SOLIDSTATE

KEYCONCEPTS
Asweknowthatmatterexistsindifferentphysicalstatesunderdifferentconditions
oftemperatureandpressure.Forexamplesolidstate,liquidgasesplasmaandBECetc.Nowwe
willstudyaboutdifferentaspectsofsolidstate.
Introduction:
1. ThestateofmatterwhoseM.Pisaboveroomtempissolidstate.Solidshavedefiniteshape
andvolume,havinghighdensityandconstituentparticlesareheldstrongly.
2. Basedonarrangementofparticlestypesofsolid:1:Crystalline
2:Amorphous
3. Crystallinesolidshaveregulararrangementofconstituentparticlesthroughout,melting
pointissharp,Anisotropicinnatureandgiveclearcutcleavage.
4. Amorphoussolidshavenoregulararrangement,nosharpM.P,isotropicinnaturetheydo
notexhibitcleavageproperty.
5. Amorphoussilicaisusedinphotovoltaiccells.(Applicationsofamorphoussolid)
6. Spacelatticeistheregular3D,arrangementofconstituentparticlesinthecrystallinesolid.
Itshowshowtheconstituentsparticles(atoms,moleculesetc.)arearranged.
7. Smallestrepeatingunitinaspacelatticeiscalledunitcell.
8. Thereare4typesofunitcells,7crystalsystemsand14bravaislattices.
9. Typesofunitcell

No.ofatomsperunitcell

i.Simplecubicunitcell

8*1/8=1

ii.FCC(Facecenteredcubic)

8*1/8+6*1/2=4

iii.BCC(Bodycenteredcubic)

8*1/8+1*1=2

10. Hexagonalclosepackingandcubicclosepackinghaveequalefficiencyi.e74%
11. Packingefficiency=volumeoccupiedbyspheres(Particles)/volumeofunitcell*100
12. Forsimplecubicunitcellthep.f.=1*4/3*r3/8*r3*100=52.4
13. Thepackingefficiencyinfcc=4*4/3*r3/16*21/2r3*100=74

14. Thepackingefficiencyinbcc=2*4/3*r3/64*33/2r3*100=68
15. Thepackingefficiencyinhcp=74
16. Packingefficiencyinbccarrangementin68%andsimplecubicunitcellis52.4%
17. Unoccupiedspacesinsolidsarecalledinterstitialvoidsorinterstitialsites.
18. Twoimportantinterstitialvoidsare(I).Tetrahedralvoidand(II).Octahedralvoid.
19. Radiusratioistheratioofradiusofvoidtotheradiusofsphere.
a. Fortetrahedralvoidradiusratio=0.225
Foroctahedralvoidradiusratio=0.414
20. No.oftetrahedralvoid=2*N(N=No.ofparticles)
21. No.ofoctahedralvoid=N
22. Formulaofacompounddependsuponarrangementofconstituentofparticles.
23. Densityofunitcell
D=Z*M/a3*NA

D=density,M=Molarmass,a=sideofunitcell,NA=6.022*1023
24. Therelationshipbetweenedgelengthandradiusofatomandinteratomicorinterionic
distancefordifferenttypesofunitisdifferentasgivenbelow
a. Simplecubicunitcell

a=2R

b. FCC

a=4R/

c. BCC

a=4R/

25. Interatomicdistance=2R
26. Interionicdistance=Rc+Ra(Rc=Radiusofcation,Ra=Radiusofanion)
27. Imperfectionistheirregulartyinthearrangementofconstituentparticles.
28. PointdefectorAtomicdefect>itisthedeviationfromidealarrangementofconstituent
atom.Pointdefectsaretwotypes(a)Vacancydefect(b)Interstitialdefect
29. Vacancydefectlowersthedensityand

