Namma Kalvi

www.nammakalvi.org PH RAJ

UNIT - 1 METALLURGY
Answer the following questions:

1. What is the difference between minerals and ores?

Minerals Ores
A naturally occurring substance which Minerals that contains a high percentage of
contains metal in free state or in the form of metal, from which it can be extracted
compounds is called a mineral. conveniently and economically are called ores.

2. What are the various steps involved in extraction of pure metals from their ores?

The extraction of a metal from its ore consists of the following metallurgical processes.
(i) Concentration of the ore (ii) Extraction of crude metal (iii) Refining of crude metal

3. What is the role of Limestone in the extraction of Iron from its oxide Fe 2O3?

Limestone in the extraction of Iron from its oxide Fe 2O3 is used as a flux.
CaO (s) + SiO2 (s) CaSiO3 (s)
Flux Gangue Slag

4. Which type of ores can be concentrated by froth floatation method? Give two examples
for such ores.

Sulphide ores can be concentrated by froth floatation method

Ex. Galena (PbS) and Zinc blende (ZnS)

5. Out of coke and CO, which is better reducing agent for the reduction of ZnO? Why?

(i) Above 1273 K The ∆Go for the formation of 2C + O2 2CO (g) is lower
than the formation of ZnO on comparing the ∆Go of formation of 2CO + O2 2CO2
(g) it is higher than the ∆Go of formation of ZnO.
(ii) Therefore C is always considered as better reducing agent than CO for the reduction
of Zn from ZnO
(iii) In Ellingham diagram ∆Go of ZnO is below the ∆G of formation of CO

6. Describe a method for refining nickel.

Mond process for refining nickel:

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+2 CHEMISTRY www.nammakalvi.org Dr. C. ARUL JOSEPH RAJ

Principle: Impure metal is treated with a suitable reagent which can form a volatile
compound with the metal.
Then the volatile compound is decomposed to give the pure metal.
Process: The impure nickel is heated with carbon monoxide at 350 K.
The nickel reacts with CO and forms a volatile nickel tetracarbonyl.
Ni (s) + 4 CO (g) Ni(CO)4 (g)

On heating the nickel tetracarbonyl around 460 K, the complex decomposes and gives pure
metal. Ni(CO)4 Ni (s) + 4 CO (g)
7. Explain zone refining process with an example

Method: Fractional Crystallisation.

Principle: . Impurities are more soluble in the melt than in the solid state metal.
Process:
Impure metal is taken in the form of a rod.
One end of the rod is heated using a mobile induction heater .
The metal rod melts
When the heater is slowly moved to the other end the pure metal crystallises
The impurities moves on to the adjacent molten zone formed due to the movement of the
heater.
As the heater moves further away, the molten zone containing impurities also moves along
with it.
This process is repeated several times by moving the heater in the same direction again and
again to get pure metal .
It is carried out in an inert gas atmosphere to prevent the oxidation of metals .
Example : Germanium (Ge), Silicon (Si) and Galium (Ga) are refined by this process.
8. (A) Predict the conditions under which

(i) Aluminium might be expected to reduce magnesia.

Above 1623K (1350oC ) ∆Go of formation of 4/3 Al + O2 2/3 Al2O3from Al is less

than that of MgO from Mg . Therefore above 1623K , Al can reduce MgO.

(ii) Magnesium could reduce alumina.

Temperature below the point of intersection ∆Go of formation of Al2O3 and MgO

that is below 1400oC Mg reduce Al2O3 (At the point of intersection ∆Go = 0)

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(B) Carbon monoxide is more effective reducing agent than carbon below 983K but,
above this temperature, the reverse is true –Explain.

Below 983K ∆Go of formation of 2CO(g) + O2 (g) 2CO2 (g) is favoured due to
more negative ∆Go value Thus CO is a better reducing agent .

Above 983K ∆Go of formation of 2C(s) + O2(g) 2CO (g) is favoured due to more
negative ∆Go value than the ∆Go of formation of CO2 . Thus C is a better reducing agent .

(c) it is possible to reduce Fe2 O 3 by coke at a temperature around 1200K

Around 1200K ∆Go of formation of Fe2 O 3 has more negative value than ∆Go of formation
of CO2 from C

9. Give the uses of zinc.

• Metallic zinc is used in galvanising metals such as iron and steel to protect them from
rusting and corrosion.

• It is used to produce die-castings in the automobile, electrical and hardware industries

• Zinc oxide is used in the manufacture paints, rubber, cosmetics, plastics, inks, batteries,
textiles and electrical equipment.
• Zinc sulphide is used in making luminous paints, fluorescent lights and x-ray screens.
• Brass an alloy of zinc is used in water valves and communication equipment

10. Explain the electrometallurgy of aluminium.

Hall-Herold process:

In this method, electrolysis is carried out in an iron tank lined with carbon which acts as a
cathode.

