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The particles are very closely packed in some definite geometric pattern with very small voids. Inter-particles forces are very strong.
Partcle motion is restricted to vibratory motion only.
6. SPACE LATTICE
The geometrical form consisting only of a regular array of points in space is called a lattice or space lattice or it can be defined as an
array of points showing how molecules, atoms or ions are arranged in different sites, in three-dimensional space.
10. VOIDS
10.1 Octahedral Voids
The position in a close-packed unit cell where a foregin atom is in contact with six host atoms in the form o an octahedral is called
an Octahedral Void.
i) In FCC unit cell:
A. Octahedral void is existed at the centre of
each edge and hence there are 12 such
types of octahedral void.
B. One octahdral void is located at the centre of unit cell.
C. Contribution of each octahedral void existed
at the centre of each of the 12 edge is of
the volume of a void and contribution of
octahedral void existed at the centre of unit
cell is exactly volume of a void i.e., 1.
D. Hence, no. of effective octahedral void
1
no . of octahedral void existed at each edge+1 no . of octahedral void existed at the centre of unit cell .
4
1
12+1 1=3+1=4
4
Hence, no. of effective octahedral void in fcc unit cell = 4
But we have also, no. of effective atoms (as host atmos) in fcc unit cell = 4
Number of effective octahedral void = No. of effective host atoms
or , Number of effective foregin atoms = No. of effective host atoms
ii. In HCP Unit cell :
Since, no. of effective host atoms = 6
No. of effective octahedral void = 6
Hence, no. of effective octahedral void in a face centred cubic unit cell is 4 and in a Hexagonal close-packed (or Hexagonal primitive
unit cell) unit cell is 6.
iii) Radii (r) of the octahedral void = 0.414 R
10.2 Tetrahedral void
The position in a close-packed unit cell where a foreigb atom is in contact with four host atoms in the form of an tetrahedral is called
tetrahedral void.
Since, it is noted that,
The number of effective tetrahedral voids in a unit cell is double the number of effective atoms
in that unit cell.
i.e., No. of effective tetrahedral voids = 2 no. of effective atoms
i) In fcc unit cell,
No. of effecative tetrahedral voids = 2 no. of effective atoms
2 4=8
ii) In hcp unit cell
No. of effective tetrahedral voids = 2 no. of effective atoms 2 6=12
iii) Location of tetrahedral voids: Tetrahedral voids are presented on the body diagonals, and one body diagonal contains two
tetrahedral voids, since there are four body diagonal. Hence, there are eight tetrahedral void, each presented of the body diagonal
from each corners of the cube.
iv) Radius (r) of the tetrahedral void = 0.225 R
11. TYPES OF UNIT CELLS
11.1 Simple or primitive cubic unit cell
A cubic unit cell is said to be primitive if
i) All the eight corners of the cube are occupied by the same atoms.
ii) There is no such atoms present any where in the cube except corners.
1
iii) Contribution of each atom or sphere for one unit cell is 8 of the volume of each sphere.
r= a
3
4
3
4r
vi) Therefore, volume of unit cell
a3= ( )
3
And volume occupied by the spheres in the unit cell
=Z volume of a sphere
4 3
2 r [Z=2 for bcc]
3
4 r= 2 a
r= a
2
4
1
r= a ,a=2 2r
2 2
3
vii) Therfore, volume of unit cell a3=(2 2 r ) and volume occupied by the spheres in the unit cell
Z volume of a sphere
4 3
4 r
3
Volume occupied by the spheres the unit cell
viii)
Packing fracation ( PF )=
Volume of unit cell
2 2 r 3
4
4 r 3
3
0.7406
74.06
ix) Percentage of vacant space = (100 74.06)% = 25.94%
x) If the atoms present at the corners and at the face centred positions are of different types, then the unit cell is called pseudo fcc or fcc
like.
