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'' A SPECIALLY DESIGNEDKIT FOR LEARNINGI'

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THE KEY THEATLAS EXERCISEI PROFICIENCYTEST EXERCISEII EXERCISEIII EXERCISEIV --> ---) ------) Basic principles ofsub.iects. outlineof thetopicsto be An lectures. discussedclass in ----) --> Basic layoutofsubject,Aroute mapconelatingdifferentsubtopics in coherent manner.

problems getfirsthandexperience to Introductory ofproblem solving. you > To check newlyacquired concepts. A collection goodproblems. of lbstvourobiectiveskill. ten A collection ofprevious years JEEnroblems.

----)

cLAssEs @ BANsAL
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rHE KpY
Crystalline solids: over or arrangement extending Crystalline solidsarethose whoseatom,molecules ionshaveanordered salt, a Long Range.example-(Rock NaCl). Amorphoussolids: are arrange have ordered and no whose constitutentparticles randomly Amorphous solidsarethose Glass ect. Rubber, longrange stucture.example: TYPES OF CRYSTALLINE SOLIDS: Type of Solid Intermolecular forces Ionic Molecular Covalent network Metallic Ion-lonforces Properties Brittle, hardhigh Melting Soft,low meltingnonconducting Hard:High melting and Variablehardness melting ooint conductinp Examples NaCl,KCl, MgCI2 H2O,Br2,CO2, CH4 C-Diamond SiO2 Na,Zn, Cu,Fe

Dispersion forceslDipole-Dipole /H-bond

Covalentbonds Metallicbonds

TYPES UNIT CELL: OF produce points, whole lattice called unitcell.Thewhole is a Collection lattice of whose repetition lattice of unitcell. can considered bemade repetion to by be

fl
l.

UnitCelI:

t)V
BravaisLattice Primitive,FaceCentered, Bodv Centered Primitive, FaceCentered, End Centered Body Centered, Primitive Primitive. End Centered Primitive Primitive.Body Centered Primitive Unit Cell Parameters Interceots Crvstal Angles a=b:c a*b+c
a:b:c

CrystalSystems
Cubic

o:p=y=90o o:B=y:g0o cr: B: y *90o cr,=y:90o,0*90o

2
J

Orthorhombic Rhombohedral Monoclinic Triclinic Tetrasonal Hexagonal

5 6 7

a+b*c a*b*c a=b+c a=b*c

c r, + B * y + 9 0 "
u,=B=v=90o cl=B=90o.v=120"

f f iltRt l
Simple Cubic a=b=c d=p=t=90o Trh"",t".l a = b - *a a = B= ? = 9 0 o

ID

orthorhombic a *b + c o = P= t= 9 0 o

I#

||

ilo*.ri"i. a*b*c o =l =90.,g*90"

LryI b@
Triclinic a+D tc a*B *7*90o

ll ll

f m rrl

ffi rrrl
Hexagonal Primitive a=b*o a=g=90o,I=120o

QBansat Classes

Solid &ate

t2l

1.1

in Primitive or simplecubic (PS/SC)unit cell: Spheres onelayersittingdirectlyon topofthosein previouslayer,sothat all layersareidentical.Eachspherc touchedby six other,hence is coordination number 6.52Yo available is occupied spheres. of space by Example: Polonium in cubic crystallises simple anangement.

W
t.2

z=t;c.N .=6

in Body Centeredcubic @CC) unit cell: Spheres onelayersit in thedepression madeby first layerin a-b-a-b manner. Coordination number 8, and68%of available is space occupied atoms. is by Example: Iron,sodiun and14othermetalcrystallises thismanner. in

Z=2; C.N.:8 Facecenferedcubic (FCC) unit cell: 1.3 Examples: Al, Ni, Fe,Pdall solidnoblegases etc.