The carbon blocks immersed in the electrolyte acts as a anode.

A 20% solution of alumina, obtained from the bauxite ore is mixed with molten cyrolite and
is taken in the electrolysis chamber.

About 10% calcium chloride is also added to the solution.

Here calcium chloride helps to lower the melting point of the mixture.

The fused mixture is maintained at a temperature of above 1270 K.

The chemical reactions involved in this process are as follows.

Ionisaiton of alumina Al2O3 2Al3+ + 3O2-

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Reaction at cathode 2Al3+ (melt) + 3e- Al (l)

Reaction at anode 2O2- (melt) O2 + 3e-

Since carbon acts as anode the following reaction also takes place on it.

C (s) + O2- (melt) CO + 2e-

C (s) + 2O2- (melt) CO2 + 4e-

Due to the above two reactions, anodes are slowly consumed during the electrolysis.

The pure aluminium is formed at the cathode and settles at the bottom.

The net electrolysis reaction can be written as follows.

4Al3+ (melt) + 6O2- (melt) + 3C (s) 4Al (l) + 3CO2 (g)

11. Explain the following terms with suitable examples.

(i) Gangue :Earthly waste substances occurring in ore eg. Silica

(ii) Slag : Waste matter separated from meta during smelting eg. FeSiO3

(iii) Flux: The substance which is added in the ore to convert non-fusible gangue to fusible
compound is called flux.

12. Give the basic requirement for vapour phase refining.

In this method, the metal is treated with a suitable reagent which can form a volatile compound
with the metal. Then the volatile compound is decomposed to give the pure metal.

13. Describe the role of the following in the process mentioned.

(i) Silica in the extraction of copper.

Silica is an acidic flux It removes ferrous oxide as ferrous silicate (slag).
FeO(Gangue) + SiO2(Flux ) FeSiO3(Slag)
(ii) Cryolite in the extraction of aluminium.
Cyrolite lowers the melting point of alumina and it increases the electrical conductivity .
(iii) Iodine in the refining of Zirconium.
Zr is heated in iodine vapours at about 550 K to form volatile ZrI4. which is heated over
tungsten filament at 1800K to get pure Zr.
Zr (s) + 2I2 (s) Zr I4 Zr (s) + 2I2
(Impure) (volatile) (Pure)
(iv) Sodium cyanide in froth floatation.
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NaCN is used as a depressant. It selectively prevents ZnS from coming to froth but
allows PbS to come with forth. Because NaCN reacts with ZnS to form Na2 [Zn (CN) 4].

14. Explain the principle of electrolytic refining with an example.

Let us understand this process by considering electrolytic refining of silver as an example.

Cathode : Pure silver
Anode : Impure silver rods
Electrolyte : Acidified aqueous solution of silver nitrate.
When a current is passed through the electrodes the following reactions will take place
at anode 2Ag (s) Ag+ (aq) + 1e-
at cathode Ag+ (aq) + 1e- Ag (s)
During electrolysis, silver atoms lose electrons and silver cations get electrons

15. The selection of reducing agent depends on the thermodynamic factor: Explain with an
example.

The selection of reducing agent depends on the thermodynamic factor

• The reduction of metal oxide using reducing agent can occur if the free energy
change is negative.
• The reducing reaction having large negative ∆G value is selected
Example
• Above1623K, Al has more negative ∆G° value than Mg
• Hence Al is used to reduce magnesia.
• Below 1623K, Mg has more negative ∆G° value than Al
• Hence Mg will be used to reduce Alumina.

16. Give the limitations of Ellingham diagram.

• Ellingham diagram is constructed based only on thermodynamic considerations.

• It gives information about the thermodynamic feasibility of a reaction.

• It does not tell anything about the rate of the reaction.

• It does not give any idea about the possibility of other reactions that might be taking
place.

• The interpretation of ∆G is based on the assumption that the reactants are in equilibrium
with the product which is not always true.

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17. Write a short note on electrochemical

trochemical principles of metallurgy.

In this technique, the metal salts are taken in a fused form or in solution form. The metal ion
present can be reduced by treating it with some suitable reducing agent or by electrolysis.

18, Explain Froth flotation method

thod

This method is commonly used to concentrate sulphide ores such as galena (PbS), zinc
blende (ZnS)

Principle: Metallic ore particles are wetted by oil is separated from gangue.

In this method, the crushed ore is suspended in water and mixed with frothing agent such as
pine oil, eucalyptus oil.

A small quantity of sodium ethyl xanthate which acts as a collector is also added.

A froth is generated by blowing air through this mixture.

The collector molecules attach to the ore particle and make them
them water repellent.

As a result, ore particles, wetted by the oil, rise to the surface along with the froth

The froth is skimmed off and dried to recover the concentrated ore.

The gangue particles wetted by water settle at the bottom.