11.4 Hexagonal primitive unit cell (hcp)
A hexagonal primitive unit cell is said to be an ideal hexagonal primitive unit cell if
i) All the six corner of hexagonal contained same type of atoms i.e., bottom and top hexagonal, both have same atom at their corners.
ii) Each of hexagonal face contains same type of atom as that of corners atom.
iii) Upper and lowear hexagonal planes are same type and it is said to be A layer.
iv) Another layer is B layer, it is completely inside the unit cell. There are three atoms, present at this layer which is completely inside
the unit cell and area in contact to each other.
v) Contribution of each atom present at the twelve corners (six corner at bottom + six corner at top) of hexagonal primitive units cell is
1/6 of the volume of a atom and for each atom present at two hexagonal face is 1/2 of the volume of a atom and contribution of each
atom present inside the hexagonal primitive unit cell is 1.
vi) Therefore, number of effective atoms in a unit cell
= no. of corner atoms 1/ 6+ no. of face centred atom 1/2+ no. of atoms inside the hexagonal primitive unit cell
1
1 1
12 +2 +3 1
6 2
2+1+ 3
6
vii) The face centred atom is in contact with six spheres present at the corners of hexagon and two corner sphere are also in contact with
each other.
viii) If let us consider a is the length of hexagonal unit cell and r be the radius of sphere then a = 2r
Volume occupied by spherestheunit cell
ix) Packing fraction
( PF )=
Volume of unit cell
4 3 4 3
6 r 6 r
3 3
=
base area height
(6 43 a ) (4 r 23 )
2
4 3
6 r
3
=0.74=74
6
4
3 (2 r)2 4 r 2
3
Percentage of vacant space = (10074) = 26%
12. RADIUS RATIO RULES
For the stability of an ionic compound, each cation should be surrounded by maximum numbr of anions and vice versa (for maximum
electrostatic forces of attraction). The number of oppositely cahrged ions surrunding each ion is called it co-ordination number.
+
r
r
Radius of the anion
Radius of the cation
Radius Ratio=
Evidently, greater is the radius ratio, the larger is the size of the cation and hence greater is its co-ordination number. The relationships
between the radius ratio and the co-ordination number and the structural arrangement are called radius ratio rules, and are given in
table
solids is
AB2 .
iii) If hal o the tetrahedral holes are occupied then formula is AB,
The present section includes the studies on the structures of some binary compounds of AB type and
AB 2 type. NaCl, CsCl, ZnS,
etc. are examples of compounds o AB type while CaF2 , SrF2 are examples of compounds of
AB2 type.
13.1 Structure o sodium chloride (NaCl) : Rock salt Structure
i) In sodium chloride, chloride ions (denoted by fig) can be considered as having cubic close packed structure (i.e. face centred cubic).
ii) The sodium ions (represented by O) occupy the octahedral holes in the cubic close packed type lattice o chloride ions.
iii) There are six octahedral holes around each chloride ion, thereore each chloride ion is surrounded by six sodium ions. Similarly, each
sodium ion is surrounded by six chloride ions. Therefore, in NaCl co-ordination no. of
+
Cl ion is 6 and that of Na ion is also 6 i.e. a 6:6 co- ordination.
S 2
2+ 2 2 +
Zn /r
iii) For exact fitting of Zn ions is the tetrahedral voids, in the close packing of S
ions, the ratio should be
r
0.225, however this ratio is slightly large (0.40).
There are four Zn2+ ions and four S2 ions per unit cell
Thus , the number of ZnS units per unit cell is equal to 4.
Some more examples of ionic solids having zinc blende structure are CuCl, CuBr, Cul, Agl.
13.4 Structure of Calcium Fluoride or Fluorite structure
2+
CaF 2 ,
i) In Cs ions possess face centered cubic lattice. Fluoride ions occupy all
the
2+
tetrahedral voids in the lattice of Cs ions.
2+
ii) Each Cs is in constant with eight
fluoride ions and each fluoride ion is in
contact with four calcium ions. Thus co
2+
ordination no. of Ca ions is 8 and that
of fluoride ions is 4. So calcium fluoride
has 8:4 co-ordination.
iii) In calcium fluoride each unit cell has
four calcium ions and eight fluoride
ions as shown below
Thus, numbe of
CaF 2 units per cell is 4. Other examples of compounds having fluorite stucture are SrF 2 and CdF 2 .
2 +
i) The O
ions constitue a ccp type of lattice and the Na ions occupy all the tetrahedral voids.
2 ,
ii) The oxide ion, O is in contact with eight sodium ions whereas in turn each Na+ ion is in contact with four oxide ions. Thus
13.6 Structure of
Fe3 O 4 (Magnetite)
3+
Fe2 O3 . In Fe3 O 4 , oxide ions arranged
In Fe3 O 4 , Fe ions are present in the ratio 2 : 1 and may be considered as FeO.
2+ 3+
MgFe2 O4 also has similar structure of magnetile,
in ccp. Fe ions occupy octahedral voids while Fe ions are equally
2+ 2+
in which Fe3 O 4 .
