Beruflich Dokumente
Kultur Dokumente
1. Bonding in solids
Ionic bond,
covalent bond,
Metallic Bond,
Hydrogen Bond,
Vander-Waal’s Bond,
1. Space Lattice,
2. Unit cell,
3. Lattice parameters,
4. Crystal systems,
5. Bravais Lattices,
6. Miller Indices,
9. Atomic Radius, Coordination number and packing factor of SC, BCC, FCC.,
CONTENTS
Introduction
Ionic bond,
covalent bond,
Metallic Bond,
Hydrogen Bond,
Vander-Waal’s Bond,
INTRODUCTION
Electrical forces are responsible in binding the atoms and the molecules giving different physical
properties of the solid. A solid is composed of billions of atoms packed together closely. According to the
strength and directionality, the bonds are categorized into two main groups namely primary and
secondary. Primary bonds are formed by virtue of their nature and interatomic bonds. The secondary
bonds are intermolecular bonds.
IONIC BOND
In ionic crystals one or more electrons of one type of atoms are transferred to
another atom and the result being a crystal that is composed of positive and negative ions . The
electronic configuration of the ion is essentially an inert gas configuration. The electrostatic
interaction between the ions is the source of cohesive energy that binds the crystal together.
bonding in NaCl
The minimum energy required to detach an electron from Na atom is called as its ionization
energy.
COVALENT BOND
In this bonding the valence electrons are not transferred from one atom ato the other
atom but the neighbouring atoms share their valence electrons under the formation of a strong
covalent bond.
The simplest case of a single covalent bond occurs in the hydrogen molecule
BONDING IN HYDROGEN
In the molecular orbital of hydrogen, the two electrons are equally shared between
the nuclei and cannot be specifically identified with either nucleus.
The two electrons are more likely to be found between the two nuclei and thus the electron
density is relatively high.
Consider the case of chlorine atom which has seven electrons in its outermost orbit.
The spins of six electrons are paired, whereas the spin of the seventh electron is unpaired. The
unpaired electron is always looking for another unpaired electron which comes closer to it. In
such case when another chlorine atom comes near the first chlorine atom, the two unpaired
electrons of the two chlorine atoms get paired such that their spins are anti parallel.
In metallic bonding, the valence electrons which hold the atoms together are
not bound to individual atoms or pair of atoms but move freely throughout the whole metal.
Metallic elements have low ionization energies and the atoms give their valence electrons to
form and electron cloud or electron gas throughout the space occupied by the atoms. After losing
their valence electrons, the atoms are in reality positive ions. These ions are held together by the
forces that are similar to those of ionic bond and in that they are primarily electrostatic, but are
between the ions and the electrons. Most of the metals have one or two valence electrons. These
electrons are loosely held by their atoms and therefore can be easily released to form an electron
cloud.
The electrostatic interaction between the positive ions and the surrounding electron
cloud hold the metal together. It is called as metallic bond. The metallic crystals have high
electrical and thermal conductivities. Metals may be deformed without fracture because the
electron gas permits atoms to slide fast on one another by acting as lubricant. Carbon material
also available in the form of graphite. In graphite covalency is not fully achieved, hence they
may easily reform into metallic bond and there by graphite can have good electrical conductivity.
If any potential difference is applied between the two ends of a metallic rod, electron gas flows
easily and constitutes an electric current.
As the name "hydrogen bond" implies, one part of the bond involves a hydrogen atom. The hydrogen
must be attached to a strongly electronegative heteroatom, such as oxygen, nitrogen or fluorine, which is
called the hydrogen-bond donor. This electronegative element attracts the electron cloud from around the
hydrogen nucleus and, by decentralizing the cloud, leaves the atom with a positive partial charge.
Because of the small size of hydrogen relative to other atoms and molecules, the resulting charge, though
only partial, nevertheless represents a large charge density. A hydrogen bond results when this strong
positive charge density attracts a lone pair of electrons on another heteroatom, which becomes the
hydrogen-bond acceptor.
