Chemistry Class 12 NCERT SOLUTION WITH Important Formula Ch 1' The Solid State '

The Solid State

Chapter–1 


NCERT Textbook Questions





NCERT Intext Questions

Q. 1. Why are solids rigid?

Ans. In solids, the constituent particles (atoms or molecules or ions) are not free to move but can only oscillate

about their mean positions due to strong interatomic or intermolecular or interionic forces. This imparts

rigidity.

Q. 2. Why do solids have a definite volume?

Ans. The constituent particles in solids are bound to their mean positions by strong forces of attraction. The

interparticle distances remain unchanged at a given temperature and thus solids have a definite volume.

Q. 3. Classify the following as amorphous or crystalline solids:

Polyurethane, naphthalene, benzoic acid, teflon, potassium nitrate, cellophane, polyvinyl chloride,

fibre glass, copper.

Ans. Amorphous solids: Polyurethane, teflon, cellophane, polyvinyl chloride and fibre glass.

Crystalline solids: Naphthalene, benzoic acid, potassium nitrate and copper.

Q. 4. Why is glass considered a super cooled liquid?

Ans. Glass is an amorphous solid. Like liquids, it has a tendency to flow, though very slowly. This is evident

from the fact that the glass panes in the windows of old buildings are invariably found to be slightly thicker

at the bottom than at the top. This is because the glass flows down very slowly and makes the bottom

portion slightly thicker.


Q. 5. Refractive index of a solid is observed to have the same value along all directions. Comment on the nature of this solid. Would it show cleavage property?

Ans. Since the solid has the same value of refractive index along all directions, it is isotropic and hence,

amorphous. Being an amorphous solid, it would not show a clean cleavage when cut with a knife. Instead,

it would break into pieces with irregular surfaces.

Q. 6. Classify the following solids in different categories based on the nature of intermolecular forces operating in them:

Potassium sulphate, tin, benzene, urea, ammonia, water, zinc sulphide, graphite, rubidium, argon,

silicon carbide.

Ans. Ionic solids: Potassium sulphate, zinc sulphide.

Covalent solids: Graphite, silicon carbide.

Molecular solids: Benzene, urea, ammonia, water, argon.

Metallic solids: Rubidium, tin.

Q. 7. Solid A is a very hard electrical insulator in solid as well as in molten state and melts at extremely high temperature. What type of solid is it?

Ans. Covalent.

Q. 8. Ionic solids conduct electricity in molten state but not in solid state. Explain.

Ans. In the molten state, ionic solids ionise to give free ions and hence can conduct electricity. However, in the

solid state, since the ions are not free to move about but remain held together by strong electrostatic forces

of attraction, they behave as insulators.

Q. 9. What type of solids are electrical conductors, malleable and ductile?

Ans. Metallic solids.

Q. 10. Give the significance of a ‘lattice point’.

Ans. Each lattice point represents one constituent particle of the solid. This constituent particle may be an atom,

an ion, or a molecule.

Q. 11. Name the parameters that characterise a unit cell.

Ans. A unit cell is characterised by

(i) its dimensions along the three edges, a, b and c.

(ii) angles between the edges, which are a (between b and c), b (between a and c) and g (between a and b).

Thus, a unit cell is characterised by six parameters, a, b, c, a, b and g.

Q. 12. Distinguish between

(i) Hexagonal and monoclinic unit cells (ii) Face-centred and end-centred unit cells

Ans. (i) Hexagonal and monoclinic unit cells


(ii) Face-centred and end-centred unit cells

Q. 13. Explain how much portion of an atom is located at (i) corner and (ii) body-centre of a cubic unit cell is part of its neighbouring unit cell.

Ans. (i) A point lying at the corner of a unit cell is shared equally by eight unit cells and therefore, only 1/8 of each such point belongs to the given unit cell.

(ii) A body-centred point belongs entirely to one unit cell since it is not shared by any other unit cell.

Q. 14. What is the two dimensional coordination number of a molecule in square close packed layer?                                               [CBSE (F) 2013]

Ans.  4

Q. 15. A compound forms hexagonal close-packed structure. What is the total number of voids in 0.5 mol of it? How many of these are tetrahedral voids?

