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By
S.K.Sinha
Resonance, Kota
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Solid State
1.Concept of Solid
2.Concept of crystalline Solid :
3.Solids and lattice
4. Type of Solids (Force of attraction)
5. The closest packing
6. Packing Metallic Crystals
7. Packing Ionic Solids
8. Example of Ionic Solids
9. Defect in Crystals
Solid State
1.Concept of Solid
A large majority of substances around us are solids. The distinctive features of solids are:
1.
2.
3.
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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POSSIBLE
VARIATION
EDGE
AXILE
LENGTHS ANGLE
EXAMPLES
Primitive body
Body-centered
Cubic
Face-Centered
==
a=b=c
Primitive,
Tetragonal
Body-centered
a=bc
= 90
==
= 90
CaSO4
==
Rhombic sulphur,
= 90
KNO3, BaSO4
Primitive,
Body-centered,
Face-centered,
Orthorhombic
End-centered
abc
==
90
Hexagonal
Primitive
a=bc
Rhombohedral
or trigonal
Primitive
a=b=c
Primitive,
Monoclinic
End-centered
= 120
Graphite, Zno,Cds
==
Calcite (CaCO3),
90
HgS(cinnabar)
= =90 Monoclinic
abc
120
sulphur,Na2SO4.10H2O
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.
2. If attoms are considered
c
as points,, the arran
ngement off an infinitte set of points
p
is
known as space laattice.
ny other
3. Eachh point in thhe lattice is so chosen that its environment iss the same aas that of an
point. One
O examplle each of one dimensioonal, two diimensional and a threee dimension
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.
4. The smallest reppeating mottif (pattern)) is known as a Unit ceell. If this m
motif is rep
peated in
differennt directionss it should be
b able to reegenerate th
he entire latttice.
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 the
t crystall structure.
b
m
more
than one
o repeating arrang
gements, the
t one
2. If there is a choice between
which hass the smalllest numbe
er of atomss (i.e., smallest volu
ume) is cho
osen as
the unit ce
ell. 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 are
a characteerized by th
he distance (a, b, c) oof three inteersecting
edges and
a the angles (, , ) between
b
theese axes.
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Ionic solids
Metallic solids
Covalent solids
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.
Crystal
type
Bonding
force
Ionic
Ionic
Electrostatic
attraction
between +ve Metallic
ions and sea
of electrons
Sharing
electron
pairs
Molecular
interaction
forces
Very low
Quite
Relatively (high
in NaCl,
hard and Very high
high
molten
CaO
brittle
state)
Positive
ions
in
Variable Very low Variable
electron
gas
of
Covalent Atoms
Electrical
Examples
conductivity
Very
hard
Medium
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Very high
Cu,
Ag
Fe,
Diamond,
SiC, SiO2
Ice,
I2 ,
Fullerene
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4.The packing
p
is closest
c
wheen the spherres arrange themselvess so that th
heir 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.
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.
ayer 1 and available
a
too accept atoms in layerrs 2 either oon the hollo
ows B or
Sites crreated by lay
C. It may
m be noted that whille building the second
d layer, we cannot placce spheres both on
hollowss B and C. As
A shown inn the figuree, we may build the seccond layers on hollows marked
B.
7. ABA
ABABA... Arrangemen
A
nt: When thee ABABAB
BA... arranggement of paacking is co
ontinued
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 th
he 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 hcp
p.
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The distribution of these structures among the s- and d-block metals is shown in the table.
Li b
Be h
Na
b
Kb
Mg h
Ca c Sc c h Ti h b
h
Rb
Sr c
Yh
Zr h
b
b
Cs b Ba b
La c Hf h
h
b
Vb
Cr b
Co c Ni c Cu
h
h
c
Mo b Tc h Ru c Rh c
Pd c Ag c
Nb
b
h
h
Ta b W b
Os c h Ir c
Pt c
Re
Au
h
c
Mn
Fe c b
Zn h
Cd
h
Hg
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10
6.3 Bod
dy 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.