= Z : 4 ; C. N. 1 2
2. Densityofcubic crystals:

TYPE OF PACKING: 3. (r) (ii) packing of atoms:This is themostefficientwayofpacking74%ofavailablespace occupied Closest is number 12. is by spheres coordination and Hacagonalclosepack (A-B-A-B) typepacking.'Each layerhashexagonal anangement oftouching sphere 3'dlayeris similar (exactlyontop) of first layer. and Cubicclosepach(A-B-C-A-B-C): AB layersaresimilarto HCParrangementbut third layeris offset on frombothAandB layers. fourthlayeris exactly topof first layer, The

W
(a)

I
void'a'

-#
Explodedview (a) Hexagonalclore-packed stnrcture

ff)--*td'b'
16)

ww
/\ (c) (d)

+ w
Exploded

pimitive unitcll Hexagonal

---layer A
..--layet B

,--... layer A

4. 4.1

Tlpesofvoids Tetrahedralvoid

Tetrahedal void

oftetrahedral voidsoerFCCunit cell Numher

4.2

Octahedralvoid

Ocuhedral void

An octahodral void st the cntre ofan edge in a FCC unit cell. An octahedral void at the body centerdposilion in FCC unit cell

f,.

Radius ratio

(a)

(b)

5.1

Radiusratio for co-ordinationnumber 3

n

(friangularArrangement): + r= : Jtr r+ ' 5 '-

r+ r

2*Ji
t; a/J

= 0.155

bBansatClasses

Solid &ate

14I

5.2

4 number ratiofor coordination Radius r* (Tetrahedral arrangement): * t':

_ Jta +

r+ r

J' _J1 -"-n-- = 0.225

\l z

5.3

Radiusratio for coordinationnumber6: (Octahedral Arrangement) or Radiusratio for coordinationnumber 4 plannararrangement) (Square

,*+r=r I r

,lZ,

17 r-

- = Jz - r :0.414 r

Top view ofoctahedral arrangement

5.4

Radiusratio forcoordination number 8 : (Body centeredcubic crystal)

r* + r: r* + r =

\IJ

t;

..6 r

r+ r

Jj -t = olzz

6. 6.1

Typesof ionic structures Largeratomfbrmicccp Rock saltstructure:Q'{aCl) voids. atomfilling all octahedral smaller and arrangement
Rock salt structure

EBansat Classes

Solid State

FT

6.2

Larger Zinc blende(sphalerite)structure:(ZnS) atomfilling and atomformicccparrangement smaller half of altemate voids tetrahedral
Zinc blende structure

6.3

Caz+ formingccp tr'luoritestructure:(CaF2) voids. arrangement F filling all tetnahedral and

Fluorite structure

trfl W
p#
ffi
),,W
r-_---_4,.,

6.4

Antifluoritestructure:(LirO)d-ionformingccp andLi*taking all tetahedralvoids.

structure Antifluorite

6.5

(CsCl)Cl-atthecomers Cesiumhalidestructure: ofcubeandCs+in thecenter

ffi l l .l l

Csium chloride structure

6.6 6.7 6.8

filling}l3 octahedral voids. CorundumStructure:(Al2O3)CP-forminghcpandAl3* half Rutile structure: (TiOr) 02- forminghcpwhileTia*ionsoccupy of theoctahedral voids. Pervoskite structure:(CaTiO.) Ca2+ inthe comerof ofcube. cube02- atthefacecenterandTia*at thecentre

Peruoskite slructure

Iffi W

6.9

formingfcc,Mg2*filling 1/8oftetrahedral Spinelandinverse spinelstructure: Gt4gAlrO.)CPvoids spinelstrucfire,02- ion form FCClattice, ions andAl3+ takinghalf of octahedral voids.Inaninverse A.2+ ll8 l/8 occupy ofthe tetrahedral voidsandtrivalent cationoccupies of thetetrahedral voidsand1/4of voids. *re octahedral Crystal defects: position, is called pointdefect. this Pointdefects: Whenionsor atoms notholdthetheoretical do Point defects oftwo types: are Stoichiometric defects: Schottlrydefect:Dueto missingof ionsfrom latticepoint in pairs. as Frenkel defect: It is caused to the creationof latticevacancy a resultof misplaced in due ion interstitial site. number. NaCl,KCl, KBr Schottkydefect commoninionicsolidwithhighcoordination Frenkeldefect:-Solidwithlow coordinationnumberZnS,AgBr. ion Non^stoichiametric defec*:Ratroofpositiveandnegative differ from that indicated chemical by formula. Metal-excess defect : Anegativeionreplacedbyelectron.(F-centre) in Extrametal present lattice electron present interstitial ion in and also site. point,electroneutality from lattice Metal-deficiency defect caused : Cation by missing maintained by metalionswith higheroxidationstate F"os+oO. as

7,

0) (a) (b) * * (il) * (a) (b) *

EBansalClasses

Solid State

t6I

TITE

ATLAS

TYPESOF SOLIDS

Crystallinesolids have long rangeorder i.e. the constituentparticles are arrangedin a regular fashion and this symmetrical arrangementextends throughoutthe crystallength.

