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Culture Documents
By
S.K.Sinha
Resonance, Kota
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Solid State
1.Concept of Solid
9. Defect in Crystals
1
Solid State
1.Concept of Solid
A large majority of substances around us are solids. The distinctive features of solids are:
1. The constituent units of solids are held very close to each other so that the packing of
the constituents is very efficient. Consequently solids have high densities.
2. Since the constituents of solids are closely packed, it imparts rigidity and hardness to
solids.
3. The constituents of solids are held together by strong forces of attraction. This results
in their having define shape and fixed volume.
Information regarding the nature of chemical forces in solids can be obtained by the study of
the structure of solids, i.e. arrangements of atoms in space. There are two types of solids:
Amorphous and crystalline.
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Note 1:There are 7 crystal systems ,defined on the basis of axis of symmetry.
Note 2: It was shown by A. Bravais in 1848 that all possible three dimensional space lattice
are of fourteen distinct types. These fourteen lattice types are derived from seven crystal
systems
Primitive body
Body-centered ==
Cubic Face-Centered a=b=c = 90 NaCl, Zinc blende, Cu
Primitive,
Body-centered,
Face-centered, == Rhombic sulphur,
Orthorhombic End-centered abc = 90 KNO3, BaSO4
==
90
Hexagonal Primitive a=bc = 120 Graphite, Zno,Cds
K2Cr2O7, CuSo4.5H2O,
Triclinic Primitive abc 90 H3BO3
Table: Seven Primitive Unit Cells and their Possible Variations as Centred Unit Cells
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3.Solid
ds and latttice
1. As already
a menntioned crysstalline soliids consist of
o regular arrangemen
a nt of atoms in three
dimensiions.
3. Eachh point in thhe lattice is so chosen that its environment iss the same aas that of an
ny other
O examplle each of one dimensioonal, two diimensional and a threee dimension
point. One nal space
lattice is shown in the figure.
It may be
b understoood here thaat it is the arrrangement of the poinnt which is a lattice and
d not the
line whhich are joinning them.
The un
nit cell is so
o chosen as
a to fulfil th
he followin
ng conditio
ons:
1. It should possess
p the
e same sym mmetry as thet crystall structure.
2. If there is a choice between
b m
more than one
o repeating arrang gements, the
t one
which hass the smalllest numbe er of atomss (i.e., smallest volu
ume) is choosen as
the unit ceell. Such a unit cell iss often labe
elled as the
e primitive
e ( or simp
ple) unit
cell repressentation.
The natture of a soolid is deterrmined by thhe size, shaape and conntents of itss unit cell. The
T size
and thee shape of a unit cell area characteerized by th he distance (a, b, c) oof three inteersecting
edges and
a the angles (, , ) between
b theese axes.
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We have earlier discussed the classification of crystals on the basis of symmetry elements and
in terms of interrelation of lengths (a, b and c) and angles (, and ) between different
crystal axes. It is equally useful to classify solids by the units that occupy the lattice sites and
in terms of the bond type. Solids may be occupy the lattice sites and in terms of the bond
type. Solids may be distinguished and classified in four different bond type, each representing
different type of force between their constituent units in the crystal lattice:
1. Ionic solids
2. Metallic solids
3. Covalent solids
4. Molecular solids
These are the main groups in which solids can be broadly classified. Examples of solid
substances are, however, known which exhibit properties characteristic of more than one of
these groups. This type of intermediate behaviour may be observed either due to the presence
of two different types of bonds in these solids or these solids may consist of bonds which are
intermediate in character. Some of the physical properties associated with these solids are
summarized in the following table.
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The force of attraction between the ions is purely electrostatic. Examples of ionic solids are:
NaCl, CsCl and ZnS. Since these ions are held in fixed positions, there, ionic solids do not
conduct electricity in the solid state. They conduct electricity in the fused state.
The constituent units of metallic solids are positive ions. This array of positive ions are held
together by the free moving electron charge cloud.. Examples of metallic solids include Cu,
Ag, Au, Na, K etc.