The seccond layer of
o spheres ( marked B)
B may be placed
p
on thhe top of thhe first layerr, so the
layer beelow it. Succcessive buuilding of thhe third layeer will be exactly
e
like the first lay
yer (i.e.,
on top of
o A). If this pattern off building laayers is repeeated infinittely we get aan arrangem
ment bcc
as show
w in the figuure.
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 stru
ucture is knnown as boody centereed cubic
A has alreeady been mentioned,, this arran
ngement of packing iss not exacttly close
(bcc). As
packed,, and only 68%
6
of the total
t
volumee is actually
y occupied.
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Cubic close
packed
close packed
Body centered
cubic
not close packed
74%
ABACABC...
12
74%
ABABABAB....
12
68%
8
Malleable and
ductile
Cu, Ag, Au, Pt
Malleable and
ductile
alkali metals, Fe
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12
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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13
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.
Limiting ratio r+/r-
C.N
Structural arrangement/Holes
Example
12
metals
1-0.732
CsCl
0.732-0.414
NaCl
0.414-0.225
ZnS
0.225-0.155
Boron oxide
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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.
In an eqquilateral triiangle ABC
C
AD=ra and AE=ra+rc
cos ( EAD) = AD
A / AE
i.e.
s
we gett
On inveerting both side,
Proof:22
Lim
miting Radiius Ratio foor Tetrahed
dral hole
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15
Face diagonal
Since thhe two anionns are touchhing each otther, BC=2
2ra (where ra is the radiuus of the an
nion)
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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Lim
miting Radiius Ratio foor Cubic ho
ole
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17
The em
mpty space at
a the centerr of the cube, formed by
b eight idenntical spherres is called
d a cubic
interstiitial site. The
T largest void
v
and caan accomm
modate a sphhere of radiius 0.732 tiimes the
radius of
o the large sphere
Structurre of variouus substancees can be modified
m
by the introduuction of other ions off varying
sizes innto differentt interstitiall sites. Exaamples may
y include thhe introduction of smalll atoms
(such as
a non metaals like carbbon, boron, etc.) into the
t interstittial sites off metals wh
hich will
change their properties.
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18
5.
6.
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.
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.
As there is only one octahedral site for every chloride ion, the stoichiometry is 1 : 1.
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.
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.
The structure of sodium chloride consists of eight ions in one unit cell, four Na+ ions
and four Cl- ions.
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19
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20
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.
8.3 The Wurtzite structure
It is an alternative form in which ZnS occurs in nature. Its unit cell representation is shown in
the figure
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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.
Examples : ZnO, CdS, and BeO.
8.4 The CaF2 (fluorite) structure
A unit cell representation of fluorite structure is shown in the figure.
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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.
Coordination Fraction
Examples
number
filled
Na+
Cl- 6
(ZnS- Zn+2
S-2 4
Wurtzite (ZnS-type)
Zn+2
S-2 4
Fluorite (CaF2-type)
Ca+2
F- 4
Cesium
Chloride Cs+
(CsCl-type)
Cl- 8
Zinc Blende
type)
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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 its
i 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.
Stooichiometriic Defects. In
I stoichiom
metric comp
pounds irregularity in the arrangeement of
thee ions in thee lattice cann occur duee to a vacan
ncy at a catiion and an aanion site or
o by the
miggration of an
a ion to some other interstitial site. These defects aree of two ty
ypes: (a)
Schhottky defecct; (b) Frenkkel defect.
(a) Schottky defect:
d
Thiss defect connsists of a vacancy
v
at a cation siite and this will be
acccompanied by a vacancy at an annion site so as to mainttain the elecctrical neuttrality of
thee system. Thhe missing cations andd anions move to the suurface. The defect is illlustrated
in the
t followinng figure.
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
predom
minantly 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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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 constan
nt 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 sp
peaking,
Schhottky defects are easieer to form thhan Frenkel defects as the former require lesss energy
forr their formaation.
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