10H

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Lecture-4
VOIDS
Voids: Iitsthred
e imensionspacienthseolidwhichisempty.
Intwd
o imensions0moetfhveoidsaraes,

Squarveoid Triangulavroid
Inthred e imensionwaerheavingtwtoypesovfoids.
(1)TetrahedraVl oid (2)OctahedraV
l oid
TetrahedraV l oid: In
casoetfetrahedravloid
fouartomosironfsorm
tetrahedralI.nwhichthreaetoms/ionaroenthbeasaendone
iosnthteop.

Iitshavingfollowingproperties:

(a) Coordinationnumbe= r4
(b) Irfadiuosvfoiirs anradiuostfhaetom
void
irs then,
atom
rvoid
ratom 0.225
(c) Inthveoidgenerallycationsarpelacedso,
r+
0.225
r—
(d) w.r.tt.hgeivenatomnumbeortfetrahedravloidasrtewo. OctahedraV l
oid: Incasoeofctahedravloidwaerheavingfour
atomsonthbeasaendtwaotomonthteo pandbottomotfhe
fouartoms.
Iitshavingfollowingpoints.
(a) Coordinationnumbeirsixfoorctahedravloid.
(b) Irfadiuostfhveoid
irs anradiuosaftom
void
irs atom
then,

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d tate
rvoid
ratom 0.415
(c) Iifnthveoidcationisplacedthen
r+
r — 0.415
(d) W.r.tg.ivenatomnumbeorofctahedravloidsisone.
ExamplI:iefnano xidA
einte trahedravloidBinoctahedral
void then thfeormulaotfhoexidies.
Solution: Len t umbeorofxygen atom
iosntehennumbeorf
tetrahedral voidstwoandnumbeorofctahedravloid
one.
Sof,ormulw a ilblei,n
tetrahedravloid
:
2A O B or 2O B
A
:
Thereforef,ormulaA, 2
B
O
Q.1 Iw f .r.to.xygenAishaving60%otfetrahedravloid
andBihsaving 80%oofctahedravloidT.hen
find
out,
(a) Formulaofoxide (b)Formulaofnitride
Solution: (a)Withrespectoxygennumbeorfoctahedral void
one. Withrespecttoxygennumbeortfetrahe- dral
void twoB. ut 60%otfetrahedravloidand80%
ofoctahedravloidarpeacked.
Tetrahedral void Octahedral void
60 80
2A O B
100 100
A 120 B 80 O 100
or A 12 B 8O 10 or OBA6 4 5

Iittshfeormulaoofxide.
(b) Inf itridieu
s sed then
charged ibsalanced.
Whicihes quatclohargoe5 .–, 10
aftomosofxygeni.,e=
—10 chargiebsalanced
by5
oxygen atom
—10 chargiebsalanced
by10/3 nitrogenatom
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Soi,nplacoeA
f B4O5
6

waerheavingA 6
B4N10/3 or A18B12N10
MeansA
, 6
B4O5×3 or
A18 B12 Oi1sr5eplacedbyA 18
B12N10
Soa,nionivcacancyi,nthiscasiesfiveb,ecausfeive
oxygenatomsarme ortehannitrogenatoms.

RadiusRatioofOctahedralVoid
OctahedravloidisshowninfigureT . houghanoctahedravloid
isurroundedbysixspheresO . nlyfourarsehownT.hsepheres
presenatbovaendbelowthveoidarn e osthownL. eu
t sassume
thatthleengthotfhu
e nictelilsacma.ndradiusoofctahedral
voidisrandtheradiusofsphereisR.
Ifthelengthoftheunitcelilsacmt,hen
InrightangledDABC, AB=BC=acm
ThediagonalACis:

AC AB 2 BC 2 a2 a 2 2a
D
AC 2a 2 R
c
Also,
AB a 1 2r

R
Now AB 2R
A B

AC R 2r R 2R 2r
Octahedral Void with
2R 2r 2 Radius r

2R 1
r 2
or 1
R 1

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SoliS
d tate
r
or 2 1 0.414
R
or r 0.414 R
Thusf,oranatomtooccupyanoctahedralvoidi,ts
radiusmustbe0.414theradiusofthesphere.

