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,

34
SoliS
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
35
 10H
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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

36
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

37
 10H
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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

38
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d tate
SoliS
d tate

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Questions
ProblemsbasedonthisLecture

Q.1 Definevoid.
Ans. Theemptyspacespresentbetweenthemetalatomsortheionswhenthey
arepackedwithinthecrystalarecalledvoids.
Q.2 Whatisnumberotfetrahedrav l oidsinanunitcelo
la
fcubicclose-packed
structure?
Ans. Thereare8tetrahedralvoidsinaunitcell.
Q.3 Whatisthecoordinationnumberofanoctahedralvoid?
Ans. Six.
Q.4 Acompoundformshexagonalclose-packedstructure.Whatisthetotal
numberofvoidsin0.5molofit?Howmanyofthesearetetrahedaral
voids?

39
 23 23
Ans. Noo. fatomsintheclosepacking0.5mo=
l 0.5×6.022×10 =3.011×10

39
 10H
0 ou1r0s0Mark s
23
No.ofoctahedralvoids=1×No.ofatomsinthepacking=3.011×10
23
No.oftetrahedralvoids=2×No.ofatomsinthepacking=2×3.011×10
=6.022×10 23
23
TotaN l oo. fvoids=3.011×10+6.022×10 =9.33×10 23.
Q.5 Whatistherelationofnumberofvoidsintermsofnumberofatoms?
Or
InaclosepakedarrangementofN-spheresh , owmany(i)tetrahedraa l nd
(ii)octahedralsitesarepresent?
Ans. Numberofoctahedralvoids=Noo . fatomsintheclosepakedarrangement.
Numberoftetrahedralvoids=2×No .ofatoms
Q.6 Iftheradiusofthetetrahedralvoidis‘r’andradiusoftheatomclose
packingisR .Whatistherelationbetween‘r’andR?
Ans. ‘r’ =0.225R
Q.7 Iftheradiusofoctahedralvoidis‘r’andradiusoftheatominclose
packingisR .whatistherelationbetween‘r’andR?
Ans. ‘r’=0.414R .
Q.8 InasolidXY‘,Xa ’ tomsareinccparrangementand‘Ya ’ tomsoccupyall
theoctahedralsites.Ifallthefacecentredatomsalongoneoftheaxes
areremovedt,henwhaw t ilb
l etheresultansttoichiometryotfhecompound?
Ans. Inaccptypesstructure,8Xatomsareatthecornersand6Xatomsareat
thefacecentresofthecubeR . emovaol faltlhefacecentredatomsalongone
ofaxesmeanstheremovalof2Xatoms.Thus,only 4Xatomswillbeleft
onthecentredofthefaces.
1 1
No. of X atoms per unit cell 8(corner) 4(face centre) 3
8 2
Yatomsarepresentinalltheoctahedralsitesi.e.12atedgecentresand1
atbodycentre.
1
No. of Y atoms per unit cell 12 1 4
4
Therefore,Stoichiometryofthecompound=X Y .
3 4
Q.9 AtomsofelementBfromhcplatticeandthoseoftheelementAoccupy
2/3rd of tetrahedralvoids.Whatistheformulaofthecompoundformed
bytheelementAandB?
Ans. Suppose,thenumberofBatomsinthepacking= n
Numberoftetrahedralvoids=2n
Asonly2/3 rdoftetrahedralvoidsareoccupiedbyatomsA,
2 4
No. of atoms A 2n n
3 3
4
Ratio of A and B n n 4 3
3
TheformulaofthecompoundisA 4
B3 .