Ans. No. of atoms in the 0.5 mol close-packed structure = 0.5 × 6.022 × 1023 = 3.011 × 1023

No. of octahedral voids = 1 × No. of atoms in the close-packed structure = 3.011 × 1023

No. of tetrahedral voids = 2 × No. of atoms in the close-packed structure = 2 × 3.011 × 1023

= 6.022 × 1023

Total number of voids = 3.011 × 1023 + 6.022 × 1023 = 9.033 × 1023

Q. 16. A compound is formed by two elements, M and N. The element N forms ccp and atoms of M occupy 1/3rd of tetrahedral voids. What is the formula of the compound?

Ans. Suppose atoms of element N present in ccp = x

\ Number of tetrahedral voids = 2x

Since

1/3rd of the tetrahedral voids are occupied by atoms of element M,

number of atoms of element, M × x

x

3

1

2

3

2

` M = =

Ratio of M : N : :

x

x

3

2

= = 2 3

Hence, the formula of the compound = M2N3.

Q. 17. Which of the following lattices has the highest packing efficiency?

(i) simple cubic

(ii) body-centred cubic

(iii) hexagonal close-packed lattice.

Ans. Hexagonal close-packed lattice has the highest packing efficiency (74%).

Q. 18. An element with molar mass 2.7 × 10–2 kg mol–1 forms a cubic unit cell with edge length 405 pm. If its density is 2.7 × 103 kg m–3, what is the nature of the cubic unit cell?

Ans. Density, d = a N

z M

A

3 #

#

or z = M

d a NA

# 3 #

...(i)

Here, M = 2.7 × 10–2 kg mol–1

a = 405 pm = 405 × 10–12 m = 4.05 × 10–10 m

d = 2.7 × 103 kg m–3

NA = 6.022 × 1023 mol–1

Substituting these values in expression (i), we get

z =

.

( . ) (. )( . )

kg mol

kgm m mol

2 7 10

2 7 10 4 05 10 6022 10

–2 1

3 3 10 3 23 1

– – –

#

# # #

= 4

As there are 4 atoms of the element present per unit cell. Hence, the cubic unit cell must be face-centred.

Q. 19. What type of defect can arise when a solid is heated? Which physical property is affected by it and in

what way?

Ans. On heating a solid, vacancy defect is produced in the crystal. This is because on heating, some lattice sites

become vacant. As a result of this defect, the density of the substance decreases because some atoms or ions

leave the crystal completely.

Q. 20. What type of stoichiometric defect is shown by: (i) ZnS (ii) AgBr?

Ans. (i) ZnS shows Frenkel defect because its ions have a large difference in size.

(ii) AgBr shows both Frenkel and Schottky defects.

Q. 21. Explain how vacancies are introduced in an ionic solid when a cation of higher valence is added as an impurity in it.

Ans. When a cation of higher valence is added as an impurity in an ionic solid, some of the sites of the original cations are occupied by the cations of higher valency. Each cation of higher valency replaces two or more original cations and occupies the site of one original cation and the other site(s) remains vacant.



Q. 22. Ionic solids, which have anionic vacancies due to metal excess defect, develop colour. Explain with the help of a suitable example.

Ans. In ionic solids with anionic vacancies due to metal excess defect, when the metal atoms deposit on the surface, they diffuse into the crystal and after ionisation, the metal ion occupies cationic vacancy while electron occupies anionic vacancy. Such anionic sites occupied by an electron are known as F-centres.

These electrons get excited to higher energy levels by adsorption of suitable wavelengths from the visible white light and therefore appear coloured. When Na vapours are passed over NaCl crystals such defect is created and the crystals become yellow due to excess Na+ and presence of F-centres.

Q. 23. A group 14 element is to be converted into n-type semiconductor by doping it with a suitable impurity. To which group should this impurity belong?

Ans. n-type semiconductor means conduction due to presence of excess of electrons. Therefore, to convert group 14 element into n-type semiconductor, it should be doped with group 15 element e.g., As.

Q. 24. What type of substances would make better permanent magnets, ferromagnetic or ferrimagnetic? Justify your answer.

Ans. Ferromagnetic substances make better permanent magnets. This is because the metal ions of a ferromagnetic substance are grouped into small regions called ‘domains’. Each domain acts as a tiny magnet. These domains are randomly oriented. When a ferromagnetic substance is placed in a magnetic field, all the domains get oriented in the direction of the magnetic field and a strong magnetic field is produced. Such order of domains persists even when the external magnetic field is removed. Hence, the ferromagnetic substance becomes a permanent magnet. On the other hand, the net or resultant magnetic moment of ferrimagnetic substances is small.