RadiusRatioofTetrahedralVoid

Atetrahedravloidmaybreepresentedbyplacingfousrpheraet
thealternatecornersofacubeasshowninfigureI.tmaybe
notedthaatstablteetrahedraalrrangemenh t asfourspheresat
thceornertsouchingeachotherH . owevefrosrimplicitythsephere
areshownbydistancecircles.Actuallyallthespheresare
touchingoneanother.Letusassumethatthelengthofeach
sidoefthceubiesacmandradiusoftetrahedravloidisarnd
theradiusofsphereisR.
InthefigureA , Cisafacediagonal.
Inrightangled ABC,
AC2=AB 2
+BC 2 or
AC AB 2 BC 2
a2 a 2 2a
AsspheresAandCathefacediagona(lthroughshown
bydistantcircles)areactuallytouchingeachothersothat
AC=R+R=2R
2.a
2R 2 .a or R .....(i)
2
Nowintherightangledtriangle, ACDA
, Disbodydiagonal
and AD2=AC 2
+CD 2

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AD AC 2 CD 2
2a2 a2 3a
Thteetrahderavloidispresenatthceentroetfhbeodydiagonal
ADshowthahtalfthelengthofthisdiagonailsequatlothe
sumoftheradioifRandrT. hus,
AD 3.a
R r .............(ii)
2 2
Dividingequation(ii)by(i)w
, eget,

R r 3.a 2 3 Face diagonal

R 2 2a 2 C

a
r 3

Body diagonal
A
1 a B
R 2 2r

r 3 3 2
or 1
R 2 2
D
1.732 1.414
0.225
1.414
0.22r 5R

Thusf,oa
r natomtoccupyatetrahedravloidi,tsradiusmust
be0.225timestheradiusofthesphere.
Foragivenatomnumberofoctahedralvoid=Noo.fatoms
Numberoftetrahedralvoid=2×Numberofatoms

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d tate
SoliS
d tate
.

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s k s

ExtraShoot
Q.1. Explainwhyamorphousolidsareisotropic.

Q.2. Howmanydifferentypesou
f nict ellsarepossiblefortwodimensional
lattices?

Q.3. Itfhre elementsXY,andcrystallizeinacubicsolidlatticewithXatoms

athecornersY,atomsactubecenterandatomsaetdgesthenwhaitsthe
formulaotfhesolid?

Q.4. WhaitsFranked
l efec?t

Q.5. Whaitsthecoordinationnumbeo
r afn
atom
presenitn
anoctahedrav
l oid?

Q.6. WhaitsF-center?

Q.7. Compare
the
size
oefnergy
gap
in
conductorss,emiconductorasnd
insulators?

Q.8. DefinethetermamorphousG
. ivefourexamplesoa
f morphousolids.

Q.9. AcompoundisformedbytwoelementsMandNT , heelemenN t forms

hcpandatomsMoccupy2/3rdoo
f ctahedrav
l oidsW. haitstheformula
otfhecompound?

Q.10. Acompoundcontainstwotypesoa f tomsX -andYI.ctrystallisesina

cubiclatticewithatomsXathecornersotfheunictelal ndatomsYat
thebodycentresW . haitsthe
simplespt ossibleformulaotfhiscompound?
WhaitsthecoordinationoY f?

Q.11. Itfhre elementsP ,Q

, andRcrystallizeinacubicsolidlatticewithP
atomsathecornersQ ,atomsathecubecentreandRatomsathecen-
treotfhefacesotfhecubet,henwritetheformulaotfhecompound.

Q.12. Describethefollowing:
(iH) exagonacllosepacking
(iiC
) ubi closepacking
(iii)Bodycentredcubicpacking
Drawunictelol ef achtype.

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