The hydrogen bond is not like a simple attraction between point charges, however. It possesses some
degree of orientational preference, and can be shown to have some of the characteristics of a covalent
bond. This covalency tends to be more extreme when acceptors bind hydrogens from more
electronegative donors.
Strong covalency in a hydrogen bond raises the questions: "To which molecule or atom does the
hydrogen nucleus belong?" and "Which should be labelled 'donor' and which 'acceptor'? According to
chemical convention, the donor generally is that atom to which, on separation of donor and acceptor, the
retention of the hydrogen nucleus (or proton) would cause no increase in the atom's positive charge. The
acceptor meanwhile is the atom or molecule that would become more positive by retaining the positively
charged proton. Liquids that display hydrogen bonding are called associated liquids.
The most ubiquitous, and perhaps simplest, example of a hydrogen bond is found between water
molecules. In a discrete water molecule, water has two hydrogen atoms and one oxygen atom. Two
molecules of water can form a hydrogen bond between them. The oxygen of one water molecule has two
lone pairs of electrons, each of which can form a hydrogen bond with hydrogens on two other water
molecules. This can repeat so that every water molecule is H-bonded with four other molecules (two
through its two lone pairs, and two through its two hydrogen atoms.)
H-O-H...O-H2
Liquid water's high boiling point is due to the high number of hydrogen bonds each molecule can have
relative to its low molecular mass. Water is unique because its oxygen atom has two lone pairs and two
hydrogen atoms, meaning that the total number of bonds of a water molecule is four.
In ice, the crystalline lattice is dominated by a regular array of hydrogen bonds which space the water
molecules farther apart than they are in liquid water. This accounts for water's decrease in density upon
freezing. In other words, the presence of hydrogen bonds enables ice to float, because this spacing
causes ice to be less dense than liquid water.
Were the bond strengths more equivalent, one might instead find the atoms of two interacting water
molecules partitioned into two polyatomic ions of opposite charge, specifically hydroxide and hydronium.
(Hydronium ions are also known as 'hydroxonium' ions).
H-O- H3O+
Indeed, in pure water under conditions of standard temperature and pressure, this latter formulation is
applicable only rarely; on average about one in every 107 molecules gives up a proton to another water
molecule, in accordance with the value of the dissociation constant for water under such conditions.
Vander-Waal’s Bond
A weak force of attraction between electrically neutral molecules that collide with or
pass very close to each other. The van der Waals force is caused by the attraction
between electron-rich regions of one molecule and electron-poor regions of another
(the attraction between the molecules seen as electric dipoles). The attraction is
much weaker than a chemical bond. Van der Waals forces are the intermolecular
forces that cause molecules to cohere in liquid and solid states of matter, and are
responsible for surface tension and capillary action.
NaCl is the best example for ionic crystals . First consider Na atom with electronic configuration
1s2 2s2 2p6 3s1 .
There is a single electron in its outermost orbital . It can be detached easily . It takes minimum
energy to detach an electron from Na. This energy is called Ionisation energy .
Na + I.E Na+ e-
Consider chlorine atom with electronic configuration 1s2 2s2 2p6 3s1 3s5 .
It needs one electron to attain inert gas configuration . It accepts an electron and releases some
energy is called electron affinity .
The next energy required to create Nal+ and Cl- pair is equal to 5.1 eV - 3.6 eV = 1.5 eV .
= joule
2.1 INTRODUCTION
One has to understand the crystal structure (arrangement of atoms) thoroughly
because solids have specific properties which depend on the structure. The materials are
generally classified into (i) solids, (ii) liquids and (iii) gases. Solids are further classified into
Crystalline and Non-Crystalline (Amorphous) solids depending on the arrangement of atoms. If
the atoms are arranged periodically throughout the solid then it is said to be crystalline otherwise
it is said to be non crystalline solid. The atoms / molecules are electrically neutral. But when
atoms or molecules are brought closer together, a repulsive force operates between the similar
charges in the atoms or molecules. An attractive force operates between the dissimilar charges.