Lattice- Unit Cells

(i) A unit cell is the smallestrepeatingstructuralunit the crystallinesolid. Bravaishas predictedthat thereare only 14 unit cells that existsin nature. (ii)The relation between the edge length (a) and the radius of atom (r) forming lattic: :'[2 are as follows . PC :t-4, BCC : f3 a=4;FC.C a=4r& HP: aF2rheight(c) O, F

fractionanddensitydetermination
(i) The ratio of volume occupiedby the effectiveatomsto the volume of the unit is calledpackingfraction.Its valuesfor variousunit cellsarePC = 0.52, B CC: 0 .6 8 , F C C& H P = 0 .7 a . (ii)Density (p) of cubic crystal is calculated where using the relationp S{3 '
N A V "a"

n=numberof effectiveatoms,M=Atomic mass,N6y:Avogadro'snumberand a: Edge length.

of void andradiusratio rule

(i) Tetrahedral octahedral The & voids areprosentonly inclosestpackedstructures. effective number of octahedralvoids in a unit cell is equal to the effective voids is equal numberof atomsin the unit cell & effectivenumberof tetrahedral to doublethe numberof effeotiveatomsin the unit cell. (ii)The sum ofradius ofthe atom ofhost lattice(rf and the radiusofatom occupying void(r1,yor rq6) is given by Ji" void,r1,+r11,1= For oci'ihedril'void, r6+rnir= fA fo. tetrahedral ]Jg (iii)Limiting radiusis definedis ttiEminimum ratio of cationto anioi radius.It is definedwhen cation is in contactwith anionsand anionsare also in contact with eachother. number.The limiting radiusratio for on iv)Radiusratio depends the co-ordination the various co-ordinationnumbersare planar) 0.414, t :0.225,C.N.4(Square C.N.3: 0.155, C.N.4(Tetrahedral) C.N.6(Octahedral) 0.414,C.N.8(BCC) : 0.732,C.N.l2 (IdealFCC) : I :

Ionic lattice has 2 major defects.Schottky defect occurs due to the cation-anionpair vacancy, the which decreases densityof crystal,Frenkeldefect occurs when an ion leavesits lattice site and fits into an interstitialspace.Due to Frenkeldefect, densityof crystalremainsunaffected.

bBansal Clrcses

Solid&ate

fvI

EXERCISE I
Formula of ionic solid from unit cell description Q.1 Q.2 of A A cubicsolidis madeup of two elements andB. AtomsB areatthecorners thecubeandA at the r0fhat theformulaof compound. is bodycenhe. point whichgoldoccupytlnt lattice inacubiclatticein Acompoundalloyofgoldandcoppercrystallizes ofeach ofthe cubefaces.What is the ofthe cubeand copperatomoccupythe centres at corners formulaof thiscompound. packarrangementB occupyingone. Fourthoftetahedral Acubicsolidismade byatomsAforming close voids.Whatis theformulaof compound. void andC occupying of theoctahedral half Titaniumandoxygen, stucture if Whatis thepercent mass by oftitanium in rutile,amineralthatcontain holes. aray of oxideions,with titaniumin onehalf ofthe octahedral canbedescribed aclosetpacked as oftianium? Whatis theoxidationnumber of in is of Spinel a important class oxidesconsisting two types metalionswith theoxideionsananged of by CCPpattem. normalspinelhasone-eight The ofthe tetahedralholesoccupied onetypeofmetal ion type andonehalf of theoctahedral occupied another of metalion, Sucha spinelis formedby hole by Givethefonnulae ofspinel. and02-,withzn2+ inthetetahedralholes, Zn2*,A13* of Ifthe radius K" ions 132pm andthatofF- ion is 135pm, intheNaCl typestructure. I(F crystallizes lengthofthe unit cell? Whatis theclosetK-K Whatis theedge whatis theshortest K-F distance? distance? packed the A closed structure uniformspheres theedgelengthof 534pm. Calculate radiusof has of sphere, ifitexistin (c) FCC lattice (b) BCC lattice (a)simplecubiclattice cubicskucture Calculate densityof diamondfrom thefactthatit hasfacecentered the witl two atoms perlattice pointandunitcell edge A. length 3.569 of rryhich bedescribed a cubictypeofunit cell havingone by crystallizes a structure into may An element If on atomon eachcomerofthe cubeandtwo atoms oneof its bodydiagonals. thevolumeofthis unit calculate number atoms present is7.2 gcm-3, the of cellis 24x10'.4cm3 density element and of in 200gofelement. of To Silverhasanatomicradiusof 144pm andthedensity silveris 10.6g cm-3. whichtypeof cubic crystal, silverbelongs? lengthof unit cell of AgCl is foundto be555pm stuctureasthatofNaCl. Theedge AgCl hasthesarne percentage sites areunoccupied. of that andthe density ofAgCl is 5,561g cm-3.Findthe