Mg ions are present in place of Fe ion in
13.7 Normal Spinel Structure
2+ 1
In spinel, a mineral
MgAl 2 O4 , oxide are arranged in ccp with th of tetrahedral voids and
Mg ions occupied 8
3+ 1
ZnFe 2 O4 also possess spinel structure. These are very
Al occupied 2 of octahedral voids. Many ferites (such as
important magnetic materials and are used in telephones and memory loops, in computers.
Fe
Magnetic also possess spinel structure. Hence divalent ions 2+ are in octahedral voids while the trivalent ions are in a set of
tetrahedral voids.
13.8 Structure of Calcium Carbide
The structure of
CaC 2 is similar to that of sodium chloride in which sodium ions are replaced by calcium ions while chloride ions
by carbide ions. The carbon atoms in carbide are associated in pairs, which are aligned in parallels.
Unlike sodium chloride, the cubic symmetry is distorted in calcium carbide.
The structure of
FeS2 similar to that of CaC 2 , the S 2 units in FeS2 , do not align parallel.
4 + 2 2
In rutile structure each Ti ion is surrounded by six O ions arranged in a distorted octahedron and each O ion is
4 +
Ti ions arranged in a planar triangular manner. Thus, the co-ordination numbers of Ti and O and 6 and
4+ 2
surrounded by three
3, respectively.
The structure of titanium dioxide cannot be considered to be cubic as one of the axes is shorter than the other by 30 percent.
The brief study on some ionic cubic solids is reported in table.
13.10 Characterstic of Some Cubic Ionic Solids.
13.11 Effect of Temperature and pressure on Crystal Structure Conversion of NaCl into CsCl Structure and Vice versa. On
applying high pressure, NaCl structure having 6 :6 co-ordination changes to CsCl structure having 8:8 co-ordination. Similarly, CsCl
having 8 : 8 co-ordination on heating to 760 K changes to NaCl structure having 6 : 6 co-ordination. Thus increase of pressure
increases the co-ordination number whereas increase of temperature decreases the co-ordination number.
2+
3+ 2+
number of Fe ions in these octahedral voids are replaced by Fe ions (of course every three Fe ions would be replaced by two
Fe3+ ions to maintain electric neutrality). Consequently we get Fe deficient crystal.
ii) Structure of Fe2O3. If all the Fe2+ ions are replaced by Fe3+ ions, then as every three Fe2+ ions can be replaced by two Fe3+ ions, then
as every three Fe2+ions can be replaced by two Fe3+ ions to maintain electrical neutrality, the ratio between Fe and O will now be 2:3
and not 1:1 i.e. we get the oxide Fe2O3.
iii) Structure of Fe3O4 (magnetite). This oxide is obtained by replacing exactly two thirds of Fe2+ ions (in the structure of FeO) by Fe3+
ions. The remaining Fe2+ ions as well as 50% of the Fe3+ ions occupy the octahedral voids whereas the remaining 50% of the Fe3+ ions
occupy the tetrahedral voids.
iv) Ferrites. In the structure of Fe3O4, if Fe2+ ions are replaced by divalent cations such as Mg2+, Zn2+ etc. the compounds obtained are
called ferrites. Thus ferrites are the compounds having the general molecular formula A Fe2O4 where A is a divalent cation such as
Mg2+ orZn2+ i,e. these of Fe3O4 by divalent cation such as Mg2+or Zn2+ i.e. these are obtained by replacing Fe2+ ions in the stucture of
Fe3O4 by divalent cations. These belong to the general category of compounds having the formula AB2O4 where A is a divalent cation
and B is a trivalent cation e.g., B3+, Fe3+ or Al3+. In these compounds, divalent cation occupy tetrahedral voids whereas trivalent cations
occupy octahedral voids. This type of arrangment is called spinel structure. Most of the ferrites having spinel structure are used in
telephone as well as in memory loops of computers.
14. CALCULATION OF DENSITY OF A CUBIC CRYSTAL FROM ITS EDGE.
Knowing the edge of a cubic crystal from X ray studies and knowing the type of crystal structure possessed by it so that the number
of particles per unit cell are known, the density of the crystal can be calculated.