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Lecture-5

IMPERFECTORDEFECTSINSOLIDS

Anydeparturferomperfectlyorderedarrangmenotcfonstitu-
enptarticlesincrystailscalledimperfectionod r efect.Waere
havingtwotypesofdefectsoniespoind t efecatnotheirsline
defecw t aerd
e isscussingpoindt efect.
Typoepfoindtefects:
(A)Stoichiometricdefect
(B) Non -stoichiometricdefect
(C)Impuritydefects
(A)Stoichiometricdefect: Inthistypeofdefectt,hecrystal
ratiboe tweenthceationsandanionsremainsthseamaesrep-
resentedbythem olecularformulam . eansstoichiometryor
formulaotfhseolidisnodtistrubedthd e efectsarcealledsto-
ichiometricdefects.
wearehavingtwostoichiometrydefectsmainly
(i)Schottkydefect (ii)Frenkedl efect
Schottkydefec:t Inthistypoed f efecetquan l umbeorf
cationsande quan l umberofanionsaremissingfromtheir
latticseite sothathelectrican l eutralityismaintainedI.t
icsalledSchottkydefectI.nthitsypoed f efecw t aerheavinga
paiorfholesdevelopedduteomissingofcationandanion.
Ex.L.—L A tisacr+Bi–sacr
teA yass,taals,
A+ B— A+ B—

B— A+ B— A+

A+ B— A+ B—

IncaseofSchottkydefec thegivencrystaw
w
l ilblb elike,
41
 SoliS
d tate
B— A+ B—

B— A+ A+

A+ B— A+ B—

Duteothistypoefdefecftollowingproperteicsartehere.

(1) Ibtecomg e oodconductor.

(2) Massisdecreasedbecausm e issingcationsandanions
goesawayfromthseo lidS. od,ensityisdecreased.
(3) Iitsobservedgenerallyinthactasw e herceoordination
ishighandhavingsmaldlifferencienthseizoef
cationsandanions.
Ex.—NaClK , ClK
, BrA
, gBra,ndCsCl

Frenked l efects: Ifanionismissingfromit’sl atticesiteto

developaholeanditoccupiestheinterstiasliteE . lectrically
neutraalnd thsetoichiometry otfhceompound arme aintained.
Thitsypoed
f efecitcsalledFrenkedlefectL. eitnthcerystaolf
+ –
thseolidA B T.hcehangiesas,
A+ B— A+ B—

B— A+ B— A+

A+ B— A+ B—

Afted
r efect,

42
 10H
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B— A+ B—
A+
B— A+ B— A+

A+ B— A+ B—

Duteo thisd efect,

(1) Conductivityisincreased.
(2) Densityremainss ameb ecausem assisc onstant.
(3) Iitso bser veincaseo fL owcoordinationnumber
compound.
(4) Larged ifferenceinthes izeo fc ationsa ndanions.
Ex.–AgClA , gBrA , gIZ
, nS.

Note—AgBirshavingbothtypoefdefects

(B)Non -stochiometriD
c efects :
Thdeefectw
s hicd
h istrutbhsetochiometry otfhceompoundarcealled
non -stochiometrid c efects.
Thesedefectsareitherduetothepresenceofexcessmetailonsor
excessnon -metailons.

Metaelxcesd s efects:
(aM ) etaelxcesds efecdtuteaonionvsacancies
Alkalm i etahlalideshow thitsypoedfefecstuchaK
s Calnd
NaCl.
IcfrystalsoNf aCalrheeatedinNavapoursS . omseodiumatoms
—
ard e epositedonthseurfacoetfhN e aCclrystalT.hC el i onsdif-
fustetohseurfacoetfhcerystaalndcombinwe ithNatomtso
formNaCl. N
atomsloselectronswhichdiffusienttohcerystaalndoc-
+
cupyanionicstudiesS . oNa becomesmoriencrystal

43
 SoliS
d tate
ThaenionsitesoccupiedbyunpairedelectronsarcealledF-cen -
tersT.heyimpary t ellowcolourtothN
e aCclrystablecaustehe
unpairedelectronabsorbsenergyfromvisiblsepectrumI.nthe
samewayLiCclrystalsaresometimespinkandKCblecomes
violet.
(bM
) etaelxcessdefecdtuteoextracations:
Sometimesifanionsvacanciesbecomleessm , etailonsbecome
extrawhichcreatemetaelxcessdefectF.orexampleo,nheating
ZnOi,g t ivesoxygen.
1
ZnO Zn 2 O 2e
2 2
Zn2i+onbsecomeesxtrand
creatm
e etaelxcesdsefect.