The ultimate force, holding the particles together in solids, is the resultant of attractive and
repulsive forces (figure 1)
There appears a least distance, at which the particle cluster is the most stable. This minimum distance
between the particles is the equilibrium distance (r0). The arrangement of particles in crystals is decided
by the nature of bond between the particles and the value of the equilibrium distance. The atoms /
molecules in the solids are held together either by (1) Ionic bonds, (2) Covalent bonds, (3) Metallic bonds
or (4) Molecular bonds.
2.3UNIT CELL
The crystal structure of a material or the arrangement of atoms within a given type of
crystal structure can be described in terms of its unit cell. The unit cell is a small box
containing one or more atoms, a spatial arrangement of atoms. The unit cells stacked in
three-dimensional space describes the bulk arrangement of atoms of the crystal. The crystal
structure has a three dimensional shape. The unit cell is given by its lattice parameter which
are the length of the cell edges and the angles between them, while the positions of the atoms
inside the unit cell are described by the set of atomic positions (xi , yi , zi) measured from a
lattice point.
Let us consider a unit cell with volume V(incm3), which can be calculated from
the unit cell dimensions. Let ρ(gm/ cm3) be the density of the crystal. Then the weight of the
matter in the unit cell will be V x ρ.
If n be the number of atoms or molecules per unit cell and M be the atomic
(molecular) weight of one atom or molecule. The weight of the matter in the unit cell will be
given by the expression-
n * M * 1.66*10-24 gms.
Where 1.66X 10-24 is the weight of hydrogen atom in gms. used in converting molecular weight
in gms. Thus we have,
n = (V*ρ*N)/(M)
where N is the Avagadro number equal to 6.023* 10-23 The volume of the different lattice is as
given here:
1. Cubic a3
3. orthorhombic abc
4. Rhombohedral ½ a3 sin(α/2)cos(α/2)
5. Trigonal a2c
The lattice constant [or lattice parameter] refers to the constant distance between
unit cells in a crystal lattice. Lattices in three dimensions generally have three lattice constants,
referred to as a, b, and c. However, in the special case of cubic crystal structures, all of the
constants are equal and we only refer to a. Similarly, in hexagonal crystal structures, the a and b
constants are equal, and we only refer to the a and c constants. A group of lattice constants could
be referred to as lattice parameters. However, the full set of lattice parameters consist of the
three lattice constants and the three angles between them.
For example the lattice constant for a common carbon diamond is a = 3.57Å at
300 K. The structure is equilateral although its actual shape can not be determined from only the
lattice constant. Furthermore, in real applications, typically the average lattice constant is given.
As lattice constants have the dimension of length, their SI unit is the meter. Lattice constants are
typically on the order of several angstroms (i.e. tenths of a nanometre). Lattice constants can be
determined using techniques such as X-ray diffraction or with an atomic force microscope.
a≠b≠c
1 Triclinic 1 Primitive
α≠β≠γ
2 Primitive
a≠b≠c
2 Monoclinic
α = β = 90° ≠ γ
3 Body Centered
4 Primitive
5 Base Centered
a≠b≠c
3 Orthorhombic
α = β = γ = 90°
6 Body Centered
7 Face Centered
8 Primitive
a=b≠c
4 Tetragonal
α = β = γ = 90°
9 Body Centered
a=b=c
5 Trigonal 10 Primitive
α = β = γ < 120°, ≠ 90°
a=b≠c
6 Hexagonal 11 Primitive
α = β = 90°, γ = 120°
12 Primitive
a=b≠c
7 Cubic 13 Body Centered
α = β = γ = 90°
14 Face Centered
where ni are any integers and ai are known as the primitive vectors which lie in different planes
and span the lattice. For any choice of position vector R, the lattice looks exactly the same.
Two Bravais lattices are often considered equivalent if they have isomorphic
symmetry groups. In this sense, there are Fig 4(a) Bravais lattices in three-dimensional space.
14 possible
The 14 possible symmetry groups of Bravais lattices are 14 of the 230 space groups.