When a sulphide ore of a metal contains other metal sulphides as impurities, depressin
depressing
agents such as sodium cyanide or sodium carbonate are used to prevent other metal sulphides
coming to the froth.

For example, when impurities such as ZnS is present in galena (PbS), sodium
so cyanide
(NaCN) is added to depresses the flotation property of ZnS by forming a layer of zinc complex
Na2[Zn(CN)4] on the surface of zinc sulphide.

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19. Explain Van-Arkel method for refining zirconium/titanium

Principle : It is based on the thermal decomposition of metallic compounds

Process :

Titanium and zirconium can be purified using this method.

The impure titanium metal is heated in an evacuated vessel with iodine at a temperature of 550
K to form the volatile titanium tetra-iodide.(TiI4).

The impurities are left behind, as they do not react with iodine.

Ti (s) + 2I2 (s) TiI4 (vapour)

The volatile titanium tetraiodide vapour is passed over a tungsten filament at a temperature
aroud 1800 K.

The titanium tetraiodide is decomposed and pure titanium is deposited on the filament. The
iodine is reused.

TiI4 (vapour) Ti (s) + 2I2 (s)

20. What is Ellingham diagram?

The graphical representation of variation of the standard Gibbs free energy of reaction for the
formation of various metal oxides with temperature is called Ellingham diagram
21. What are the applications of copper?
Copper is used for making coins and ornaments along with gold and other metals.

Copper and its alloys are used for making wires, water pipes and other electrical parts.

22. Explain electromagnetic separation method with example.

This method is applicable to ferromagnetic ores

Principle : It is based on the difference in the magnetic properties of the ore and the impurities.
Process: Tin stone can be separated from the wolframite impurities which is magnetic.
ores such as chromite, pyrolusite having magnetic property can be removed from the non
magnetic siliceous impurities.
The crushed ore is poured on to an electromagnetic separator
It consisting of a belt moving over two rollers of which one is magnetic.
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The magnetic part of the ore is attracted towards the magnet and falls as a heap close to the
magnetic region
The nonmagnetic part falls away from it

23 .Distinguish
Distinguish between roasting and Calcination.
S. Roasting Calcination
No.
Ore is heated with excess of oxygen in a Ore is strongly heated in the absence of air
below the melting point of the metal. limited supply of air below the melting point
of the metal
It is applied for the conversion of sulphide It is applied forr the conversion of carbonate
ores into their oxides ores into their oxides
It removes impurities such as arsenic, the water of crystallisation escapes as
sulphur and phosphorous by converting moisture.
them into their volatile oxides

24. Gravity separation or Hydraulic wash

Principle : The ore having high specific gravity is separated from the gangue
.Ore
Ore is crushed to a finely powdered form and treated with rapidly flowing current of water.
During this process the lighter gangue particle
particless are washed away by the running water.
This method is generally applied to concentrate the native ore such as gold and oxide ores such
as hematite (Fe2O3), tin stone (SnO2) etc
25. What is Metallurgy?

Metallurgy relate to the science and technology of metals.

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26. What is cementation?

Gold recovered by reacting the deoxygenated leached solution with zinc .Gold is reduced to its
elemental state and the process is called cementation.
27. What is the Composition of copper matte?

Mixture of Cu2S and FeS is called copper matte

28. Define the following terms; (i) Thermite, (ii) Ignitation powder, (iii) Cementation.
(i) Thermite: Mixture of oxide and Al in the ratio of 3:1 is called thermite.
(ii) Ignitation powder: BaO2+Mg powder acts as ignitation powder.
(iii) Cementation: Metal is reduced to its elemental state (zero oxidation sate) and process is
called cementation.
20. State the principles of i. Leaching, ii. Smelting, iii. Distillation iv. Liquation v. Vapour
phase refining

Principle: It is based on the solubility of the ore in a suitable solvent and the reactions in
aqueous solution.
The crushed ore is allowed to dissolve in a suitable solvent, the metal present in the ore is
converted to its soluble salt or complex while the gangue remains insoluble.
Smelting
In this method, a flux and a reducing agent such as carbon, carbon monoxide (or) aluminium is
added to the concentrated ore and the mixture is melted by heating above the melting point of
the metal is called smelting,

Distillation

In this method, the impure metal is heated to evaporate and the vapours are condensed to get
pure metal.
Liquation
. The impure metal is placed on sloping hearth of a reverberatory furnace and it is heated just
above the melting point of the metal in the absence of air, the molten pure metal flows down and
the impurities are left behind. The molten metal is collected and solidified.
(v) Vapour phase refining:

The impure metal is converted into its volatile compound, which on heating is decomposed
to pure metal.
21.Why does molten copper have blister appearance?