Metadleficiency Defec:t
Manycompoundcsontainlesasmounotm f etaloscromparedttohe
stochiometripcroportionT.hitsypoedfefecigtsenerallyshownby
tran-
sition metalg s enerally.
2+
Foerxamplei,nthcerystaolF f eOs,omF ee ionsarm e issingand
losospfositivcehargiebsalanced bythperesencoef
3+
required numbeorFfe ions.

A+ B- A+ B-
A +
B -
A+
A+
A+
A+
B-
A+
B -
A+ B-
A+ B- A+ B-
B- A+ B- A+ B - B- A+ B- A+ B-
A+ B- A+ B-
A+ B- A+ B- A+ A+ B- A+ B- A+
B- A+ B- A+
B- A+ B- A+ B+ B - A+ B- A+ B+

+2
Ex. Findou%toFfe Fe +i3n
and Fe 0.9
O.
Ans. InFe 0.9
OoFre O
9 10
LeFte +a2raxend Fe +3
ar(e9–xs)ob,alancing charge
in
Fe 9O10 +2(x+)3(9–x+ )10×–2 =0

44
 10H
0 ou1r0s0Mark s
2+ –2
x27
3–x 0
=0
=
x7
7
So%
o,Ffe +2
= 100 77.7%
9
Fe+=3
107–0 7.7 =22.3%
Ex. Findou% otC
fu a+ndCu ++
in
Cu 1.5
O.
Ans. In
Cu 1.5O oCru 15O10
LeCtu +i+axsnd Cu i+(s15–xi)n
Cu O then
15 10
Totaclharge (+2)x+(15–x)×(+1+ )10×–2
2+ –5
x12x0
=0 or = x5
5
%
oC
fu ++
= 100 33.33 %
15
%
oCfu +
= – 3.33
103
0 =66.67

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45
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Questions
ProblemsbasedonthisLecture

Q.1 Whatisthemeaningofthetermimperfectioninsolids?
Ans. Inperfectionreferstothedeparturefromtheperfectperiodicarrangement
ofatoms,ionsormoleculesinthestr uctureofcrystallinesubstances.
Q.2 Whatisthetypeoflatticeimperfectionsfoundincrystals?
Ans. (a) Stoichiometricdefects,viz.,SchottkydefectandFrenkeldefectand
(b) Non-stoichiometricdefects,viz.,metalexcess,metaldeficiencyand
impuritydefects.
Q.3 Whattypeofdefectcanarisewhenasolidheated?Whichphysical
propertyisaffectedbyitandinwhatway?
Ans. Onheatingasolidvacancydefectisproducedinthecrystal.Thisis
becauseonheating.somelatticesitesbecomevacant.Asaresultofthis
defect,thedensityofthesubstancedecreasesbecausesomeatomsorions
leavethecr ystalcompletely.
Q.4 CaCl2willintroduceSchottkydefectifaddedtoAgClcrystal.Explain.
Ans. TwoAg +ionswillbereplacedbyoneCa 2+
ionstopreserveelectrical
2+
neutrality.Thus,aholeiscreatedatthelatticesiteforeveryCa ion
introduced.
Q.5 WhyisFrenkeldefectnotfoundinpurealkalimetalhalides?
Ans. Thisisbecauseofthefactthatalkalimetalionshavelargesizewhich
cannotfitintotheinterstitialsites.
Q.6 Namethenon-stoichiometricpointdefectresponsibleforcolourin
alkalihalides.
Ans. ExcessofmetalionsandformationofF-centresasaresultoftrapped
electrons.
Q.7 WhatareF-centres?
Ans. ThefreeelectronstrappedintheanionvacanciesarecalledasF-centres.
Q.8 NameonesolidinwhichbothFrenkelandSchoottkydefectsoccur.
Ans. AgBr
Q.9 WhydoesFrenkeldefectnotchangethedensityofAgClcrystals?
Ans. BecauseoftheFrenkeldefect,noionsaremissingfromthecrystalasa
whole,ther efore,thereisnochangeindensity.
Q.10 WhatisSchottkydefect?
Ans. Ifequalnumberofcationsandanionsaremissingfromtheirlatticesites,
thedefectisknownasdefect.
Q.11 Whatarenon-stoichiometriccompounds?
Ans. Iftheactualratioofthecationsandanionsisdifferentasrepresentedby
theidealchemicalformulaofthecompound,itiscalledanon-
stoichiometriccompound.Ex.F e0.9O,Cu 1.5O