Bravais Lattice
The Bravais Lattice has infinite number of lattice points in it. If a set of identical atoms /
molecules are substituted in the space lattice then the lattice is said to be Bravais lattice. The surroundings
of any atom/molecule is same as any other atom/molecule in the lattice. Otherwise it is said to be non-
Bravais lattice. Below are the some figures 4(a) to 4(e) representing both Bravais lattice and non- Bravais
+ / =
lattices.
Fig. 4(b)
Non-Bravais Lattice
2.8 MILLER INDICES
Figure-6
It is possible to define a system of parallel and equidistant planes which can be imagined to pass through
the crystal structure are called as “Crystal Planes”. The position of a crystal plane can be expressed in
terms of three integers namely “Miller indices”.
If x, y and Z are the starting co-ordinates for a plane then the Miller indices of the plane are obtained by
the following procedure:
Consider the x-m y- and z co-ordinates of the lattice points of the plane lying on the x -, y- and the z-
directions of a reference frame
Take the reciprocals of these x-, y- and z- co-ordinates values.
Convert these fractions into whole numbers by multiplying all the numbers by a common multiplier.
Then, if possible simplify these resulting numbers.
These simplified numbers, derived from the x-, y- and z- co-ordinates of the lattice points on the plane are
named as the h, k and l values of the plane and is called the Miller index of the plane. All the planes
parallel to this plane will have the same indices. So the hkl values for a plane also represent a family of
all the parallel planes. The miller index a set of parallel planes is written as <hkl).
6 3 3
X= a Y= b Z= c
5 4 2
x y z 6 3 3
a , b , c = 5 , 4 , 2
5 4 2
6 , 3 , 3
Multiplying throughout by least common multiple ‘4’ for the denominator, we have the Miller indices
(5 8 4)
If a plane is oriented parallel to a coordinate axis, its intercept with the coordinate is taken as infinity,
since the reciprocal of infinity is zero, the corresponding Miller indices value will also be zero.
Thus the Miller indices is a set of 3 lowest possible integers whose ratio taken in order is the same as that
of the reciprocals of the Miller integers of the planes on the corresponding axes in the same order. Similar
to the case of representation of directions in the space lattice, any given Miller indices set represents all
parallel equidistant crystal planes for a given space lattice. Owing the rotational symmetry, certain planes
which are not parallel to each other become in distinguishable from the crystallographic point of view. In
such cases, Miller indices are enclosed in braces {} instead of parenthesis or brackets, which represents
all the equivalent planes. For example in the case of cubic lattice, the 6 planes referring to 6 faces of a
unit cell are represented by the Miller indices as (1 0 0) (0 0 1) (010) (0 1 0) (0 0 1) collectively
designated as {1 0 0 }
Figure2
To get the interplanar distance, consider a plane ABC with Miller indices (hkl). In the reference frame,
draw a normal to the plane from the origin. Let OP is the normal to the plane ABC. Let angle POA =
α ’, and POB = β’ and POC =γ ’ be the angles made by the normal to the plane with the x, y and the z
directions. OP = d is the interplanar distance
But from the definition of Millers incise derived in the earlier section,
OP d
Cos α = =
OA a / h
OP d
Cos β = =
OB b / k
OP d
Cos γ = =
OC c / l
From solid geometry, Cos2 α + cos2 β + Cos2 γ =1
h2d 2 k 2d 2 l 2d 2
+ 2 + 2 =1
a2 b c
h2 k 2 l 2
d2 2 + 2 + 2 =1
a b c
1
d hkl = h k2 l2
2 2
2 + +
a b2 c2
1
1/ 2
dhkl = h 2 k 2 l 2
2 + 2 + 2
a b c
a
d hkl =
h + k2 +l2
2
Let us consider a unit cell with volume V(incm3), which can be calculated from the unit cell
dimensions. Let ρ(gm/ cm3) be the density of the crystal. Then the weight of the matter in the unit cell
will be V x ρ.