NCERT Textbook Exercises

Q. 1. Define the term ‘amorphous’. Give a few examples of amorphous solids.

Ans. An amorphous solid consists of particles of irregular shape. The arrangement of constituent particles in such a solid has only short range order. In such an arrangement, a regular and periodically repeating pattern is observed over short distances only. Examples: Glass, rubber and plastics.

Q. 2. What makes a glass different from a solid such as quartz? Under what conditions could quartz be converted into glass?

Ans. Glass is an amorphous solid in which the constituent particles (SiO4 tetrahedra) have only a short range order and there is no long range order. In quartz, the constituent particles (SiO4 tetrahedra) have both short range as well as long range orders. On melting quartz and then cooling it rapidly, it is converted into glass.

Q. 3. Classify each of the following solids as ionic, metallic, molecular, network (covalent) or amorphous.

(i) Tetra phosphorus decoxide (P4O10) (ii) Ammonium phosphate (NH4)3PO4

(iii) SiC (iv) I2

(v) P4 (vi) Plastic

(vii) Graphite (viii) Brass

(ix) Rb (x) LiBr

(xi) Si

Ans. Ionic: (NH4)3PO4 and LiBr; Metallic: Brass, Rb; Molecular: P4O10, I2, P4;

Network (covalent): Graphite, SiC, Si; Amorphous: Plastic.

Q. 4. (i) What is meant by the term ‘coordination number’?

(ii) What is the coordination number of atoms:  (a) in a cubic close packed structure? (b) in a body-centred cubic structure?

Ans. (i) Coordination number is defined as the number of nearest neighbours in a close-packed structure. In ionic crystals, coordination number of an ion in the crystal is the number of oppositely charged ions surrounding that particular ion.

(ii) (a) 12 (b) 8.

Q. 5. How can you determine the atomic mass of an unknown metal if know its density and the dimension of its unit cell? Explain your answer.

Ans. Refer to Basic Concepts Point 5. Atomicmass, M z

d×a ×NA

3

e = o

Q. 6. ‘Stability of a crystal is reflected in the magnitude of its melting point’. Comment. Collect melting points of solid water, ethyl alcohol, diethyl ether and methane from a data book. What can you say about the intermolecular forces between these molecules?

Ans. Higher the melting point, stronger are the forces holding the constituent particles together and hence greater

is the stability. In other words, stronger the lattice structure, higher will be lattice energy and more will

be the stability of crystal, hence higher the melting point. The intermolecular forces in water and ethyl

alcohol are mainly the hydrogen bonding. Higher melting point of water as compared to alcohol shows that

hydrogen bonding in ethyl alcohol molecules is not as strong as in water molecules. Diethyl ether is a polar

molecule and the intermolecular forces present in it is dipole–dipole attraction. Whereas methane is a nonpolar

molecule and the only forces present in it is the weak van der Waals’ forces.

Q. 7. How will you distinguish between the following pairs of terms: [CBSE (AI) 2014]

(i) Hexagonal close packing and cubic close packing?

(ii) Crystal lattice and unit cell?

(iii) Tetrahedral void and octahedral void?

Ans. (i) Refer to Basic Concepts Points 8(c) (i) and (ii).

(ii) The regular three dimensional arrangement of identical points in the space which represent how the constituent particles (atoms, ions, molecules) are arranged in a crystal is called a crystal lattice. A unit cell is the smallest portion of a crystal lattice, which when repeated over and again in different directions produces the complete crystal lattice.

(iii) A void surrounded by four spheres occupying the corners of tetrahedron is called a tetrahedral void. It

is much smaller than the size of spheres in the close packing. A void surrounded by six spheres along

the corners of an octahedral is called octahedral void. The size of the octahedral void is smaller than

that of the spheres in the close packing but larger than the tetrahedral void.

Q. 8. How many lattice points are there in one unit cell of each of the following lattices?

(a) face-centred cubic (b) face-centred tetragonal (c) body-centred.

Ans. (a) 14 (b) 14 (c) 9.

Q. 9. Explain:

(a) The basis of similarities and differences between metallic and ionic crystals.

(b) Ionic solids are hard and brittle.

Ans. (a) Similarities:

(i) Both ionic and metallic crystals have electrostatic forces of attraction. In ionic crystals, these are between the oppositely charged ions. In metals, these are among the valence electrons and the kernels.

(ii) In both cases, the bond is non-directional.