These solids are formed when a large number of the atoms are held by strong covalent
bonds. This bonding extends throughout the crystal and as covalent bond is directional, it
results in a giant interlocking structure. For example, in diamond each carbon atom is
attached to for other carbon atoms covalent bonds .
The constituent units of molecular solid are the molecules (either polar or non-polar ) rather
than atoms or ions, except in solidified noble glasses where the units are atoms.
These solids have relatively high coefficients of expansion. They melt at low temperatures
and have low heat of fusion. The bonding within the molecules is covalent and strong
whereas the forces which operate between different molecules of the crystal lattice are the
weak van der Waals forces.
As result of these weak forces, the molecular solids are soft and vaporize very readily. These
solids do not conduct electricity. The electrons are localized in the bonds in each molecule.
They are, therefore, unable to move from one molecule to another on the application of
electric field.
Examples of these solids are iodine, sulphur, phosphorus (non polar) and water, sugar (polar)
etc
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1. studyy the most efficient waay of packing of hard spheres of equal size in three dirrections
called thhe closest packing.
p
3. If a large
l numbber of spherres of equaal size are put
p in a coontainer andd shaken, thhey will
arrangee themselvess in a mannner so as to occupy
o vollume. The arrangement
a t of such sp
pheres in
a plane are showinng the figuree.
4.The packing
p is closest
c wheen the spherres arrange themselvess so that thheir centres are at
the corrners of an equilateral trianglle (see figu ure) Each sphere in tthe closest packed
arrangeement is in contact withh six other spheres
s as shown
s in the followingg figure.
5. The number
n of spheres whhich are actuually in con
ntact with a particular ssphere is caalled the
coordiination nu umber off that spheree. The coorrdination nuumber is sixx when sphheres are
arrangeed in a closee packed arrrangement inn one planee.
7.3 D arrangemen
a nt or Arranggement of layers in 3D:3 Now iff we start bbuilding succcessive
layers on
o top of thhe first layerr, spheres marked
m A, (next figure)), we soon realize that spheres
of seconnd layer maay be placed either on the hollow ws which aree marked B or on the other
o set
of holloows which are
a marked as C
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7. ABAABABA... Arrangemen
A nt: When thee ABABAB BA... arranggement of paacking is coontinued
indefiniitely, the syystem posseesses hexaggonal symm
metry. This would
w implly that the structure
s
possessses a six-foold axis of symmetry which is perpendicul
p lar to the pplanes of thhe close
packed spheres. Suuch an arranngement of three dimen nsional packking of spheeres is show
wn in the
next figgure. Because of its hexagonall symmetry y, this arrrangement is referred to as
hexagoonal close packing of spheres
s ofteen abbrevia
ated as hcpp.
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The arrangement is called cubic close packing of spheres and is often abbreviated as
ccp.
9.ccp is equivalent to fcc: In this arrangement we have a sphere at the center of each face of
the unit cube. This arrangement of spheres is also known as face centered cubic (fcc).
10 Coordination No :- In the both these arrangements, i.e., hcp and ccp, it is obvious that each
sphere is surrounded spheres. There are six spheres which are in contact in the same plane
and three each in adjacent layers, one just above, and the other just below. The coordination
number of each sphere in both these close packed arrangement is twelve. These are shown in
previous figures.
11. In both these type of close packed arrangements, maximum volume of space, i.e., 74% is
actually occupied by the spheres.
12.Strictly all arrangements are not closest :-It may also be understood here that any irregular
arrangement like ABABC-ABABC etc possesses neither cubic nor hexagonal symmetry.
13.Strictly all arrangements are not closest :- Arrangement in which atoms forming the layers
are not in direct contact donot form the closest packing.
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The structure of most the metals (from s and d Blocks of the periodical chart) belong either to
on or more of the three simple type of structures:
The distribution of these structures among the s- and d-block metals is shown in the table.
In this structure atoms are arranged at the corners and at the centres of all six faces of a cube.
In this structure each atom has 12 nearest neighbours as shown in figure. For example, the
atom at the center of the middle face has four nearest neighbours at the corners of that face
and eight more at the same distance at the center or four faces of adjoining cubes.