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The metallic copper is solidified and it has blistered appearance due to evolution of SO2 gas
formed in this process. This copper is called blistered copper.
22.Write the name of the metal refined by each of the following processes:

(i) Distillation, (ii)Liquation, (iii) Electrolysis, (iv) Zone refining, (v) Van akral method
(i) Distillation- Zn and Hg (ii)Liquation- Sb, Pb,Hg, Bi (iii) Electrolysis- Ag,Cu,Zn (iv) Zone
refining – Ge,Si,Ga (v) Van akral method-Ti,Zr.

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UNIT 6 - SOLID STATE

1.Define unit cell.
A basic repeating structural unit of a crystalline solid is called a unit cell.
2. Give any three characteristics of ionic crystals.
Ionic solids have high melting points.
They do not conduct electricity.
They conduct electricity in molten state (or) when dissolved in water
They are hard

3. Differentiate crystalline solids and amorphous solids.

S.No Crystalline Amorphous solids
solids
1 Long range orderly arrangement of Short range, random arrangement of
constituents. constituents.
2 Definite shape Irregular shape
3 Anisotropic in nature Isotropic in nature
4 They are true solids They are pseudo solids (or) super
cooled liquids
5 Definite Heat of fusion Heat of fusion is not definite
6 They have sharp melting points. They have sharp melting points.
7 Examples: NaCl , diamond etc., Examples: Rubber , plastics, glass etc

4. Distinguish between hexagonal close packing and cubic close packing.

S.NO HEXAGONAL CLOSE PACKING CUBIC CLOSE PACKING.

1 “ABA’’ arrangement is known as “ABC’’ arrangement is known as the
the hexagonal close packed (hcp) hexagonal cubic close packing. (ccp)
arrangement. arrangement.
2 The spheres of the third layer is The spheres of the third layer is not aligned
exactly aligned as first layer with those of either the first or second layer.
3 The hexagonal close packing is based The cubic close packing is based on the face
hexagonal unit cells with sides of centered cubic unit cell.
equal length
4 Tetrahedral voids of the second octahedral voids of the second layer are
layer are covered by the sphere of covered by the sphere of the third layer
the third layer
5 hcp unit cells contain 6 atoms ccp unit cells contain 4 atoms
5. Classify the following solids
a. P4 - covalent solid b. Brass – Metallic solid c. diamond- covalent solid

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d. NaCl – Ionic solid e. Iodine - Non polar molecular solid

6.. Explain briefly seven types of unit cell.

There are seven primitive crystal systems 1. Cubic 2. Tetragonal 3.Orthorhombic
Orthorhombic 4.
Hexagonal 5.Monoclinic 6. Triclinic and 7.Rhombohedral.
Rhombohedral. They differ in the arrangement of
their crystallographic axes and angles.
angles

7. Distinguish tetrahedral and octahedral voids.

S.NO TETRAHEDRAL VOIDS OCTAHEDRAL VOIDS.
1 When a sphere of second layer (b) is When the voids (y) in the first layer (a)
above the voidid (x) of the first layer (a), are partially covered by the spheres of
tetrahedral void is formed. layer (b), octahedral void is formed in
(a)
2 If the number of close packed spheres be If the number of close packed spheres
‘n’ then, the number of tetrahedral voids be ‘n’ then, the number of octahedral
generated is equal to 2n. voids generated is equal to n
3 This constitutes four spheres – three in This constitutes six spheres – three in
the lower (a) and one in the upper layer the lower layer (a) and three in the
(b). upper layer (b)
4 When the centers of these four spheres When the centers of these six spheres
are joined, a tetrahedron is formed. are joined, an octahedron is formed.

8. What are point defects?

Point defects are defects that occur only at or around a single lattice point of a crystal lattice

9. Explain Schottky defect.

Schottky defect arises due to the missing of equal number of cations and anions from the crystal
lattice.
This effect does not change the stoichiometry of the crystal.
Ionic solids in which the cation and anion are of almost of similar size show schottky
schottk defect.
Example: NaCl.
Presence of large number of schottky defects in a crystal, lowers its density.
Presence of Schottky defect in the crystal provides movement of atoms or ions within the
crystal lattice.

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10. Write short note on metal excess and metal deficiency defect with an example.
Metal excess defect :

• Metal excess defect arises due to the presence of more number of metal ions as compared to
anions.
• Alkali metal halides NaCl, KCl show this type of defect.
• The electrical neutrality of the crystal is maintained by the presence of electron present in
interstitial position.
• For example, when NaCl crystals are heated in the presence of sodium vapour, Na+ ions are
formed and are deposited
ited on the surface of the crystal.
• Chloride ions (Cl-)) diffuse to the surface from the lattice point and combines with Na+ ion.

• The electron lost by the sodium vapour diffuse into the crystal lattice and occupies the
vacancy created by the Cl- ions.
ion
• Such anionic vacancies which are occupied by unpaired electrons are called F centers.
• Hence, the formula of NaCl which contains excess Na+ ions can be written as Na Cl 1+ x .
Metal deficiency defect

• Metal deficiency defect arises due to the presence of less number of cations than the anions.
• This defect is observed in a crystal in which, the cations have variable oxidation states.
• For example, in FeO crystal.
• Some of the Fe2+ ions are missing from the crystal lattice.