30. Interstitialdefectincreasesthedensityofcrystal.
31. Pointdefectsintheioniccrystalmaybeclassifiedas:
a. Stoichiometricdefect(Ratioofcationandanionissame).
b. NonStoichiometricdefect(disturbtheratio).
c. Impuritydefects(duetopresenceofsomeimpurityionsatthelatticesites)
32. Schottkydefectlowersthedensityofcrystalitarisesduetomissingofequalno.ofcations
ofanionsfromlatticesitese.g.Nacl.
33. Frenkeldefectisthecombinationofvacancyandinterstitialdefects.Cationsleavetheir
actuallatticesitesandcometooccupytheinterstitialspacedensityremainsthesameeg.
Agcl.
34. Nonstoichiometricdefect
a. Metalexcessdefectduetoanionvacancy.
b. Metalexcessduetopresenceofinterstitialcation.
c. Metaldeficiencyduetoabsenceofcation.
SHORTANSWERQUESTION(2)
Q1.Whatdoyoumeanbyparamagneticsubstance?
Ans:Attractedbypragneticfieldandthesesubstancesaremadeofatomsorionswithunpaired
electrons.
Q2.WhichsubstanceexhibitschottkyandFrenkelbothdefects.
Ans:AgBr
Q3.NameasaltwhichisaddedtoAgclsoastoproducecationvacancies.
Ans:Cdcl2
Q4.WhyFrenkeldefectsnotfoundinpureAlkalimetalhalide.
Ans:DuetolargersizeofAlkalimetalion.
Q5.Whatistheuseofamorphoussilica?
Ans.UsedinPhotovoltaiccell.

Q6.AnalysisshowsthatametaloxidehastheempiricalformulaMo.9801.00.Calculatethe
percentageofM2+andM3+ionsinthecrystal.
Ans:LettheM2+ioninthecrystalbexandM3+=0.98x

Sincetotalchangeonthecompoundmustbezero

2x+3(0.098x)z=0
X=0.88
%ofM2+0.88/0.96*100=91.67
%ofM3+=10091.91.67=8.33
Q7.Whatisthecoordinationno.ofcationinAntifluoritestructure?
Ans:4
Q8.WhatistheCo.No.ofcationandanioninCaesiumChloride.
Ans:8and8
Q9.WhatisFcentre?
Ans:Itistheanionvacancywhichcontainsunpairedelectroninnonstoichiometriccompound
containingexcessofmetalion.
Q10.WhatmakesAlkalimetalhalidessometimescoloured,whichareotherwisecolourless?

VeryShortAnswers(1marks):

1.Howdoesamorphoussilicadifferfromquartz?
In amorphous silica, SiO4 tetrahedral are randomly joined to each other whereas in quartz they are
linkedinaregularmanner.

2.Whichpointdefectlowersthedensityofacrystal?
Schottkydefect.

3.Whyglassiscalledsuppercooledliquids?
Ithastendencytoflowlikeliquid.


4.Someoftheveryoldglassobjectsappearslightlymilkyinsteadofbeingtransparentwhy?
Duetocrystallization.

5.Whatisanisotropy?
Physicalpropertiesshowdifferentvalueswhenmeasuredalongdifferentincrystallinesolids.

6.Whatisthecoordinationnumberofatoms?
a) infccstructureb)inbccstructure

a)12

b)8

7.Howmanylatticepointsarethereinonecellof
a) fccb)bccc)simplecubic

a)14

b)9

c)8

8.Whatarethecoordinationnumbersofoctahedralvoidsandtetrahedralvoids?
6and4respectively.

9.Whycommonsaltissometimesyellowinsteadofbeingofbeingpurewhite?
Due to the presence of electrons in some lattice sites in place of anions these sites act as Fcenters.
Theseelectronswhenexcitedimpartcolortothecrystal.

10.AcompoundisformedbytwoelementsXandY.TheelementYformsccpandatomsofXoccupy
octahedralvoids.Whatisformulaofthecompound?
No.ofYatomsbeN

No.ofXatomsbe=N

No.ofoctahedralvoidsN

FormulaXY


HOTSVeryShortAnswers:

1. DefineFcenters.
2. Whattypeofstoichiometricdefectisshownby
a. Zns
b. AgBr
3. Whatarethedifferencesbetweenfrenkelandschottkydefect?
4. Definethefollowingtermswithsuitableexamples
o Ferromagnetism
o Paramagnetism
o Ferrimagnetism
o 1216and1315groupcompound
5. Intermsofbandtheorywhatisthedifference
o Betweenconductorandaninsulator
o Betweenaconductorandasemiconductor

ShortAnswers(2Marks):HOTS
1. Explain how electrical neutrality is maintained in compounds showing Frenkel and Schottky
defect.