If n be the number of atoms or molecules per unit cell and M be the atomic (molecular) weight
of one atom or molecule. The weight of the matter in the unit cell will be given by the expression-
n * M * 1.66*10-24 gms.
Where 1.66X 10-24 is the weight of hydrogen atom in gms. used in converting molecular weight in gms.
Thus we have,
n = (V*ρ*N)/(M)
where N is the Avagadro number equal to 6.023* 10-23 The volume of the different lattice is as given here:
Crystal system Volume(V)
1. Cubic a3
3. orthorhombic abc
4. Rhombohedral ½ a3 sin(α/2)cos(α/2)
5. Trigonal a 2c
The 14 Crystal lattices are represented in table1 and the crystal systems with unit cells in table2
a≠b≠c
1 Triclinic 1 Primitive
α≠β≠γ
2 Primitive
a≠b≠c
2 Monoclinic
α = β = 90° ≠ γ
3 Body Centered
4 Primitive
5 Base Centered
a≠b≠c
3 Orthorhombic
α = β = γ = 90°
6 Body Centered
7 Face Centered
4 Tetragonal 8 Primitive
a=b≠c
9 Body Centered
α = β = γ = 90°
a=b=c
5 Trigonal 10 Primitive
α = β = γ < 120°, ≠ 90°
a=b≠c
6 Hexagonal 11 Primitive
α = β = 90°, γ = 120°
12 Primitive
a=b≠c
7 Cubic 13 Body Centered
α = β = γ = 90°
14 Face Centered
Table2
2.6 LATTICE CONSTANT AND DENSITY
Density is a macroscopic property. Basically it is the mass per unit volume. In case of crystals, mass
of atoms packed in a conventional unit cell per unit volume of the cell gives the density of the crystal.
Here m is the mass of atoms packed in the conventional unit cell of the crystal. V is the volume of the
unit cell. Mass of atoms packed in the conventional unit cell of the crystal. V is the volume of the unit
cell. Mass of an atom in the structure is given by the ratio of the atomic weight or Molecular weight
( M ) to the Avogadro number (NA). Mass of atoms contained in the conventional unit cell is then the
number of atoms in the unit cell times the mass of an atom. If there are n atoms in the conventional
unit cell, then, the mass of atoms in the unit cell is given by
nM
m= ----------(ii)
Na
From equation ( i ), mass of atoms in the unit cell in terms of the density of the crystal is given by,
m = ρV --------------(iii)
nM
ρ=
N AV
nM
Therefore ρ = kg / m 3
N Aa3
1/ 3
nM
The lattice constant ‘a’ =
N ρ A0
A
2.7 Atomic packing, Atomic radius, Lattice constant and crystal structure:
The number of atoms at equal and least distance from a given atom in the structure is the
coordination number can be taken as the first nearest neighbors of an atom in the structure.
Atomic packing factor is the ratio of the volume of the unit cell occupied by atoms to the net volume
of the unit cell
The following are the possible structures found in a cubic system of crystals, resulting due to the
kinds of packing of atoms,
n = [8 X (1 /8) ] =1
Figure3
3 Atomic radius R
4 Lattice constant r = 2r
v
=
( n ) X[4 / 3πr 3 ] = (n )( 4)( πr 3 ) = nπ
APF =
V a3 3( 2r )3 6
nπ
APF = = 0.523 = (52 %)
6
In body centered cubic structure, the space lattice is cubic. Atoms are placed at all lattice
locations and there will be an additional atom at the body center of the cubic unit cell. In this
structure, the atoms stacked along the body diagonal of the cubic unit cell are in contact. That is, the
atom at the body center of the unit cell will be in contact with all other atoms at the cubic lattice
locations of the unit cell. Each atom in the structure will have eight nearest neighbors (figure 13).
Thus, the co-ordination number for a body centered cubic structure is N = 8. In a body centered cubic
structure, the lattice constant (a), is the cube edge of the conventional unit cell.