In this arrangement, atoms are located at the corners and the center of two hexagons which
are placed parallel to each other and three more atoms in a parallel plane midway between
these two planes. This arrangement is obtained when we have ABABA... type of close
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6.3 Boddy Centereed Cubic: This arranngement of spheres (or atoms) iss not exactly close
packed.. This struccture can be
b obtainedd if spheress in the first layer (m
marked A) of
o close
packingg are slightlly opened up.
u As a ressult none of these sphheres are inn contact with each
other. Such
S an arraangement iss show in the abone.figu
ure.
In a boddy centeredd cubic arranngement, thhe atoms occcupy cornerrs of a cubee with an ato
om at its
center. In this arranngement eaach sphere is in contactt with eight other spherres (four sp
pheres in
the layeer just abovve and four spheres
s in the
t layer jusst below) annd so the cooordination number
in this type of arrrangement is only eigh ht. The struucture is knnown as boody centereed cubic
(bcc). As
A has alreeady been mentioned,, this arran ngement of packing iss not exacttly close
packed,, and only 68%
6 of the total
t volumee is actually
y occupied.
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It has been observed that those metals which crystallize in cubic form are more malleable and
ductile that those which crystallize in the hexagonal system. Since and ductility are related to
deformation in crystals, it may be said that crystals with cubic symmetry are easily
deformed. Deformation in crystals may mean sliding of on plane of atoms over other planes.
Since the cubic close packed structure contains four sets of parallel close packed layers,
therefore, metals with this structure will have more opportunities for slipping of one layers
over the other. Examples of metals with cubic structure which are easily deformed are
copper, silver, gold, iron, nickel, platinum, etc.
Hexagonal close packed structure contains only one set of parallel close packed layers.
Therefore, the chances of slipping of planes in hexagonal close packed structure are very
little. Metals which show this structure, e.g., chromium, molybdenum, magnesium, zinc etc.,
are les malleable, harder and more brittle.
Since iron can adopt both these type of arrangements depending upon temperature, therefore,
this is the reason why iron can exhibit a wide variety of properties.
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The ionic solids consist of positive and negative ions arranged in a manner so as to acquire
minimum potential energy. This can be achieved by decreasing the cation-anion distance to a
minimum and reducing anion-anion repulsions.
The structures of ionic solids can be described in terms of large anions/cations forming a
close packed arrangement and the small cations/anions occupying one or the other type of
interstitial sites.
It was discussed earlier that the arrangement is close packed only when the centres of three
spheres are at the vertices of an equilateral triangle. Since the spheres touch each other only
at one point, there must be some empty space between them. This empty space (hole or void)
is called a triangular site.
tetrahedral hole: Similarly, it is observed that when a sphere in the second layer is placed
upon three other touching spheres a tetrahedral arrangement of spheres is produced.
The centres of these four spheres lie at the apexes of regular tetrahedron. Consequently, the
space at the center of this tetrahedron is called a tetrahedral site. It may be mentioned here
that it is not the shape of the void which is tetrahedral, but that the arrangement of the spheres
which is tetrahedral.
In a close packed arrangement each sphere is in contact with three spheres in the layer above
it and three other spheres below it. As result there are two tetrahedral sites associated with
each spheres.
We may also observe that the size of the empty space is much smaller than the size of the
spheres. But as the size of the spheres increases, the size of the empty space shall also
increase.
Octahedral hole :Another type of empty space in close packed arrangement is created by
joining six spheres whose centres lie at the apexes of a regular octahedron. The creation of
such an empty space in close packed arrangement may be visualized as shown in the figure.
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From this diagram, it is obvious that each octahedral site is generated by two set of
equilateral triangles whose apexes point in opposite directions.
We may also note that there is only one octahedral site for every sphere.
This means that the number of octahedral site are half as many as there are tetrahedral sites.
The size of an octahedral hole is larger than a tetrahedral hole which in turn is larger than a
trigonal hole.
But once again the size of an octahedral site will vary with the size of the spheres. The size
of each empty space is fixed relative to the size of the spheres. The radius of the small sphere
that may occupy the site can be calculated by simple geometry.