46
SoliS
d tate
Q.12 WhyisFrenkeldefectfoundinAgCl?
Ans. Itisbecauseofthereasonthatcationandaniondifferintheirsizeto
moreextent,therefore,cationsoccupyvoidsduetosmallersize.
Q.13 Whatisthenon-stoichiometricdefectincrystals?
Ans. Aresultoftheimperfectionsinthecrystal,theratioofthecationsto
theanionsbecomedifferentfromthatindicatedbytheidealchemical
formula,thenthedefectsaretermednon-stoichiometricdefects.
Q.14 Whichpointdefectbowersthedensityofacrystal?
Ans. Schottkydefect
Q.15 WhatisFrenkeldefect?
Ans. Whensomeions(usuallycations)aremissingfromthelatticesitesand
theyoccupytheinterstitialsitessothatelectricalneutralityaswellas
stoichiometryismaintained,itiscalledFrenkeldefect.
Q.16 Whattypeofstoichiometricdefectisshownby:(i)ZnS(ii)AgBr?
Ans. (i) ZnSshowsfrenkeldefects.
(ii) AgBrshowsbothfrenkelandSchottkydefects.
–2
Q.17 IfNaCIisdopedwith10 mol%ofCaCl whatistheconcetration
2
ofcationvacancies?
Ans. Ionsarereplacedby1ion.Eachioncausesonecationvacancy.Hence,
–2
concentrationofcationvacanciesonbeingdopedwith10 mol%vacancies.
10 2
6.023 1023 6.023 10 19
100
Q.18 WhydoesfrenkeldefectnotchangethedensityofAgClcrystal?
Ans. ThisisbecauseinFrenkeldefects,noionismissingfromthecrystalasa
wholesothedensityremainsunchanged.
Q.19 Whichpointdefectofitscrystalsdecreasesthedensityofasolid?
Ans. Schottkydefect.
Q.20 WhyarethesolidscontainingF-centresparamagnetic?
Ans. Thisisbecausetheelectronsoccupyingthevacantsitesareunpaired.
Q.21 If10 –5mole%ofAlCl 3
isdoppedinNaClthenfindoutvacancies
developed.
Ans. 1AlCl 3means,1Al +++willreplace3Na +
so,twovancanciesaredevelop.

–5
10 5 23
So,10 mole%or 6.01203 willdevelop
100
=2×6.023×10 16 =12.046×10 16vacancies.
Q.22 Whaa t re(iv) acancydefec(tiiI)nterstitiad
l efec?tWhatypeocfompounds
showthesedefect?
Ans. (i)V acancydefect. Whensomelatticesitesinacrystallinesolidarevacant,
thenthecr ystalssufferfromvacancydefectT . hisdefectcanbecreatedupon
heating.Asaresult,thedensityofthesoliddecreases.
(ii) Interstitialdefect. Whensomeconstituentparticlesinaparticularsolid
occupyinterstitia l sitest,hisdefectiscreatedA . saresultt,hedensityotfhesolid
increases.Boththesedefectareshownbynon-ionicsolids.
47
 10H
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Particles in the
Vacant lattice sites interstitial sits

Vacancy defect Interstitial defect

Q.23 Whydoeswhitezincoxide(ZnO)becomeyellowuponheating?
Ans. ZnOonheatinglosesoxygenas:
Theionsar etrappedininterstitialsiteandelectronsintheother.Asa
result,thecrystalappearsyellow.