Differences:

(i) In ionic crystals, the ions are not free to move. Hence, they cannot conduct electricity in the solid state. They can do so only in the molten state or in aqueous solution. In metals, the valence electrons are not bound but are free to move. Hence, they can conduct electricity in the solid state.

(ii) Ionic bond is strong due to electrostatic forces of attraction. Metallic bond may be weak or strong depending upon the number of valence electrons and the size of the kernels.

(b) Ionic solids are hard because there are strong electrostatic forces of attraction among the oppositely charged ions. They are brittle because ionic bond is non-directional.

Q. 10. Calculate the efficiency of packing in case of a metal crystal for

(a) simple cubic (b) body-centred cubic (c) face-centred cubic

Ans. Do yourself

Q. 11. Silver crystallises in fcc lattice. If edge length of the cell is 4.07 × 10–8 cm and density is 10.5 g cm–3, calculate the atomic mass of silver.


Q. 12. A cubic solid is made up of two elements P and Q. Atoms of Q are at the corners of the cube and P at the body centre. What is the formula of the compound? What are the coordination numbers of P and Q?

Ans. Number of P atoms per unit cell = 1 (at the body centre) × 1 = 1

Number of Q atoms per unit cell = 8 (at the corners) ×1/ 8= 1

Hence the formula is PQ.

Coordination number of each of P and Q = 8.

Q.13. Niobium crystallises in body-centred cubic structure. If density is 8.55 g cm–3, calculate atomic radius of niobium using its atomic mass 93u.

Q. 14. If the radius of the octahedral void is r and the radius of the atoms in close packing is R, derive relationship between r and R.
Ans. A sphere fitting into the octahedral void is shown by shaded circle. The spheres present above and below
the void are not shown in the figure. As ABC is a right-angled triangle, Pythagoras theorem is applied.
AC2 = AB2 + BC2
(2R)2 = (R + r)2 + (R + r)2 = 2(R + r)2
B
r r
R
R R
A R C
4R2 = 2(R + r)2
2R2 = (R + r)2
( 2 R)2 = (R + r)2
2 R = R + r
r = 2 R – R
r = ( 2 – 1) R = (1.414 – 1)R
r = 0.414 R
Q. 15. Copper crystallises into a fcc lattice with edge length 3.61 × 10–8 cm. Show that the calculate density is in agreement with its measured value of 8.92 g cm–3.
Q. 16. Analysis shows that nickel oxide has the formula Ni0.98O1.00. What fractions of nickel exist as Ni2+ and Ni3+ ions?
Ans. 98 Ni atoms, are associated with 100 O atoms. Out of 98 Ni atoms, suppose Ni present as Ni2+ = x.
Then Ni present as Ni3+ = 98 – x.
Total charge on x Ni
2+ and (98 – x) Ni3+ should be equal to charge on 100 O2– ions.
Therefore, x × 2 + (98 – x) × 3 = 100 × 2
or 2x + 294 – 3x = 200
or x = 94
\ Fraction of Ni present as Ni2+ =
94
98
× 100 = 96%
Fraction of Ni present as Ni3+ =
4
98
× 100 = 4%
Q. 17. What is a semiconductor? Describe the two main types of semiconductors and contrast their
conduction mechanisms.
Ans. DO Yourself
Q. 18. Non-stoichiometric cuprous oxide, Cu2O can be prepared in laboratory. In this oxide, copper to
oxygen ratio is slightly less than 2 : 1. Can you account for the fact that this substance is a p-type
semiconductor?
Ans. The ratio less than 2 : 1 in Cu2O shows that some cuprous (Cu+) ions have been replaced by cupric (Cu2+)
ions. For maintaining electrical neutrality, every two Cu+ ions will be replaced by one Cu2+ ion thereby
creating a hole. As conduction will be due to the presence of these positive holes, hence it is a p-type
semiconductor.
Q. 19. Ferric oxide crystallises in a hexagonal close packed array of oxide ions with two out of every three octahedral holes occupied by ferric ions. Derive the formula of the ferric oxide.
Ans. Let the number of oxide ions (O2–) in the close packing be x.
\ Number of octahedral voids = x
As 2/3rd of the octahedral voids are occupied by ferric ions, number of ferric ions present
= x x
3
2
3
2
# =
\ Ratio of Fe3+: O2– = x
3
2
: x = 2 : 3
Hence, the formula of ferric oxide is Fe2O3.
Q. 20. Classify each of the following as being either a p-type or a n-type semiconductor:
(i) Ge doped with In (ii) Si doped with B.
Ans. (i) Ge is Group 14 element and In is Group 13 element therefore, an electron deficit hole is created. Thus,
semiconductor is p-type.
(ii) Since Si is Group 14 element and B is Group 13 element, therefore, an electron deficit hole is created.
Thus, semiconductor is p-type.
Q. 21. Gold (atomic radius = 0.144 nm) crystallises in a face-centred unit cell. What is the length of a side of the cell?
Ans. For fcc, a = 2 2 r = 2 × 1.414 × 0.144 nm = 0.407 nm.
Q. 22. In terms of band theory, what is the difference
(i) between a conductor and an insulator
(ii) between a conductor and a semiconductor?
Ans. (i) The energy gap between the valence band and conduction band in an insulator is very large while in a
conductor, the energy gap is very small or there is overlapping between valence band and conduction
band.
(ii) In a conductor, there is a very small energy gap or there is overlapping between valence band and conduction band whereas in semiconductor there is always a small energy gap between them.
Q. 23. Explain the following terms with suitable examples:
(i) Schottky defect (ii) Frenkel defect (iii) interstitials (iv) F-centres.
Ans. do yourdelf 
Q. 24. Aluminium crystallises in a cubic close packed structure. Its metallic radius is 125 pm.
(a) What is the length of the side of the unit cell?
(b) How many unit cells are there in 1.00 cm3 of aluminium? [CBSE (F) 2011]
Ans. (a) For a fcc unit cell, r =a
2 2
a = 2 2 r = 2 × 1.414 × 125
= 353.5 pm
(b) Volume of unit cell = a3 = (353.5 × 10–10 cm)3
= 442 × 10–25 cm3
Number of unit cell =
cm
cm
442 10
1
25 3
3
– #
= 2.26 × 1022 unit cells
Q. 25. If NaCl is doped with 10–3 mol % SrCl2, what is the concentration of cation vacancies?
Ans. As NaCl is doped with 10–3 mol % of SrCl2
i.e., 100 mol of NaCl are doped with 10–3 mol of SrCl2
\ 1 mol of NaCl is doped with Sr Cl2 =
100
10
–3
mol = 10–5 mol
As each Sr2+ ion introduces one cation vacancy, therefore, concentration of cation vacancies
= 10–5 × 6.02 × 1023 mol–1
= 6.02 × 1018 mol–1
Q. 26. Explain the following with suitable examples:
(a) Ferromagnetism (b) Paramagnetism
(c) Ferrimagnetism (d) Antiferromagnetism
(e) 12-16 and 13-15 group compounds.