14.1 For cubic crystals elements.
Suppose the edge of the unit cell = a pm
Number of atoms present per unit cell = Z
Atomic mass of the element = M
a pm
Volume of the unit cell pm
Massof the unit cell
Density of the unit cell
Volume of the unit cell
Mass of the unit cell = Number of atoms in the unit cell Mass of each atom Z m
Atomic mass M
m= =
Where Avogadro s number N 0
'
Z M /N o
Density of the unit cell = 3 30
a 10
i.e.
14.2 For cubic crystal of ionic compounds. The formula is the same except the now Z is the number of formula units present in one
unit cell and M is formula mass.
ZM
kg m3
Note. In terms of SI units, M is kg mol1, a is in meters, than 3
a No
15. SOME IMPORTANT RELATIONSHIPS
Let radius of the atom in the packing = r, edge length of the cube = a, volume of the cube V =a3
4 vz 3
Volume of the atom (spherically)
v = r 3 z , thn packing density = 3
3 Z a
A few examples of ionic compound exhibiting Schottky defect are NaCl, KCl, KBr and CsCl.
Effect on density. As the number of ions decreases as a result on this defect, the mass decreases whereas the volume remains the
same. Hence the density of the solid decreases.
17.1.2 Frenkel defect. If an ion is missing from
Its lattice site (causing a vacancy or
a hole there) and it occupies the interstitial
site, electrical neutrality as well as the
stoichiometry of the compound are
maintained. This type of defect is called
Frenkel defect. Since cations are usually
smaller, it is more common to find the
cations occupying interstitial sites.
The above two defects are called intrinsic defects or thermodynamic defects.
The Frenkel defect in which one cation is called missing from the lattice site and is occupying the interstitial site is shown in fig.
Types of compounds exhibiting Frenkel defects. This type of defect is present in those compounds, which have
i) low co-ordination number and
ii) larger difference in the size of cations and anions
A few examples of ionic compounds showing this defect are AgCl, AgBr, Agl, ZnS etc.
Effect on density. Since no ions are missing from the crystal as a whole, therefore density of the solid remains unchanged.
17.1.3 Some other consequences of Schottky and Frenkel defects
Solids having these defects conduct electricity to small extent. This is because if an ion moves from its lattice site to occupy a hole it
creates a new hole. In which way a hole moves across the crystal, which as a result moves a charge in the opposite direction.
Due to presence of holes, the stability (or the lattice energy) of the crystal decreases. In Frenkel defect, similar charges come closer.
This results in the increase of dielectric constant of the crystals.
17.1.4 Differnece between Shottky and Frenkel defects. The main points of difference are listed below
17.2 Non Stoichiometric Defects. If, as a result of the imperfections in the crystal, the ratio of the caions to the anion becoms different
from that indicatd by the idea chemical formula, the defects are called non stoichiometric defects.
These defects result in either excess of the metal atoms or excess of the non-metal atoms (or deficiency of the metal atoms). These can
occur as follows
17.2.1 Metal excess. This may occur in either of th following two ways:-
i) By anion vacancies. A negative ion may be missing form its lattice site, leaving a hole which is occupies by an electron, thereby
maintaining the electrical balance. The electrons thus trapped in the anion vacancies are called F centres F centres because they
are responsibl for imparting colour to the crystals (F Farbe which is a German word for colour).
For example, which NaCl is heated in an atmosphere of Na vapour, the excess of Na atoms deposit on the surface of NaCl crystal. Cl
ions then diffuse to the surface where they combine with the Na atoms, which become ionized by losing electrons.
This defect is similar to Schottky defect and is found in crystals having Schottky defects.
ii) By the presenc of extra cations
in the interstitial sites. Metal excess
may also be caused by an extra cation
occupying the interstitial site. Electrical
neutrality is maintained by an electron
present in another intrstitial sit. This
defct is similar to Frenkel defect and
is found in crystals having Frenkel defects.
For example, when ZnO is heated, it loses oxygen and turns yellow due to
following reaction.
1
2++ O2 +2 e
2
ZnO Zn
2+
The excess of Zn ions thus formed get trapped into the vacant interstitial sites and the electrons in the neighbouring interstitial
sites.
Crystals with either type of metal excess defects contain some free electrons. Hence such materials acts as semi-conductors.
17.2.2 Metal Deficiency. This defect occurs when the metal shows variable valency i.e. for transition metals. The defect usually occurs
due to the missing of a cation from its lattice site and the presence of the cation having higher charge (e.g., +2 instead of +1) in th
adjacent lattice site. Examols include FeO, FeS and NiO.
