNI KAKSHA 105

(PHYSICAL CHEMISTRY) SOLID STATE
⇒ Number of unit cells on 𝟏𝟎−𝟏𝟐 𝐦𝟐 surface

𝟏𝟎−𝟏𝟐
= = 𝟔. 𝟐𝟓 × 𝟏𝟎𝟔
𝟏. 𝟔 × 𝟏𝟎−𝟏𝟗

∵ There are two atoms (effectively) on one face of unit cell

Number of atoms on 𝟏𝟎−𝟏𝟐 𝐦𝟐 surface = 𝟐𝐱 number of unit cell = 𝟏. 𝟐𝟓 × 𝟏𝟎𝟕 .

⇒𝒙=𝟕
13. 4R = L 2
So, L= 2 2 R

( )
2
 Area of square unit cell = 2 2 R = 8R2

R R
R 4R=
R So, L=
R r

 R 2 
Area of atoms present in 1 unit cell = R 2 + 4·  = 2R
2
 4 

2R 2
 Packing efficiency = 100 = 78.54 %
8R 2
14. Frenkel defect is a dislocation defect Trapping of an electron in the lattice leads to the
formation of F-centres
Paragraph for Question No. 15 to 17
 1  1
15. Total number of atoms in 1 unit cell = 12   + 3 +  2   = 6
 6  2
2
16. C=  4r
3
3
Area of Base = 6  (2r)2
4
   
 volume of Hexagon = Area of base × height =  6 3  4r 2    2  4r  = 24 2 r
3
   
 4   3 

APNI KAKSHA 106

(PHYSICAL CHEMISTRY) SOLID STATE
4
6  r3
Volumeof atomin1unit cell 3 100 = 74%
17. Packing fraction = 100 =
Volumeof 1unit cell 24 2r3
 Empty space = 26%
18. (A) simple cubic & FCC
Have the cell parameters a = b = c & a = b = g = (p) & are 2 crystal systems (Q)
(C) Cubic & Tetragonal are 2 crystal system. (Q)
(D) Hexagonal & Monoclinic are 2 crystal system (Q) have 2 crystallographic angles of 90° (R).
Z M
19. r=
a 3  NA

 a 3  NA 2  (5 10–8 )3  6 1023
Z= = =2
M 75
So, it is a B.C.C. unit cell

3a 3 5
R= =  R = 216.5 pm
4 4
20. In a cubic crystal system, there are 2 types of void known as octahedral & Tetrahedral voids.
It r1 is the radius of void & r2 is the radius of atom creating these voids, then
 r1 
  = 0.414
 2 octahedral
r

 r1 
  = 0.225
 r2 tetrahedral
The above radius ratio values indicate that octahedral void has larger radius, have for maximum
diameter of atom to be present in interstitial space
r1 = 0.414r2

Also in F.C.C., 4r2 = 2a

2  0.414  a 0.414  400
 Diameter required (2r1) = 2 × 0.414 r2 = =
2 2 2
i.e. 117.1 pm
21. In C.C.P, number of tetrahedral voids = 2 × number of atoms.
As there are 4S–2 ions at lattice points & they need 4 zn+2, which are adjusted in alternate
tetrahedral voids.
22. (i) 5 kg m–3
(ii) There is a huge difference density & observed density. It is only possible if some foreign
species occupy interstitial space i.e. substitution defect.
APNI KAKSHA 107
(PHYSICAL CHEMISTRY) SOLID STATE
(i) In Rock salt like crystal AB, there are 4 AB units per unit cell
Z M 4  6.023y
 density = =
a  NA 8y 10–27  6.0231023
3

1 1
= 5 × 03 g/m3 [ a = 2y 3
nm or 2y 3 10–9 m ]
or 5kg/m3
23. To have maximum number of spheres, the packing must be hcp.
Maximum number of spheres = 25.

Area of figure = 2 × Area of equilateral triangle of side = 40 mm or 4 cm.

3 2 25
= 2 (4) = 13.856 = 1.804 marbles/cm2
4 13.856
1
24. Number of atom of A per unit cell = 8 i.e. 1
8
1
Number of atoms of B per unit cell = 6 i.e. 3
2
 formula is AB3

25.

1 1
26. Number of atoms A per unit cell =   8 + 4   = 3
8 2
 1 
Number of atom B per unit cell = 4· 12  +1  Formula is (A3B4)
 4 
27. Factual
28. 3 - consecutive layers of atom in hcp are there.

APNI KAKSHA 108

(PHYSICAL CHEMISTRY) SOLID STATE
Atom X is in correct of 12 like atoms, 6 from layer B and 3 from to and bottom layer A each.
 C.N. = (6 + 3 + 3) i.e 12
Z
29. Density 
a3
d.F.C.C 4 (3)3
=  = 1.259
dB.C.C (3.5)3 2

APNI KAKSHA 109