Lecture-6
ElectricaP
l roperties

(a) Conductors: Solidshavingconductivityrangferom10 t4o

–1
10o7hm –m 1
.
(b)Insulators: Solidshavingconductivityrangferom
–1
10–2t01o0 –1o0hm –m 1
.
(c)Semi-conductors: Solidshavingconductivityrangferom
–1
10–t61o0 o4hm –m 1
.

Conductionofelectricityinmetals
Metalcsonducetlectricity througehlectronsIo.nicconductoarnd
electrolytesconducetlectricitythroughions.
Conductivityofmetalsdependuponnumberofvalencelec-
tronsA. tomiocrbitalfsormmoleculaorrbitalw s hicharceompa-
rablienenergytfoormabondIt.fhibsondipsartiallyfilledor
iotverlapswithahigherenergyunoccupiedconductionband,
thenelectronscanfloweasilyunderanappliedelectricfield
48
SoliS
d tate
andmetalsconductselectricity.
Itfhisenergygapislarget,helectronscannojtumpandcon -
ductiondoesnootccur.

Conductioninsemi-conductors
Insemi-conductorst,henergygapbetweenvalencbeandand
conduction band ismaalnld
som eelectronm
s ayjumtpcoon -
ductionbandandshowsamceonductivityandthicsonductiv-
ityincreaseswithtemperature.
Fewsubstanceslikseiliconandgermaniumarcealledintrin -
sicsemi-conductorsT . hislawofconductivityisincreasedby
addingaforeignsubstanceasismpurityT.hiiscsalledDoping.

(CI)mpuritesdefec:t

(a) Electron -richimpurities:—

Whengroup-14elementsard e opedwithgroup15elemenltike
PhosphorusoA r rsenicT.histypoeifmpurityoccurs.
Group14hav4 evalenceelectronw s hicharu e sedfotrhfeorma-
tiono4
fcovalenbtondswith4electronsog f roup-15elements
andthusonelectronog f roup-15remainsfrew e hichconducts
electricityA. sthceonductionisduteno egativelychargedelec-
tronSothesetypeofsemi-conductorsarecalledn -typ semi-
conductor.

(b)ElectronD- eficiItmpurities:—
Whengroup-14elementasrdeopedwithgroup-13elementsO.ut
of ourvalencelectronsofgroup-143 ,arebondedwith3va-
lencelectronsofgroup-13T . heplacewherethefourthvalence
electronsismissingiscalledelectron -holet.hiselectronhole
canbefilledbyanelectronfromtheneighbouringatomB . ut
49
 10H
0 ou1r0s0Mark s
thiselectronleavesanelectronholaeittsoriginaplositionI.ift
happensi,w t ouldappeaarsitfhelectronholheas movedinthe
directionopposittetohaottfheelectronthaftilleditO
.n applying
theelectrifcieldse,lectronm s ovetsowardtshpeositivelycharged
plattehroughelectronicholesB . uitsteemsthaetlectronsholes
arep ositivelychargedandarem ovingtowardsnegatively
chargedplateT.hisiscalledp-typseemi-conductor.

Group-13 Group-14 Group-15

B C N(gas)
Al Si P
Ga Ge As
In Sn Sb
Th Pb Bi

Applicationofn -typaendp-type
(1)Formakingelectronicomponents
(2F) om
r akingnpnandpnptypteransistors.