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• To maintain the electrical neutrality, twice the number of other Fe2+ ions in the crystal is
oxidized to Fe3+ ions.
• In such cases, overall number of Fe2+ and Fe3+ ions is less than the O2- ions.
• It was experimentally found that the general formula of ferrous oxide is FexO, where x
ranges from 0.93 to 0.98.

11. Calculate the number of atoms in a fcc unit cell.

Nc + Nf 8 6
No of atoms in fcc unit cell = ---- ---- = ------ + --------- = 1 + 3 = 4
8 2 8 2
12. Explain AAAA and ABABA and ABCABC type of three dimensional packing with the
help of neat diagram.

i. AAAA three dimensional packing

• It occurs in simple cubic arrangement
• This type of packing arrangements is obtained by repeating the AAAA type in three
dimensions.
• Spheres in one layer sitting directly on the top of those in the previous layer so that all layers
are identical.
• All spheres of different layers of crystal are perfectly aligned ho
horizontally
rizontally and also vertically,
• The unit cell of this arrangement is simple cubic
• In this each sphere is in contact with 6 neighbouring spheres
• Four in its own layer, one above and one below
• Hence the coordination number of the sphere in simple cubic arrangement is 6.

ii. ABABA three dimensional packing

• It occurs in body centered cubic arrangement

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• In this arrangement, the spheres in the first layer ( A type ) are slightly separated and the
second layer is formed by arranging the spheres in the depressions between the spheres in
layer A as shown in figure.
• The third layer is a repeat of the first.
• This pattern ABABAB is repeated throughout the crystal.
• In this arrangement, each sphere has a coordination number of 8, four neighbors in the layer
above and four in the layer below.

iii. ABCABC three dimensional packing

• The first layer ‘a’. formed by arranging the spheres as in the case of two dimensional
arrangements
• The second layer ‘b’ is formed by placing the spheres in the depressions of the first layer
• A tetrahedral void (x) is formed in the second layer (b) a octahedral void (y) is formed. in
the first layer (a)
• The third layer is placed over the second layer in such a way that all the spheres of the third
layer fit in octahedral voids.
• This arrangement of the third layer is different from other two layers (a) and (b),
• hence, the third layer is designated (c).
• If the stacking of layers is continued in abcabcabc… pattern, then the arrangement is called
cubic close packed (ccp) structure.
• In ccp arrangements, the coordination number of each sphere is 12 – six neighbouring
n
spheres in its own layer, three spheres in the layer above and three sphere in the layer below.

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13. Why ionic crystals are hard and brittle?

• In ionic crystal cations and anions are bound together by strong electrostatic attractive
forces.
• To maximize the attractive force, cations are surrounded by as many anions as possible and
vice versa.

14. Calculate the percentage efficiency of packing in case of body centered cubic crystal.
In ∆ ABC

AC2 = AB2 + BC2

AC = √ AB2 + BC2

AC = √ a2 + a2 = √2 a2 = √2
√ a
In ∆ ACG

AG2 = AC2 + CG2

In ∆ AGC

AG= √ AC2 + CG2

AG = √ (√2 a) 2 + a2

= √2 a2 + a2 = √3 a2

AG = √3 a2

i.e. √3 a2 = 4r

√3 a2
r = ___
4

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4
Volume of the sphere with radius ‘r’ = --- πr3
3
3
4 √3
= --- π ---- a
3 4
4 √3 x √3 x √3
=---- x ------------------- πa3
3 4x4x4

√3
= ------ π a3
16

No of spheresof of unit cell BCC = 2

√3 π a3 √3 π a3
Hence total volume of all spheres = 2 x ---------- = ------------
16 8 8

Total volume occupied by spheres in unit cell

packing fraction =-------------------------------------------------------------- x 100
volume of unit cell

√3 π a3
----------
8
= --------------- x 100
a3

= √3 π x 12.5

= 1.732 x 3.14 x 12.5

Percentage efficiency of packing in bcc = 68%

15. What is the two dimensional coordination number of a molecule in square close packed
layer?
The two dimensional coordination number of a molecule in square close packed layeris 4 In
this arrangement each sphere is in contact with four of its neighbours.

16. Experiment shows that Nickel oxide has the formula Ni O 0.96 1.00 . What fraction of
Nickel exists as of Ni2+ and Ni3+ ions?