 

(i) Ferromagnetism
Certain substances exhibit very strong magnetic property. They can be permenently magnetised. They contain large number of unpaired electrons and the magnetic moment associated with it are equal in magnitude and aligned in the same direction.
Examples: Iron, cobalt, nickel, gadolinium, CrO 2  etc.

(ii) Paramagnetism
When unpaired electrons revolve in the orbitals, a net magnetic field is associated with the substance containing these unpaired electrons.
Due to presence of unpaired electrons, certain substances experiences pull in magnetic field. The number of unpaired electrons determine the extent of paramagnetism.
Examples : Oxygen, Cu 2+ , Fe 3+  and Cr 3+
 
(iii) Ferrimagnetism
Unequal magnitude of magnetic moment associated with unpaired electrons are aligned in the same directions, the net magnetic moment is not zero.
Example: Ferrite Fe 2
 O 3
(iv) Antiferromagnetism
Equal magnitude of magnetic moment associated with unpaired electrons are aligned in opposite directions, the net magnetic moment is zero.
Example: MnO, Mn 2 O 3
 and MnO 2

(v) 12-16 and 13-15 group compounds: The 12-16 group compounds are prepared by combining group 12 and group 16 elements and the 13-15 group compounds are prepared by combining group 13 and group15 elements. These compounds are prepared to stimulate average valence of four as in Ge or Si. Indium (III) antimonide (IrSb), aluminium phosphide (AlP), and gallium arsenide (GaAS) are typical compounds of groups 13-15. GaAs semiconductors have a very fast response time and have revolutionised the designing of semiconductor devices. Examples of group 12-16 compounds include zinc sulphide (ZnS), cadmium sulphide (CdS), cadmium selenide (CdSe), and mercury (II) telluride (HgTe). The bonds in these compounds are not perfectly covalent. The ionic character of the bonds depends on the electronegativities of the two elements.

                     
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