MagneticProperties:—
Themagneticpropertiesofthesubstancedependonelectrons.
Everyelectronsrevolvesaroundthenucleusandalsorotates
arounditsown axisandthuseveryelectronbehaviourslikea
magnetO.n thbeasiosm
f agnetipcropertietshseubstancm
e ay
b;e

(i)Paramagnetism:
Thseubstancews hich
arw
e eaklyattracted bymagnetifcield are
calledparamagneticsubstancesT.heyarem agnetisedina
magneticfieldinthseamde irectionThisisduteopresencoef
onoem
r oruenpaired
electronsT.heseelectronasttractedby
mag-
neticfield.
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SoliS
d tate
(ii)Diamagnetic:
Thseubstanceswhicharw e eaklyrepelledbymagnetifcieldare
calle diamagnetiscubstancesT.heyarw e eaklymagnetisedin
oppositde irectionD. iamagnetismishownbythosseubstances
whichdno ohtavue npairedelectronse.g.N
, aClH, 2
OC, H6
6

(iii) Ferromagnetism:
manysubstancelsikFeeC,oN,iC,rO e,t2ca.raettracted
strongly
bymagneticfields,uchsubstancesarecalledferromagnetic
substancesI.nsolidstattehm
e etailonsosfuchsub stancesare
grouped
togetheirntsomalrlegioncsalledomainsI.n
thaebsencoef
magnetifcieldt,hesdeomainasrreandomly oriented
and magnetic
momentsgectancelled. Buw t hensuchsubstancesarpelacedin
magneticfielda,ltlhde omainsgeotrientedinthde irectionof
thm
e agnetifcield
and thusastrong
magnetifcield ipsroduced.
Thisorderingpersisotnremovin gtheelectricaflieldandthuist
becomesapermanenm t agnet.

(iv)Antiferromagnetism:
Itfhiaslignmenotdfomainisisn
such
way
a thatthey
cancel
magneticmomentofeachothert,henno-netmagneticmo-
menitsproducede.g.M , nO.

(v)Ferrimagnetism:
Itfhiaslignmenrtesultasnem
t agnetim
c omentt,hiiscsalled
ferrimagnetisme..g.F,e 3O.4

51
 10H
0 ou1r0s0Mark s
10H
0 ou1r0s0Mark s
MechanismofElectricalConduction

Thceonduction in
mosottfhseolidistshroughelectron movement
underanelectricalfield.However,insomeionicsolids,the
conduction ibsy
ionsT.hereforien thseolidw
s hertehceonduction
isbythemovementofelectrons,theelectricalconductivity
dependsonthenumberofelectronsavailiabletoparticipatein
theconductionprocess.
Thsepacesbetweenvalencbeandandconductionbandrepresent
energiesforbiddentoelectronsandwecalledenergygapor
forbiddenzone.
(i) Inmetalst,heconductionbandisclosetovalenceband
andthereforet,helectronscaneasilygointothe
conductionband T . hereforem , etalsaregoodconductros.
(ii) Ininsulatorst,henergygapbetweenvalencebandand
conductionandthereforee,lectronsfromvalenceband
cannotmoveintotheconductionband. (iii)Severasl
olidshavepropertiesintermediatebetweenmetals andinsul
atorsT.hesaercealledsemi-metalsosremiconductors.
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SoliS
d tate
ConductionofElectricityinSemiconductors

GeandSiarethemostimportantcommercialexamplesof
semiconductorsT.hcerystasltructuresoG f aendSairseimilar
ttohaotd
f iamondA. tomosbfothGaendShiavfeouerlectrons
inthoeutermossthellT.hereforeachatomsiscovalentlybonded
3
withneighbouringatomsthroughsp hybrid.

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 10H
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Questions
Problemsbasedonthisconcept