17.3 Impurity Defects. These defects arise when foreign atoms are present at the lattic site (in place of host atoms) or at the vacatn
interstitial sites. In the formers cas, we get substitutional solid solutions while in the latter case, we get interstitial solid solutions. The
formation of the former depends upon the electronic structure of the impurity while that of the latter on the size of the impurity.
17.3.1 Introducing impurity defect in covalent
solids. For example group 13 elements such P
and As enter Ge or Si of group 14
substitutionally. The group 15 elements have
one excess valence electron (compared to Si or
Ge) after formed by group 14 elements. The
Excess electrons give rise to electrical
conduction.
A group 13 element, which has only three valence electrons forms an electron
Deficient bond or a hole. Such hols can move across the crystal giving rise to electrical conductivity. Thus impurity doped * Si and
Ge and semi conductors whose conductiveiy increases with increasing temperature. This is unlike metals whose conductivity
decreases with increase of temperature.
Group 14 elements doped with group 15 elements are called n type semi conductore, the symbol n indicating that negative charge
flows in them. Group 14 elements doped with group 13 elements are called p type semiconductors, the symbol p indicating the
movement of positive hole through the lattice.
17.3.2 Introducing impurity defect in ionic solids. In case of ionic solids, the impuritis are introudced by adding impurity of ions. If
the impurity ions are in a different valence state from that of the host ions, vacancies are created. For example, if molten NaCl,
containing a little SrCl2 as impurity is allowed in cool, in the crystal of NaCl formed, atsome lattice sites Na+ ions are substituted by
Sr2+ ion. For every Sr2+ ion. For every Sr2+ ion thus introduced, two Na+ ions are removed to maintain electrical neutrality. One of thse
lattice sites is occupied by Sr2+ ion and the other remains vacant. These vacancies result in th highr electrical conductiveiy of the solid.
18. PROPERTIES OF SOLIDS
The three main properties of solids which depend upon their structure and composition are briefly described below:-
18.1 Electrical Properties. Based on their conductivity, solids can be divided into three categories:
i) Conductors. The solids through which electricity can flow to a large extent are called conductors. They are further classified as
metallic conductors and electrolytic conductors. In the metallic conductors, the flow of electricity is due to flow of electrons
(electronic conductors) without any chemical change occuring in the metal. In case of electrolytic conductors like NaCl, KCl etc., the
flow of electricity takes place to a good extent only when they are taken in the molten state or in aqueous solution. The flow of
electricity is due to flow of ions. However, in the solid state they conduct electricity only to a small extent which is the due to the
presenc of defects (holes, electrons etc).
ii) Insulators. The solids which almost do not allow the electricity to pass through them are called inculators e.g. S, P, lastic, wood,
rubber, etc.
iii) Semi conductors. The solids whose conductivity lies between those of metallic conductors and inculators are called semi-
conductors. The electrical conducativiey of semi conductors and insulators is due to the presence of impurities and defects. Their
conductivity increases with increase in temperature as the defects (such as holes) increase with increase of temperature.
Similar variation is observed among the sulphides of transition elements.
18.2 Magnetic Properties. Based on the behaviour in the external magnetic field, the substances are divided into different categories as
explained below:-
i) Diamagnetic substances. Substances, which are weakly repelled by the external magnetic field are called diamagnetic substances e.g.
TiO2, NaCl, benzene etc. the property thus exhibited is called diamagnetism. This property is shown only by those substances which
contain fully filled orbitals i.e. no unpaired electrons is present. the magnetic moment possessed by an electron with spin in one
direction is cancelled by that with spin in the opposite direction.
ii) Paramagnetic substances, Substances, which are attracted by the external magnetic field are called paramagnetic substances. The
property thus exhibited is called parmagnetism. This property is shown by those substances whose atoms, ions or molecules contain
unparied electrons e.g. O2, Cu2+ , Fe3+ etc. These substances, however, lose their magnesium in the absence of the magnetic field .
iii) Ferromagnetic substances. Substances which show permanent magnetism even in the absence of the magnetic field are called
ferromagnetic substances, e.g., Fe; Ni, CO, CrO2 show ferromagnetism. Such substances remain permanently magnetized, once they
have been magnetized. This type of magnetism areises due to spontaneous alignment of magnetic moments due to unpaired electrons
in the same direction, as shown in fig. this is a case of large amount of paramagnetism.
iv) Anti-ferromagnetism substances. Substances which are expected to possess paramagnetism or ferromagnetism on the basis of
unpaired electrons but actually they possess zero net magnetic moment are called anti-ferromagnetism is due to the presence of equal
number of magnetic moments in the opposite directions as shown in fig.
v) Ferrimagnetic substances.