Figure4
Let d be diagonal distance between the atoms in a plane of the unit cell. Then,
d 2 = (a 2 + a 2 ) = 2a 2 − − − − − − − (i)
D 2 = (d 2 + a 2 ) = ( 2a 2 + a 2 ) = 3a 2 − (ii )
But, the atoms along the body diagonal, are in contact, Therefore D = 4r
D2 = (4r)2 = 3a2,
Thus, the relation between the lattice constant (a ) and atomic radius is,
4r
a=
3
The atoms at the lattice locations are shared by eight unit cell. Therefore, each atom at the
lattice location of the unit cell contributes ( 1/8 ) to the unit cell. The number of atoms contained in
the unit cell of the structure is given by the number of lattice locations in the unit cell multiplied by
the contribution of the atom at each location plus the atom at the body center of the unit cell. That is
the number of atoms in a unit cell the simple cubic structure is given by
n = (no. of lattice locations X contribution of atoms at these location ) + ( atom at the body
center)
n = [ 8 X ( 1 X 8 ) ] + 1 =2
The parameters describing the structure of a body centered cubic structure are :
3 Atomic radius r
v = (n ) X [ 4/3π r3]
( n )( 4 / 3)( πr 3 ) 3 π(n )
APF =
[64 r 3
/( 3 3) ] =
16
= 0.68 (68 %)
In a face centered cubic structure, the space lattice is cubic. The conventional unit cell consists of
eight small cubelets. Atoms are placed at alternate lattice locations. The atoms stacked along the face
diagonal of the cubic unit cell are in contact. The atom at any lattice location of the unit cell will have
twelve nearest neighbors (figure14)
Fig-5
Let d be the diagonal distance between the atoms in a plane of the conventional unit cell. Then,
But, the atoms along the face diagonal of the conventional unit cell are in contact. Therefore,
d = 4r - - - - - - - ( ii )
d2 = ( 4r)2 = 2a2 ,
Thus, the relation between the lattice constant ( a ) and atomic radius is,
4r
A=
2
The atoms at the lattice locations of the conventional unit cell are shared by eight such
cells. Therefore each atom at the lattice location of the unit cell contributes ( 1 /8 ) to the unit cell.
The number of atoms belonging to the unit cell in the structure is given by the number of lattice
locations in the unit cell multiplied by the contribution of the atom at each location plus the
contributions of the atoms at the face centered locations. The number of atoms in a unit cell of the
face centered cubic structure is given by
( No. of atoms at the face centers X their contribution to the unit cell )
n = [ 8 X (1 /8 )] + [ 6 X ( 1 / 2)] = ( 1 +3 ) = 4
The parameters describing the structure of a face centered cubic structure are :
3 Atomic radius r
Atomic packing factor is the ratio of the volume of the unit cell occupied by atoms to the net
volume of the unit cell
v = (n ) X [ 4 / 3 π3 ]
( n )( 4)( πr 3 ) 2 π(n )
APF =
[
3 64 r 3 /( 2 2) ]= 24
= 0.74 (74 %)
Sodium chloride is an ionic crystal. It is a compound of the alkali halide family. Due to the proximity
of the sodium atom with a chlorine atom, the valence electron from the sodium atom is transferred to
the chlorine atom. With this transfer of an electron, the sodium atom becomes a cation and the
chlorine is converted to an anion. Then, these ions are held by the ionic force and the bond that holds
the atoms together is ionic.
A conventional unit cell of the structure consists of eight cubic primitive cells (figure 18). In the
conventional unit cell of the crystal, sodium atoms occupy the FCC positions of a cubic structure.
Chlorine atoms are placed at the intermediate positions between the sodium atoms. Chlorine atoms
independently from an FCC structure similarly sodium atoms also from an independent FCC
structure. The lattice constant of both the FCC structures is a = 5.63Au. A unit cell of a sodium
chloride crystal can be regarded as the structure formed by the inter-penetration of sodium FCC
lattice with the Chlorine FCC lattice through one half of the lattice constant. This can be treated as the
graphical representation of the crystal structure.