In compound showing Frenkel defect, ions just get displaced within the lattice. While in
compounds showing Schottky defect, equal number of anions and Cations are removed from
thelattice.Thus,electricalneutralityismaintainedinbothcases.
2. Calculatethenumberofatomsinacubicunitcellhavingoneatomoneachcornerandtwo
atomsoneachbodydiagonal.
8corner*1/8atomperunitcell=1atom
Therearefourbodydiagonalsinacubicunitcellandeachhastwobodycentreatoms.
So4*2=8atomsthereforetotalnumberofatomsperunitcell=1+8=9
3. GoldcrystallizesinanFCCunitcell.Whatisthelengthofasideofthecell(r=0.144mm)
r=0.144nm
a=2*2r
=2*1.414*0.144nm
=0.407nm

4. Classifyeachofthefollowingaseitheraptypeorntypesemiconductor.
a)GedopedwithIn
b)BdopedwithSi
(a) Ge is group 14 elements and In is group 13 element. Therefore, an electron deficit hole is
created.Thussemiconductorisptype.
(b)Sincebgroup13elementandSiisgroup14elements,therewillbeafreeelectron,thusitisn
typesemiconductor.

5. Intermsofbandtheorywhatisthedifferencebetweenaconductor,aninsulatorandasemi
conductor?
Theenergygapbetweenthevalencebandandconductionbandinaninsulatorisverylargewhilein
a conductor, the energy gap is very small or there is overlapping between valence band and
conductionband.

6. CaCl2willintroduceScottydefectifaddedtoAgClcrystal.Explain
Two Ag+ ions will be replaced by one Ca2+ ions to maintain electrical neutrality. Thus a hole is
createdatthelatticesiteforeveryCa2+ionintroduced.

7. Theelectricalconductivityofametaldecreaseswithriseintemperaturewhilethatofasemi
conductorincreases.Explain.
Inmetalswithincreaseoftemperature,thekernelsstartvibratingandthusofferresistancetothe
flow of electrons. Hence conductivity decreases. In case of semiconductors, with increase of
temperature,moreelectronscanshiftfromvalencebandto conduction band.Henceconductivity
increases.
8. What type of substances would make better permanent magnets, ferromagnetic or
ferromagnetic,why?
Ferromagnetic substances make better permanent magnets. This is because the metal ions of a
ferromagnetic substance are grouped into small regions called domains. Each domain acts as tiny
magnetandgetorientedinthedirectionofmagneticfieldinwhichitisplaced.Thispersistsevenin
theabsenceofmagneticfield.

9. Inacrystallinesolid,theatomsAandBarearrangedasfollows:
a. AtomsAarearrangedinccparray.
b. AtomsBoccupyalltheoctahedralvoidsandhalfofthetetrahedralvoids.Whatisthe
formulaofthecompound?
Letno.ofatomsofAbeN
No.ofoctahedralvoids=N

No.oftetrahedralvoids=2N
i)
Therewillbeoneatomofbintheoctahedralvoid
ii)
TherewillbeoneatomofBinthetetrahedralvoid(1/2*2N)
Therefore,total2atomsofbforeachatomofA
Thereforeformulaofthecompound=AB2
10. In compound atoms of element Y forms ccp lattice and those of element X occupy 2/3rd of
tetrahedralvoids.Whatistheformulaofthecompound?

No.ofYatomsperunitcellinccplattice=4
No.oftetrahedralvoids=2*4=8
No.oftetrahedralvoidsoccupiedbyX=2/3*8=16/3
Thereforeformulaofthecompound=X16/3Y4
=X16Y12
=X4Y3

HOTSShortAnswer:
1. Howmanylatticepointsarethereinoneunitcellofthefollowinglattices?
o FCC
o BCC
o SCC

2. AcubicsolidismadeoftwoelementsXandY.AtomYareatthecornersofthecubeandX
atthebodycenters.Whatistheformulaofthecompound?
3. Silver forms ccp lattice and X ray studies of its crystal show that the edge length of its
unitcellis408.6pm.Calculatethedensityofsilver(Atomicwt=107.9u).
4. A cubic solid is made up of two elements P and Q. Atoms of the Q are present at the
corners of the cube and atoms of P at the body centre. What is the formula of the
compound?WhatarethecoordinationnumberofPandQ.
5. Whathappenswhen:
o CsClcrystalisheated
o PressureisappliedonNaClcrystal.