Substances which are expected to
possess large magnetism on the basis
of the unpaired electrons but actually
have small net magnetic moment are
called ferrimagnetic substance e.g.,
2+ Fe2 O 4
Fe3 O 4 , ferrites of the formula
M
where M =Mg , Cu , Zn etc .
Ferromagnetism arises due to the unequal number of magnetic moments in opposites direction
reulting in some net magnetic moment, as shown in fig.
It may be noted that ferromagnetic, anti ferromagnetic and ferrimagnetic solids change
into paramagnetic ato some temperature. For examole, ferrimagnetic Fe 3O4 on heating to 850 K becomes paramagnetic. This is due to
greater alignment of spins in one direction on heating. It may be further. Pointed out here that each ferromagnetic substance has a
characterstic temperature above which no ferromagnetism is observed. This is known as curie temperature.
MAGNETIC PROPERTIES OF SOLIDS
18.3
Dielectric Properties. Insulators do not conduct electricity because to the electrons present in them are held tightly to the individual
atoms or ions and are not free move. However, when electric field is applied, polarization takes place because nuclei are attracte to
one side and the electron cloud to the other side. These newly formed dipoles may align themselves in an ordered manner so that
such crystals have a net dipole moment. Such polar crystals show the following interesting electrical properties:
dispersion forces these forces are attractive is nature and the interaction energy due to this is propotional to ( r1 ) .
6 Thus, these
1
forces are important at short distance ( )
r
6 Thus, these forces are important at short distances ( 500 pm this force also
the information of an induced dipole moment. The interaction energy is also proportional to 1/r 6 and also depends upon (1)
dipole moment of the permanent dipole and (2) the polarizability of the second molecule. molecules of larger size have higher
polarizability. Interaction between tow dipolar molecules also includes additive dipole-dipole induced interactions.
20. SUPERCONDUCTIVITY
When any material loses its resistance for electric current, then it is called superconductor. Kammerlingh Onnes (1913) observed
this phenomenon at 4 K in mercury. The materials offering no resistance to the flow of current at very low temperature (2-5 K) are
called superconducting materials and phenomenon is called superconductivity.
Examples are :
i) Nb3Ge alloy (before 1986)
ii) La1.25Ba0.15CuO4(1986)
iii) Yba2 Cu3O7 (1987)-superconductive at a temperature upto 92 K.
Superconductore find applications in
i) electronics
ii) building supermagnets
iii) levigation transport
iv) power transmission.
The temperature at which a material enters the superconducting state is called the superconducting transition temperature, Tc.
Superconductivity was also observed in lead at 7.2 K and in tin at 3.7 K. Among the more familiar superconductors are those described
as A 15 superconductors (A 15 is acrystallographic symbol for the -tungstn structure)
The phenomenon of superconductivity has also been observed in other materials such as polymers and organic crystals. Example are
i) (SN)x, polythiazyl, the subscript x indicates a large number of variable size.
ii) (TMSF)2PF6. TMTSF is tetra methyl tetra selena fulvalene.
21. LIQUID CRYSTALS
At a certain temperature, many-substances (about 0.5% of known compounds) exist in a phase that is neight fully liquid nor fully
solid. The molecules in these liquid can move around, as in viscous liquids, but have a restricted rang of motion, as in solids. Several
different liquid crystalline phases exist, depending on the amount ordering. Two of the most common are the
Nematic phase: in which the ends of the molecules are randomly arrange.
Smectic phase : in which the molecules are arranged in layers.
The widespread use of liquid crystals for displays (LCD) in digital watches, pocket calculators and laptop computer screens hinges on
the fact that the orientation of liquid-crystal molecules in extremly sensitive to the presence of small electric fields and to the nature of
nearby surfaces.
EXAMPLES
Example:1. An element crystallizes into a structure which may be describd by a cubic type of unit cell having one atom on each
24 3
corner of the cube and two atoms on one of its diagonals. If volume of this unit cell is 24 10 cm and density of the
element is 7.2 g cm3, calculate the number of atoms present in 200 g of the element.