Q.3 Q.4

Q.5

Edge length, density ond number of iloms per unit cell Q.6

Q.7

Q.8 Q.9

Q.l0 Q.I I

cubic lattice and the edge of the unit cell is Q.l2 Xenon crystallisesin the face-centred and 620pm.Whatis thenearest neighbour distance whatis theradius ofxenonatom? Q.l3 Q.I 4 Q.l5 packed In radii88and200pmrespectively.theclosed crystal ofcompound Thetwo ionsA+ B- have and AB,predict theco-ordination numberofA*. length 400pm.Calculate interionic is and the CsClhas bccarrangement itsunitcelledge the distance CsCl. in in of Goldcrystallizes a facecentered cubiclattice.If thelengthof the edge theunit cell is 407pm, assuming to be spherical. it Atomic mass calculate density goldaswell asits atomicradius the of of gold: 197 amu,

ofthe unit cell is 654pm. ShowthatKBr has Q. I 6 ThedensityofKBr is 2.75g cmr . Thelengthofthe edge facecentered cubicstructure. : 6.023x 1023 : mol-l . At. mass K : 39.Br : 80

Closses

Solid State

crystallizes a structure 200 the in having FCCunitcellof anedge pm.Calculate density, if Q, I 7 An element 200g of thiselement atoms. contains 1023 24x Calculate density its Q,18 Theeffectiveradiusof the iron atomis | -42A. It hasrock saltlike structure. (Fe= 56 amu) In distance between Pb+2 ion Q.I 9 A crystalof lead(Il) sulphidehasNaCl structure. this crystaltheshortest of and52-ion is 297 pm.Whatis thelength theedge theunitcellin leadsulphide? calculate Also of the uritcellvolume. into with Cl- ionsatth Q.20 If thelengthof thebodydiagonalfor CsClwhich crystallises acubicstructure comers Cs+ionsat thecente of theunit cellsis 7 A andtheradiusof theCs+ion is L69 A, wha is and theradii of Cl- ion?

PROFICIENCY TEST l. 2. 3. 4. 5. 6. 7. 8. 9. 10, I 1. 12. 13. 14. 15. 16. 17. 18. 19. 20. solids isotropic. Crystalline are possiHe. Rhombohedral, triclinicandhexagonal theunitcells,whichhave are onlyprimitivearangement RankofFCC andHP unitscellsaresame. havingonly onetypeof atomandall voids Theminimumvoid fractionfor anyunit cell in anyshape is unfilled 0.26. Packing fractionof a latticestructure on depends theradiusof theatomcrystallizingin it. Thelocationoftetrahedral of voids in FCCunit cell arethecenters I minicubes forminga largecubeEffective nrnnber ofoctahedral voidsin aunitcellis equal theeffective to number atoms theunitcell. of in planargeomebry same. and Radius ratio for co-ordination number4 havingtetrahedral square is planargeometry co-ordination number4havingsquare Theradius ratiovaluefor co-ordination and geometry same. number havingoctahedral 6 is a Ametallicelement crystallises a latticecontaining sequence layers into of ofAB AB AB Any packing spheres of larnce26%percent volumeof this latticeis emptyspacby leaves voidsin the out Therelation between edge length(a)andradius atom(r) for BCC latticeis_. of Therelation between length(a)andradius ofatom(r) forFCC latticeis_. edge pattem called is ABCABC......layering -*packing, pattem called ABABAB...,,layering is foundin-lattice. lattice. packing,foundin-*

primitiveunitcellintermsofradiusofatom(r) is_, Height(c)oftlrchexagonal otheronlyifthe cationtoanionradius fora givenco-ordinatim Anionswouldbein contactwith each numberis primitiveunit cell is oftetrahedral voidsin hexagonal Thenumber number is_. Thelimitingradituforco-ordination 8 (in chloride distance termsofedgelength, is equal Forcesium structure, interionic the a) to and Density crystal ofa defect _due to Schottky dueto Frankel defect.