For example, it may be shown that the radius of small sphere which can fit into a trigonal site
is 0.155 times the radius of large close packed spheres.
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Proof:11 Lim
miting Radiius Ratio fooe Triangullar hole
Let rc and
a ra the raadii of the caation and annion, respecctively.
i.e.
Proof:22 Lim
miting Radiius Ratio foor Tetrahed
dral hole
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Face diagonal
or
Body diiagonal
Also boody diagonaal = 2ra+2rc (where rc iss the radius of the catioon)
Proof:33 Lim
miting Radiius Ratio foor Octahed
dral hole
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Proof:44 Lim
miting Radiius Ratio foor Cubic ho
ole
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A large number of ionic solids exhibit one of these five structures which are discussed here:
1. Chloride ions are ccp type of arrangement, i.e., it contains chloride ions at the corners
and at the center of each face of the cube.
2. Sodium ions are so located that there are six chloride ions around it. This is equivalent
to saying that sodium ions occupy all the octahedral sites.
3. As there is only one octahedral site for every chloride ion, the stoichiometry is 1 : 1.
4. For sodium ions to occupy octahedral holes and the arrangement of chloride ions to be
close packed the radius ratio, rNa+/rCl-, should be equal to 0.414. The actual radius
ratio 0.525 exceeds this limit. To accommodate large sodium ions, the arrangement of
chloride ions has to slightly open up.
5. It is obvious from the diagram that each chloride ion is surrounded by six sodium ions
which are disposed towards the corners of a regular octahedron. We may say that
cations and anions are present in equivalent positions and the structure has 6 : 6
coordination.
6. The structure of sodium chloride consists of eight ions in one unit cell, four Na+ ions
and four Cl- ions.
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In this structure, each cornerr ion is sharred between n eight unitt cells, eachh ion on thee face of
the celll is shared by
b two cells, and eachh ion on the edge is shared by fou ur cells and
d the ion
inside thhe cell beloongs entirelyy to that uniit cell.
A unit cell
c represenntation of zinc blend iss shown in the
t figure.
1. The zinc attoms are ccpp type of arrrangement, i.e., zinc atoms
a at thee corners an
nd at the
center of eaach face of the
t cube.
2. Sulphur ato oms are so located thaat there are four zinc atoms
a arounnd it. Or it may be
said that suulphur atomss occupy tettrahedral sittes and their coordinatiion numberr is four.
3. As there arre eight tetrrahedral site
es availablee; four sulphhur atoms ooccupy only y half of
tetrahedral sites. So the stoichiometry off the comppound is 1:1. Only alternate a
tetrahedral sites are filled by sulphhur atoms.
4. Each zinc atom
a is surrrounded by four sulphu ur atoms annd in turn eaach sulphurr atom is
also surrouunded by fouur zinc atom ms which are
a also dispposed towarrds the corn ners of a
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regular tetrahedron. We may say that cations and anions are present in equivalent
positions and the coordination of zinc blende structure is described as 4:4.
5. For the arrangement of sulphur atoms to be truly close packed and zinc atoms to
occupy tetrahedral voids, the radius ratio (rZn2+/zS2-) should be 0.40. This value is
greater than 0.225 and so we may say that the arrangement of sulphur atoms is not
actually close packed.
This structure is found in 1:1 compounds in which the cation is smaller than the anion.
Examples : Copper(I) halides (CuCl, CuBr, CuI), silver iodide and beryllium sulphide.
It is an alternative form in which ZnS occurs in nature. Its unit cell representation is shown in
the figure
1. Sulfur atoms form the hcp type of arrangement and are yellow spheres in the diagram.
2. Zinc atoms are violet spheres and are located that there are four sulphur atoms around
each zinc atom. It may be said that zinc atoms occupy tetrahedral sites.
3. As there are two tetrahedral sites available for every sulphur atom, zinc atoms occupy
only half of tetrahedral sites. The alternate tetrahedral sites remain vacant. The
stoichiometry of the compound is 1:1.
4. Each zinc atom is surrounded by four sulphur atoms and in turn each sulphur atom is
also surrounded by four zinc atoms (which are also disposed towards the corners of a
regular tetrahedron). The coordination of the compound is 4:4. Again we may say that
cations and anions are in equivalent positions.