ShortAnswers(3marks):
1. The density of chromium is 7.2g cm3. If the unit cell is a cubic with length of 289pm,
determinethetypeofunitcell(AtomicmassofCr=52uandNA=6.022*1023atomsmol1).

d=Z*M

a3*NA

Z=?,a=289pm=2891010cm,M=52gmol1,d=7.2gcm3

Z=d*a3*N=7.2(gcm3)*[289*1010cm]3*6.022*1023(atommol1)

52gmol1

2. An element crystallizes in FCC structure; 200 g of this element has 4.12*1024 atoms. If the
densityofAis7.2gcm3,calculatetheedgelengthofunitcell.
3. Niobiumcrystallizesinbccstructure.Ifitsdensityis8.55cm3,calculateatomicradiusof[At.
MassofNiobium=92.9u,NA=6.022*1023atomsmol1].
4. IfradiusofoctahedralvoidisrandradiusofatominclosepackingisR,derivetherelationship
betweenrandR.
5. Nonstoichiometriccuprousoxidecanbepreparedinthelaboratory.Inthisoxide,copperto
oxygenratioisslightlylessthan2:1canuaccountforthefactthatthesubstanceisap=type
semiconductor?
6. Theunitcellofanelementofatomicmass50uhasedgelength290pm.Calculateitsdensity
theelementhasbccstructure(NA6.02*1023atomsmol1).
7. Calculate the density of silver which crystallizes in face centered cubic form. The distance
betweennearestmetalatomsis287pm(Ag=107.87gmol1,NA=6.022*1023).

8. What is the distance between Na+ and Clions in NaCl crystal if its density 2.165g cm3. NaCl
crystallizesinFCClattice.

9. AnalysisshowsthatNickeloxidehasNi 0.98 O 1.00 whatfractionsofnickelexistasNi2+ ionsand

Ni3+ions?

10. Find the type of lattice for cube having edge length of 400pm, atomic wt. = 60 and density
=6.25g/cc.

HOTSShortAnswer:

1. Aluminiumcrystallizesincubicclosedpackstructure.Itsmetallicradiusis125pm
o Whatisthelengthofthesideoftheunitcell?
o Howmanyunitcellaretherein100cm3ofAluminium.

2. Classifythefollowingaseitherptypeorntypesemiconductors.
GedopedwithIn
BdopedwithSi

3. Zincoxideiswhitebutitturnsyellowonheating.Explain.

LongAnswer(5Marks):
1. ItisfacecenteredcubiclatticeAmetalhascubiclattice.Edgelengthoflatticecellis2A0.The
densityofmetalis2.4gcm3.Howmanyunitscellarepresentin200gofmetal.

2. Ametalcrystallizesasfacecenteredcubiclatticewithedgelengthof450pm.Molarmassof
metalis50gmol1.Thedensityofmentalis?

3. Acompoundformshexagonalclosepackedstructure.Whatisthetotalnumberofvoidsin0.5
molofit?Howmanyofthesearetetrahedralvoids?

4. Copper Crystallizes into FCC lattice with edge length 3.61*108 cm. Show that calculated
densityisinagreementwithmeasuredvalueof8.92g/cc.

5. Niobium crystallizes in bcc structure with density 8.55g/cc, Calculate atomic radius using
atomicmassi.e.93u.

HOTSLongAnswer:
1.ThecompoundCuClhasFustructurelikeZnS,itsdensityis3.4gcm3.Whatisthelengthoftheedge
ofunitcell?
Hint:d=ZXM/a3XNA
a3=4X99/3.4X6.022X102.3
a3=193.4X1024cm3
a=5.78X108cm

2.IfNaClisdroppedwith103mol%SrCl2.Whatistheconcentrationofcationvalancies?

3.IftheradiusoftheoctahedralvoidisrandtheradiusoftheatomintheclosepackingisR.derive
relationshipbetweenrandR.

4. The edge length of the unit cell of mental having molecular weight 75g/mol is A0 which
crystallizesintocubiclattice.Ifthedensityis2g/cm3thenfindtheradiusofmetalatom(NA =
6.022*1023)
5. ThedensityofKBr.Is2.75gmcm 3 .thelengthofedgeoftheunitcellis654pm.Predictthe
typeofcubiclatticetowhichunitcellofKBrbelongs.
NA=6.023*1023;atmassofK=39:Br.=80
Ans.Calculatevalueofz=4soithasfcclattice

6. CsCl has bcc arrangement and its unit cell edge lenth is 400 pm . calculate the interionic
distanceofCsCl.Ans.34604pm
7. TheradiusofanIronatomis1.42A0 .Ithasrocksaltstructure.Calculatedensityofunitcell.
Ans.5.74gcm3
8. What is the distance between na+ and Cl in a NaCl crystal if its density is 2.165 gcm3 NaCl
crystallineinthefcclattice.Ans.281PM
9. Copper crystalline with fcc unit cell. If the radius of copper atom is 127.8 pm. Calculate the
densityofcoppermetal.At.MassofCu=63.55uNA=6.02*1023Ans.a=22.r,a3=4.723*1023,
d=8.955.74gcm3