&Bansal Classes

Solid State

try-

EXERCISE II
Q.l foundto honhasbodycenteredcubiclatticestructure.Theedgelengthoftheunitcellis be 286 pm. ofan iron atom? Whatis theradius of oftheunitcell.Thelength ofthesideoftheunitcellis 412pm andCl- ionhasa radius bodydiagonal the l8 I pm.Calculate radiusof Cs+ion. packed the structure mixedoxides latticeis madeup of oxideions,oneeighthof of Q.3 In acubicclosed while onehalfof&e octahedral voids areoccupiedbydivalentions(A2+) voidsoccupied tetrahedral hivalentions@3*;.Whatis theformulaofthe oxide? structure.Iftheanionhasaradiusof250 pm, what AsolidA+ andB-hadNaCl typeclosedpacked shouldbetheidealradiusof thecation?Cana cationC+havinga radiusof 180pm be slippedinto the for siie tetrahedral ofthe crystalofA+B- ? Givereasons your answer. Calculate valueofAvogadro's the fromthefollowingdata: number Density NaCl= 2.165 cm-3 of Distance between andCl- in NaCl : 281pm. Na* IftheradiusofMg2*ion,Cs*ion,02-ion,52-ionandCl-ionare0.65A,l.69A,l.40A,1.84A,a ofthe cations thecrystals l.8l A respectively. Calculate co-ordination the numbers in ofMgS, MgO andCsCl. thedensityofiron in boththese structures.

alongthe clrlorideformsa bodycentered cubiclattice.Cesiumandchlorideionsarein contact Q .2 Cesium

Q.4

Q.s
Q.6

Q.7 Ironoccursasbccaswell asfcc unit cell. Ifthe effectiveradiusof anatomof iron is 124pm. Compute
f'' + f- , +

Q.8

Giventhatt c l KClcrystallizesintfresametypeoflatticeasdoesNaCl. fL*'t (a)Theratioofthe sides unit cell for KCI to thatforNaCl and of (b) Theratioof densities ofNaCl to thatfor KCl.

analA=o tK*

7 Cahulate:

Q.9

weight=I00)havingbcc hasunitcell fuielementA(Atomic stucture edge length400pm. Calculatefte ofA andnumberof unit cellsandnumber atomsin I 0 gm ofA. density of

percentage zincblende is25o/o. structure that in Q.10 Prove thevoid space has of chloride four formulaunits.Theedge lengthof thewrit cell is 0.564nm. Q.l I A unitcellof sodiurn of Whatis thedensity sodiumchloride. : the of are by Q.I 2 In acubiccrystal CsCl(density 3.97gm/cm3) eightcomers occupied Cl- ionswith Cs+ ionsatthecentre. Calculate distance the the between neighbouring andCl- ions. Cs+ NaCl structure. K" Whatis thedistance between andF* in KF if density KF is 2.48gm/cm3 of . Q.I 3 I(F has percentage ironis present theform of is What of of of in Q.l4 . Thecomposition a sample wustite F"o.rrO,.o.

Fe(rtr)?

may in sffucfure. structure bedescribed a cubiclatticewith This as Q.l 5 BaTiO,crystallizes theprevoskite ionsoccupyingthecornerofthe barium unitcell,oxideionsoccupyingthe face-centersandtitanium ion occupying center theunit cell. the of (a) If titaniumis described occupying as holesin BaOlattice,whattypeof holesdoesit occupy? (b) Whatfractionof thistypeholedoesit occupy? Q.l6 Q.l7 Q.l8 Rb+is surrounded eightiodideionseach Rbl crystallizes bccstructure whicheach in in by ofradius 2.17A. Findthelengthofone sideof RbIunit cell. IfNaCl is dopped with l0-3 mol % SrClr,whatis thenumbers ofcationvacancies? void Findthesizeof largest sphere will fit in octahedral in anidealFCCcrystalasa functionof that not atomicradius't'.Theinsertion thissphere void does distorttheFCClattice. of into the Calcuiate packingfraction voidsarefilled by thissphere. ofFCC latticewhenall theoctahedral