Example:2 In the compound AX, the radius of A+ ion is 95 pm and that of X- ion is 181 pm. Predict the crystal structure of AX
and write to co-ordination numbers of each of the ions.
Example:3 A compound formed by elements X and Y crystallises in a cubic closed packed lattice of Y atoms and all octahedral
voids are filled by X atoms. What is the formula of the compound?
Example:4 The unit cell length of NaCl is observed to be 0.5627 nm by X-ray diffraction studies; th measurd density of NaCl is
2.164 gcm3. Correlate the difference of observed and calculated density and calculate % of missing Na + and Cl ions.
Example:5 In a cubic lattic, the closed packed structure of mixed oxides of the lattice is made up of oxide ions; one fourth of the
tetrahedral voids are occupied by divalent ions (A2+) while one half of th octahdral voids are occupied by trivalent ions (B3+).
What is the formula of the oxides?
Example:6 At 14250C Fe crystallizes in a body-centred cubic lattice whose edg length is 2.393 . Assuming the atoms to be packed
spheres, calculate:
a) the radius of the spheres,
b) the distance between centres of neighbouring spheres,
c) the number of atoms of Fe per unit lattice, and
d) the total volume occupied by an atom of F.
Example:7 CsCl has cubic structure of ions in which Cs+ ion is present in the body centre of the cube. If density is 3.99 g cm3
a) Calculate the length of the edge of a unit cell
b) What is the distance between Cs+ and Cl ion?
c) What is the radius of Cs+ ion if the radius of Cl ion is 182 pm.
Example:8 The metal ion-halide ion distance in several alkali metal halides are given below:
Distance nm,
Cl
I
+ 0.310 0.249
Li
+ 0.317 0.279
Na
+ 0.352 0.314
K
+ 0.367 0.329
Rb
Suggest why there is such a small difference in internuclear distance between LiI and NaI compound to that between LiCl and
NaCl.
Examample:9 Suggest the probable structure of the unit cells of the following:
Species r+ r
a) RbBr 1.48 1.95
b) MgTe 0.65 2.21
c) MgO 0.65 1.40
d) BaO 1.35 1.40
Example: 10 The redius of calcium ion is 94 pm and of an oxide ion is 146 pm. Predict the crystal structure of calcium oxide.
Example:11 The diffraction of barium with X radiation of wavelength 2.29 gives a first order reflection at 30 0. What is the
distance between the diffracted planes?
Example:12 The length of the unit cell edge of a bcc lattice metal is 352 pm. Calculate radius of the atom of the metal.
Example:13 The composition of a sample of wustite is Fe0.93O. What percentage of the iron is present in the form of Fe(III)?
Example:14 If NaCl is doped with 103 mol% of SrCl2, calculate the concentration of cation vacancies.
Example:15 Ice crystallises in a hexagonal lattice. At the low temperature at which the structure was determined, the lattice
constants were a = 4.53 and b = 7.4 . How many H2O molecules are contained in a unit cell? d(ice) = 0.92 g/cm3.
Example:16 Calcium crystallises in a face-centred cubic unit cell with a = 0.556 nm. Calculate the density, if
i) It contained 0.1% Frankel defects,
ii) It contained 0.1% Schottky defects.
Example:17 Zeolite is not a silicate of:
a) Al b) Hg
c) Na d) Na and Al containing X number of H2O moles.
Example:18 Potassium has a bcc structure with nearest neighbour distance 4.52 . Its atomic weight is 39. Its density will be:
a) 454 kg m3 b) 804 kg m3
3
c) 852 kg m d) 908 kg m3
Example 19 In a crystal, th atoms arelocated at the position of
a) maximum P.E. b) minimum P.E.
c) zero P.E. d) infinite P.E.
Example :20 In the crystalline state of an ionic comound MX of a metal M. having cations and anions of radius r M and rX
respectivel, the co-ordination number of M will be 4 if the value of rX/rM and rX respectively, the co-ordination number of M will
be 4 if the value of rX/rM is between:
a) 1 and 1.4 b) 1.4 and 2.4
c) 2.4 and 4.6 d) 4.6 and 5.6
Example:21 The second order Bragg diffracation of Xray with =1.0 from a set of parallel planes in metal occurs at an
angle 600. The distance between the scattering planes in the crystal is
a) 0.57 b) 1.00
c) 1.15 d) 2.00
Example:22 The number of unit cells in 119 g of KBr is nearly:
a) 6 1020 b) 3 1022