Formula Ni O 0.96 1.00

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So ratio of Ni: O = 98: 100

Let the no of Ni2+ is = x

Let the no of Ni3+ is = 98 – x

Charge on Ni = charge on O

3(98 –x) +2x = 2(100)

294-3x + 2x = 200

-x = 200 – 294

x = 94

Atoms of Ni +2
Percentage of Ni +2 = ----------------------- x 100
Total no. of Ni

94
= ------ x 100 =96 %
98

Percentage of Ni +3 = 100 -96 = 4%

17. What is meant by the term “coordination number”? What is the coordination number
of atoms in a bcc structure?
The neighbouring atoms surrounded by each atom is called coordination number. In the body
centre, each atom is surrounded by eight nearest neighbours and coordination number is 8.

18. An element has bcc structure with a cell edge of 288 pm. the density of the element is
7.2 gcm-3. how many atoms are present in 208g of the element.

Given

Edge of bcc (a) = 288pm = 288 x 1010 cm

Density7.2 gcm-3

Mass of element : 208g

Volume of unit cell a3 = (288 x 10 -10 cm ) 3 =2.39X10-23 cm3

M 208 g
Volume of 208g of element = -------- =------------- = 28.89 cm3
D 7.2 gcm-3

Total volume 28.89 cm3

No. of unit cells = ------------------------ = -------------------- = 12.09 x 1023

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Volume of unit cell 2.39X10-23 cm3

For a bcc umber of atoms per unit cell = 2

No of atoms present in 208g = No of atoms per unit cell x No of unit cell = 2 x 12.09 x 1023

= 24,18 x 1023
No of atoms present in 208g = 2.418 x 1024

19. Aluminium crystallizes in a cubic close packed structure. Its metallic radius is 125pm.
calculate the edge length of unit cell.

Given : r = 125pm.

For ccp a = 2√2 r

= 2 x 1.44 x 125 pm = 354 pm (approximate)

20. If NaCl is dopped with 10-2 mol percentage of strontium chloride, what is the
concentration of cation vacancy?

Given
1 Cation of Sr2+ will create 1 cation vacancy in Nacl.
Number of cation vacancies created in the lattice of Nacl = to the number of divalent Sr2+ ions
added.

Given Conetration of SrCl2 = 10−2 mol%

Concentration is in percentage so that take total 100 mol of solution
Number of moles of NaCl = 100 – moles of SrCl2
Moles of SrCl2 is very negligible as compare to total moles so
Number of moles of NaCl = 100
1 mol of NaCl is dopped with = 10−2/100 moles of SrCl2
= 10–4 mol of SrCl2
So cation vacancies per mole of NaCl =10–4 mol
1 mol = 6.022 x1023 particles
So
So cation vacancies per mole of NaCl = 10–4 x 6.022 x1023
= 6.02 x1019
So that, the concentration of cation vacancies created by SrCl2 = 6.022 × 1019

21. KF crystallizes in fcc structure like sodium chloride. calculate the distance between K+
and F− in KF.( given : density of KF is 248 3 .g cm−3)

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+2 CHEMISTRY Dr. C. ARUL JOSEPH RAJ

Step 1. Calculate the numbers of K+ and F- ions in a unit cell

Ne Nb 12 1
Number of K+ ( Edge centre and in body centre ) = ---------- + ------ = ----- + ----- = 4
4 1 4 1

Nc Nf 8 6
-
Number of F ( Corner and in face cerntr ) = ---------- + ------ = ----- + ----- = 4
8 2 8 2
There are four K+ and four F- ions or four KF formula units (FU)

Step 2. Calculation of mass of a unit cell

Mass of 6.022×1023FU = 58.10 g mol-1

58.10 g mol-1 x 4
Mass of 4 FU = ------------------------- = 3.86 x 1022 g
6.022×1023

Step 3. Calculation of volume of a unit cell

Density of KF is = 2.48 g cm−3
M 3.86 x 1022 g
∴ Volume of a unit cell = ------- = -------------- = 1.56 x 1022 cm-3
D 2. 48 g cm−3

Step 4. Calculation of edge length of the unit cell

V= l3
∴ l = 3√V = 3√1.56 × 10-22 cm3 = 5.38×10-8 cm = 538 pm

Step 5. Calculation of interionic distance

In NaCl unit cell, the edge length is twice the interionic distance.
∴ Interionic distance = 538 / 2 pm = 269 pm

22. An atom crystallizes in fcc crystal lattice and has a density of 10 3 gcm−3 with unit cell
edge length of 100pm. calculate the number of atoms present in 1 g of crystal.