5. It may be concluded that the structure of Wurtzite is very similar to the structure of
zinc blende. The only difference is in the sequence of the arrangement of close packed
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layers of sulphur atoms. In zinc blende, sulphur atoms follow the sequence
ABCABC... etc. whereas in wurtzite the sequence is ABABAB... etc.
The calcium ions are marked as green spheres, and fluoride ions are marked as light blue
sphere.
1. The calcium ions form the ccp arrangement, i.e., these ions occupy all the corner
positions and the center of each face of the cube.
2. Fluoride ions are so located that there are four calcium ions around it. It may be said
that the fluoride ions occupy tetrahedral sites and the coordination number of fluoride
ion is 4.
3. As there are two tetrahedral sites available for every calcium ion, the fluoride ions
occupy all the tetrahedral sites. The stoichiometry of the compound is 1:2.
4. Each fluoride ion is surrounded by four calcium ions whereas each calcium ions is
surrounded by eight fluoride ions which are disposed towards the corners of a cube.
The coordination of the compound is 8:4
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The structure of CsCl is shown in the figure at the left and its unit cell representation is
shown in figure at the right.
Figures. (left) Structure of CsCl and (right) unit cell representation of CsCl.
This structure is observed only when the cations are comparable in size to the anions.
Coordination Fraction
Name Examples
number filled
Na+ 6 Li, Na ,K, Bb halides, NH4Cl, NH4Br, NH4I,
Rock salt (NaCl-type) 1
Cl- 6 AgF, AgCl, AgBr.
Zinc Blende (ZnS- Zn+2 4
ZnS, BeS, CuCl, CuBr, CuI, AgI
type) S-2 4
Zn+2 4
Wurtzite (ZnS-type) ZnS, ZnO, CdS, BeO
S-2 4
Ca+2 8
Fluorite (CaF2-type) 1 CaF2, SrF2, BaF2, SrCl2, BaCl2, CdF2, HgF2
F- 4
Cesium Chloride Cs+ 8
1 CsCl, HgBr, CsI
(CsCl-type) Cl- 8
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9. Defeect in Cryystals
Real cryystals have always impperfect struuctures. Thee arrangemeent of consttituent unitss are not
very reggular. Ideall crystals with
w no impeerfections are a possiblee only at abbsolute zero. Above
this tem
mperature all
a crystallinne solids coontain somee defects inn the arranggement of itsi units.
The following disccussion is only restricteed on simplle compounnds are mainnly ionic co onsisting
of A+B B- units. Deffects in crysstals may giive rise to
Stoichiomeetric, and
Non-stoichhiometric strructures.
This defect
d is moost predominant in com mpounds wiith high cooordination nnumbers an nd where
the ions (both cattions and anions)
a aree of similarr sizes. Som me of the compounds which
predomminantly shoow this defeect are the alkali
a halidees such as NaCl
N and CssCl. Since there
t are
lesser number
n of ioons in the laattice, the deensity of solid will decrease.
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In compouunds whichh have low w coordinattion numbeers. In com mpounds with w low
coordinatioon numbers the attractivve forces beeing less, arre easy to ovvercome so o that the
cation can easily
e movee into the innterstitial sitte.
This defect is more com
mmon in coompounds which w have ions of differrent sizes.
In compouunds where we have highly h polaarizing catioon and an easily pollarizable
anion.
Exxamples of compounds
c which show
w this defecct are ZnS (bboth zinc bllende and wurtzite),
w
AggBr etc. Thhis type of defects leaads to an in ncrease in the dielectrric constannt of the
meedium. the density
d of thhe medium, however, remains uncchanged.
Solids generallly contain both these types of deefects, but one o is moree predominant than
thee other. Thee crystal is then said too possess only that parrticular defe
fect. The nu
umber of
deffects in a crrystal generrally increaase with thee rise of tem
mperature. N
Normally sppeaking,
Schhottky defects are easieer to form thhan Frenkel defects as the former require lesss energy
forr their formaation.
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