The crystal structure can also be illustrated in terms of the co-ordinates of the atoms in the
structure. For this, an orthogonal co-ordinate system is considered. The origins of the co-ordinate
system can either be at the location of a chlorine atom or at the location of a sodium atom. With the
origin at the location of the sodium atom, the co-ordinates of the sodium and chlorine atoms in the
crystal structure are shown below. Sodium chloride is an ionic crystal formed by the transfer of the
valence electron from sodium atom to the chlorine atom. Due to this transfer the sodium atom is
converted to a cation and the chlorine is converted to an anion. These ions are held by the ionic force
and the bond that holds the atoms together is ionic bond. In the unit cell of the compound, chlorine
atoms occupy the FCC positions of a cubic structure. Sodium atoms occupy edge center positions.
Figure6
Atoms Co-ordinates
½½0,1½½,½½1,0
Sodium ½½,
½ 0, 10 ½, ½ 01 , 00 ½ ,
1 ½ 0, 1 ½ 1, 0 ½ 1, 0 ½ 0,
½½ ½
Chlori
ne ½ 1 0, 1 ½ ½ , ½ 1 1, 0 1
½
nA
ρ= kg / m 3
NAV
Here n is the number of sodium chloride molecules in a conventional unit cell. In place of A the
molecular weight of sodium chloride molecule is to be considered. V is the volume of the
conventional unit cell with a lattice constant a = 5.63 Au. This is the distance between any two
neighboring sodium atoms or the neighboring chlorine atoms. The number of molecules in a unit
cell is equal to the sum of sodium atoms [n (Na)] contained in the cell and the chlorine atoms
[n(CI)]. The number of sodium chloride molecules in a unit cell are :
N = [ n (Na) ] + [ n ( CI ) ]
[ n ( CI ) ] = 4 ( 1/4 )+ 4 ( 1/4 )+ 1 = 4
A = ( 58.43 X 10-3 ) Kg
nA 4(58.43X10−3 )
ρ= = 23 10) 3
= (2.174Ξ103 )kg / m3
N A V (6.023X10 )(5.63X10 −
Some of the common ceramic materials are those in which there are equal numbers of
cations and anions. These are often referred to as AX compounds, where A denotes the
cation and X the anion. There are several different crystal structures for AX compounds;
each is normally named after a common material that assumes
Perhaps the most common AX crystal structure is the sodium chloride (NaCl), or rock salt,
type. The coordination number for both cations and anions is 6, and therefore the cation–
anion radius ratio is between approximately 0.414 and 0.732. A unit cell for this crystal
structure (Figure 12.2) is generated from an FCC arrangement of anions with one cation
situated at the cube center and one at the center of each of the 12 cube edges. An
equivalent crystal structure results from a face-centered arrangement of cations. Thus, the
rock salt crystal structure may be thought of as two interpenetrating FCC lattices, one
composed of the cations, the other of anions. Some of the common ceramic materials that
form with this crystal structure are NaCl, MgO, MnS, LiF, and FeO.
Figure 12.3 shows a unit cell for the cesium chloride (CsCl) crystal structure; the
coordination number is 8 for both ion types. The anions are located at each of the corners of
a cube, whereas the cube center is a single cation. Interchange of anions with cations, and
vice versa, produces the same crystal structure. This is not a BCC crystal structure because
ions of two different kinds are involved.
Zinc Blende Structure
A third AX structure is one in which the coordination number is 4; that is, all ions are
tetrahedrally coordinated. This is called the zinc blende, or sphalerite, structure, after the
mineralogical term for zinc sulfide (ZnS). A unit cell is presented in Figure 12.4; all corner
and face positions of the cubic cell are occupied by S atoms, while the Zn atoms fill interior
tetrahedral positions. An equivalent structure results
if Zn and S atom positions are reversed. Thus, each Zn atom is bonded to four S atoms, and
vice versa. Most often the atomic bonding is highly covalent in compounds exhibiting this
crystal structure (Table 12.1), which include ZnS, ZnTe, and SiC.