Given:

Density =10 -3 gcm−3 a = 100 pm = 100 x 10 -10 cm Mass = 1g

No of atoms in Fcc unit cell = 4

Volume of unit cell a3 = (100 x 10 -10 cm)3 = 10-24 gcm−3

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+2 CHEMISTRY www.nammakalvi.org Dr. C. ARUL JOSEPH RAJ

M 1g
Volume of crystal = -------- = --------------- = 10 3 gcm−3
D 10 -3 gcm−3

Volume of crystal 10 3 gcm−3

No of unit cells in 1 g of crystal = ------------------------- = ---------------- = 10 3 x 10 24
Volume of unit cell 10-24 gcm−3

= 10 27
No of atoms in each fcc unit cell = 4

Total no of atoms in 10 27 unit cells = 4 x 10 27

No of atoms in 1 g of crystal = 4 x 10 27

(OR)

ZxM 4 x 1g 4
Total no of atoms 1 g of crystal = ---------- = ----------------------------------- = -----------------
a3 x d (100 x 10 -10 cm)3 x 10 -3 gcm−3 10- 24 x 10 -3

= 4 x 10 27

23. Atoms X and Y form bcc crystalline structure. Atom X is present at the corners of the
cube and Y is at the centre of the cube. What is the formula of the compound?

Nc 8
No of corner (X ) atoms = ----------- = ------ = 1
8 8
Nb 1
No of body centre (Y ) atoms = ----------- = ------ = 1
8 1
Formula of the compound = XY

24. Sodium metal crystallizes in bcc structure with the edge length of the unit cell
4.3 ×10−8 cm. calculate the radius of sodium atom.

Given: a = 4.3 ×10−8 cm.

√3 √3 1.732 x 4.3 ×10−8

For BCC r =----- a = -------- x 4.3 ×10−8 cm. = ---------------------- = 1. 786 x 10−8 cm
4 4 4

25. Explain what happens when ZnO is heated?

ZnO is colourless at room temperature.
When it is heated, it becomes yellow in colour.

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+2 CHEMISTRY Dr. C. ARUL JOSEPH RAJ

On heating, it loses oxygen and thereby forming free Zn2+ ions.

The excess Zn2+ ions move to interstitial sites and the electrons also occupy the interstitial
positions.

26. Explain Frenkel defect.

Frenkel defect arises due to the dislocation of ions from its crystal lattice.
The ion which is missing from the lattice point occupies an interstitial position.
This defect occurs when cation and anion differ in size.
Unlike Schottky defect, this defect does not affect the density of the crystal.
For example AgBr
In
n this case, small Ag+ ion leaves its normal site and occupies an interstitial position as shown in
the figure.

27. Explain hcp arrangement ( ABABA )

It is a hexagonal closed packing arrangement
• The first layer ‘a’. is formed by arranging the spheres as in the case of two dimensional
arrangements.
• The second layer ‘b’ is formed by placing the spheres in the depressions of the first layer.
• The formation
ion of second layer is obtained by placing the spheres on the depression (x) or (y).
• A tetrahedral void is formed. in the second layer (b) just above the void (x) off the first layer
(a)
• This constitutes four spheres – three in the lower (a) and one in the upper layer (b).
• When the centers of these four spheres are joined, a tetrahedron is formed.
• At the same time, the voids (y) in the first layer (a) are partially covered by the spheres of
layer (b), a octahedral void is formed in (a).
• This constitutes six spheres – three in the lower layer (a) and three in the upper layer (b).

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+2 CHEMISTRY www.nammakalvi.org Dr. C. ARUL JOSEPH RAJ

x – Tetrahedral void
y- Octahedral void

• When the centers of these six spheres are joined, an octahedron is formed. Simultaneously
new tetrahedral voids (or holes) are also created by three spheres in second layer (b) and one
sphere of first layer (a)

• The third layer is arranged as a first layer as shown in the figure. This “aba’’ arrangement is
known as the hexagonal close packed (hcp) arrangement.

• In this arrangement, the tetrahedral voids of the second layer are covered by the spheres of
the third layer.

• In hcp arrangements, the coordination number of each sphere is 12 – six neighbouring

spheress in its own layer, three spheres in the layer above and three sphere in the layer below.

28. How are crystalline solids classified?

i.Ionic solids ii. covalent solids iii. molecular solids iv. metallic solids
29. Explain Ionic solids.
• The structural units of an ionic crystal are cations and anions.
• They are bound together by strong electrostatic attractive forces.
• To maximize the attractive force, cations are surrounded by as
many anions as possible and vice versa.
• Many Ionic solids are cubic close packed. Example: NaCl crystal.

30 . Explain covalent solids.

• In covalent solids, atoms are bound together in a three dimensional network by covalent
bonds. Examples:
s: Diamond, silicon carbide
• Such crystals are very hard, and have high melting point.
• They are poor thermal and electrical conductors.

31 . Explain molicular solids.

• In molecular solids, the constituents are neutral molecules.

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+2 CHEMISTRY Dr. C. ARUL JOSEPH RAJ

• They are held together by weak van der Waals forces.