Q.1 Whatispiezoelectricity?Whattypeofcrystalsexhibitpiezoelectricity?
Ans. Thecrystals,whichonapplyingamechanicalstressproduceelectricity,are
calledpiezoelectriccr ystalsandthephenomenoniscalledpiezoelectricity.
Polarcrystalsinwhichthedipolesalignthemselvesinanorderedmanner
undertheinfluenceofanelectricfieldexhibitpiezoelectricity.
Q.2 Definethe‘forbiddenzone’ofaninsulator.
Ans. Thelargeenergygapbetweenvalencebandandtheconductionbandinan
insulatorcalledforbiddenzone.
Q.3 Whatissuperconductivity?Whodiscoverdit?
Or
Definesuperconductivityofasubstance.
Ans. Asubstanceissaidtobesuperconductorwhenitoffersnoresistancetoflowof
electricity.Thispropertyiscalledsuperconductivity.Mostmetalsbecome
superconductingatverylowtemperature(2-5K)K. ammerlingOnnesdiscoveredit.
Q.4 Definephotovoltaiccompound.
Ans. Acompoundwhichgeneratescurrentwhenexposedtolightiscalled
photovoltaiccompound.
Q.5 Agroup14elementsistobeconvertedinton-typesemiconductorby
dopingitwithasuitableimpurity .Towhichgroupshouldthisimpurity
belong?
Ans. n-typesemiconductormeansconductionduetopresenceoef xcessoef lectrons.
Thereforet,oconvertgroup14elementsinto n-typesemiconductor,itshould
bedopedwithgroup15elements.
Q.6 Classifyeachofthefollowingaseitherap-typeorn-typesemiconductor:
(a)GedopedwithIn (b)BdopedwithSi
Ans. (a) GeisGroup14elementandInisGroup13element.Thus,an
electrondeficitholeiscreatedandtherefore,itisp-type.
(b) BisGroup13elementandSiisGroup14element,therewillbea
freeelectron.Thus,itisn-type.
Q.7 Whatisdoping?Whyisitdone?
Ans. Itisprocessofaddingimpuritiesinacrystallattice.Doppingisdoneby
addingcalculatedamountofimpurities.Itincr easestheconductivity.
Q.8 Whatisthedifferenceinthesemi-conductorsobtainedbydopingsilicon
with AlorwithP?

54
SoliS
d tate
Ans. SilicondopedwithAlformsp-typesemiconductors,i .e.,flowofcurrentis
becauseofcreationofpositiveholeswhilesilicondopedwithPproduces
n-typesemiconductorsi.e .,flowofcurrentisduetoextraelectronshaving
negativecharge.
Q.9 Whattypeofcrystaldefectisproducedwhensodiumchlorideisdoped
withMgCl 2?
Ans. Itiscalledimpuritydefect.Acationvacancyisproduced.Asubstitutional
+ 2+
solidssolutionisformed(because2Na ionsarereplacedbyoneSr ionthe
latticesite).
Q.10 Howdoestheelecricalconductivityofmetallicconductorsvarywith
temperature?
Ans. Electricalconductivitydecreaseswithriseintemperaturebecausekernels
begantovibrateandcreatehindranceintheflowofelectrons.
Q.11 Whatismeantby‘doping’inasemiconductor?
Ans. Dopingmeansincorporatingsmallamountofforgienimpurityincrystals.
Dopingofgroup14elementswithgroup15elementsgiverisetoexcess
electron( n-typesemiconductors)whereaswithgroup13elementsgiveriseto
holes( p-typesemiconductors).
Q.12 Accountforthefollowing:
(i) Phosphorusdopedwithsiliconisasemiconductor.
(ii) Someoftheglassobjectsrecoveredfromancientmonuments
lookmilkyinsteadofbeingtransparent.
(iii) Schottkydefectlowerthedensityofasolid.
Ans. (i) Phosphorusdopedwithsiliconhasholesandhenceactsasn-type
semiconductor.
(ii) Glassobjectsrecoverfromancientmonumentslookmilkybecause
ofsomecr ystallizationtakenplaceinthem.
(iii) Thisbecausesomeofthecationsandanionsaremissingfromthe
crystallattice.
Q.13 Howdoestheelectricalresistivityof(i)asemiconductor(ii)metallic
conductorsvar ywithtemperature?
Ans. Electricarlesistivityofmetallicconductorsincreaseswithtemperaturewhilethat
ofsemiconductorsandsuperconductorsdecreaseswithtemperature.

55
 100H our100Mar
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.

56