• Molecular solids are soft and they do not conduct electricity.
• These molecular solids are further classified into three types.

i. Non polar molecular solids

In non polar molecular solids constituent molecules are held together by weak dispersion forces
or London forces.
They have low melting points.
They are in liquids or gaseous state at room temperature.
Examples: naphthalene and anthracene

(ii) Polar molecular solids

The constituents molecules have polar covalent bonds.
They are held together by strong dipole-dipole interactions.
They have higher melting points than the non-polar molecular solids.
Examples are solid CO2 and solid NH3

iii. Hydrogen bonded molecular solids

The constituent molecules are held together by hydrogen bonds.
They are soft solids under room temperature.
Examples: solid ice (H2O), glucose, urea

32 . Explain Metallic solids:

In metallic solids, the lattice points are occupied by positive metal ions and a cloud of electrons
pervades the space.
They are hard, and have high melting point.
They possess excellent electrical and thermal conductivity.
They possess bright lustre.
Examples: Metals and metal alloys Cu, Cu- Zn alloy

33. Calculate the number of atoms in ecc and bcc unit cell.
Nc + Ne 8 12
No of atoms in ecc unit cell = ---- ---- = ------ + --------- = 1 + 3 = 4
8 2 8 4

Nc + Nb 8 1
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+2 CHEMISTRY www.nammakalvi.org Dr. C. ARUL JOSEPH RAJ

No of atoms in bcc unit cell = ---- ---- = ------ + --------- = 1 + 1 = 2

8 2 8 1

34. Barium has a body centered cubic unit cell with a length of 508pm along an edge. What
is the density of barium in g cm-33?
Solution:
nM
ρ =−−−−−−
a 3 NA

Given:
n =2 M = 137.3 gmol-1 a = 508pm = 5.08 X 10-8cm

2 atoms × 137.3 g mol-11 274.6

ρ = −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−
−−−−−−−−−−−−−−−−−−−−−−−−−−−−− = −−−−−−−−
(5.08 × 10 -8 cm )3 × (6.023
6.023 × 10-8 atoms mol-1 ) 131.10 x 10-24 x 6.023 x 10 23

274.6 274.6 x 10
= --------------------------- = ------------------- = 0.347 x 10 = 3. 47 g cm-3
131.10 x 6.023 x 10-1 789.6

35.. Calculate the percentage efficiency of packing in case of Sc cubic crystal.

Consider a cube with an edge leng

length = ‘a’.
Volume of the cube with edge length a is = a × a × a = a3
a
Let ‘r’ is the radius of the sphere. From the figure, a = 2r = r = ---------
4 2
Volume of the sphere with radius ‘r’ = --- πr3
3
4 a 3
= --- π ( ---- )
3 2

4 a3
=---- π x --------
3 8

π a3
= ------
6

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+2 CHEMISTRY Dr. C. ARUL JOSEPH RAJ

No of spheres of of unit cell S

SC = 1

π a3
Hence volume of sphere = 1 x ----------
6

Total volume occupied by spheres in unit cell

packing fraction =--------------------------------------------------------------
-------------------------------------------------------------- x 100
volume of unit cell

π a3
----------
6 100 π
= --------------- x 100 = ------------
a3 6

100 x 3.14
= --------------- = 52.3 %
6

Percentage efficiency of packing in SC = 52.3%

36.. Calculate the percentage efficiency of packing in case of face centered cubic crystal.

From the figure

AC = 4r

4r = a√2

a√2
r = ---------
4

In ∆ ABC

AC2 = AB2 + BC2

AC = √ AB2 + BC2

AC = √ a2 + a2 = √2 a2 = √2
√ a
4
Volume of the sphere with radius ‘r’ = --- πr3
3
4
3
= --- π (√2 a / 4)

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+2 CHEMISTRY www.nammakalvi.org Dr. C. ARUL JOSEPH RAJ

3
4 2√2 a3
=---- π x -------------------
3 4x4x4
2
√2 π a3
= -----------
24

No of spheres of unit cell FCC = 4

2√2 a3 2√2 a3
Hence total volume of all spheres = 4 x ---------- = ------------
24 6 6

Total volume occupied by spheres in unit cell

Packing efficiency = -------------------------------------------------------------- x 100
volume of unit cell

2√2 a3
----------
6
= --------------- x 100
a3

√2 π x 100
= -------------------
6

= 1.414 x 3.14 x 100

= -----------------------
6

Percentage efficiency of packing in fcc = 74. %

37. Write note on Impurity defect:

• Due to the presence of impurity ions in ionic solids causes vacancies in the crystal
lattice of the host.
• For example, addition of CdCl2 to silver chloride yields solid solutions where the
divalent cation Cd2+ occupies the position of Ag+.
• This disturbs the electrical neutrality of the crystal.
• In order to maintain the same, proportional number of Ag+ ions leaves the lattice.
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+2 CHEMISTRY Dr. C. ARUL JOSEPH RAJ

• This produces a cation vacancy in the lattice, such kind of crystal defects are called
impurity defects.

Dr. C. Aruljosephraj
P.G. Assistant in Chemistry,
St. Joseph’s Hr. Sec. School,
Manjakuppam,
Cuddalore – 607 001
9865480887

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