EBansatClasses

Solid State

TOI

and manganese at thecomers fluoride ionsat thecenterof eachedge. ions Q. I 9 A cubic unit cell contains (a) Whatis theempiricalformulaofthe compound? Whatistheco-ordinationnumberoftheMnion? O) of (c) the lengthofthe unit cell,ifthe radius Mn ion is 0.65A andthatof F ion is I .36A Calculate edge length ofthe cubicunit cellofNall is in structure thatofNaCl.Theedge as Q.20 NaHcrystallizes thesame 4.S8 A. ofNa* is 0.95A. (a) the the of Calculate ionicradius H-, provided ionicradius (b) CalculatethedensityofNaH. ofthe cubicunit cell is a: 4.07A. The in Q.2l Metallicgoldcrystallises fcc lattice. tength goldatoms. (a) between Whatis theclosestdistance in calculated (a). (b) neighbours" doeseachgoldatomhaveat thedistance How many"nearest (c) Whatis thedensityofgold? (d) thatthepacking fractionofgold is 0.74. Prove Q.22Icecrystallizesinahexagonallattiee.AtthelowtemperatweatwhichthestructureR^ wasdetermined,thelauiceconstantswerea=4.53A,andb:7'60A(seefigure).I I I Il | lI Howmanymoleculesarecontainedinaunitcell? [density(ice)=0.92gmlcm3)] t--tG to belongs. find thetypeof cubiclattice whichthecrystal the Q.23 Using datagivenbelow, Pd FeV 388 301 286 ainpm 12.16 p ingm cm-3 5.96 7.86

\tr>r

with edge a= length, 5.2A. cubic Potassium crystallizes a body-centered lattice in neighbours? between nearest Whatis thedistance neighbours? between next-nearest Whatis thedistance each atomhave? K neighbours does How manynearest does neighbours eachKatomhave? How manynext-nearest Whatisthecalculateddensityofcrystallinepotassium? per in Q.25 Provethatvoid space fluorite structure unit volumeofunit cell is 0.25I . in whereX is at thecomers d X formedby elements & Y Crystallizes a cubicstructure, Q.26 A compound If is theformulaof thecompound? sidelengthis 5A, estimc What ttrecubeandY is at six facecenters. atomicweightofXandYas 60and90respectively. thedensityofthe solidassuming Its is cubicstructure. density 8.9gm/cml.Calculate in Q.27 Themetalnickelcrystallizes a facecentred (a) ofthe edge theunit cell. of thelength (b) ofthe nickelatom.[AtomicweightofNi = 58.89] theradius foreachottcr ofcrystalsin whichFeandMg ionsmaysubstitute ofmineralsconsists Q.28 Theolivineseries the changing volumeof theunitcell.In olivineseriesd without substitutional impuritydefect causing ions voidsanddivalent occupyiqg 1/4m occupyrng ofoctahedral oxideionexistasFCCwith Sia+ minerals, ll4moftetrahedralvoids.Thedensityofforsterite(magnesiumsilicate)is3.2lglc*andthatoffayalir and (fenoussilicate)is 4.34g/cc.Findtheformulaof forsterite fayalitemineralsandthepercentaged of in fayalite anolivinewith a density 3.88g/cc. Q.24 (a) (b) (c) (d) (e) lengttr5.874" with edge in hawleyite, form of CdS,crystallizes oneofthe cubiclattices, one Q.29 Themineral is Thedensityofhawleyite 4.63g cm-r. gcm-3. FindtheSchottkydefectin (r) Inwhichcubiclatticedoeshawleyitecrystallize? (ii) crystaldecreases densityd the a through germanium boronpassed cunentof tivalent gaseous Q.30 A strong createdfol by of thecrystaldueto partreplacement germanium boronanddueto interstitialvacancies is one missingGeatoms.In onesuchexperiment, glam of germanium takenandtheboronatomsG lhc by of foundto be 150 ppm by weight,whenthedensity theGecrystaldecreases 4%. Calculate whicharefilledupbyboronatoms. percentage duetogermanium, ofmissingvacancies Atomicrlt, Ge :72.6. B = I I

Classes Ei,Bansat

Solid State

FU

EXERCISE III
Q.1 ' Q.2 Q.3 at of in are A solidhasa structure which W atoms located thecorners a cubiclattice,O atomat the is centre theedges Na atomat cente of thecubic.Theformulafor the compound of and (C) NarWO, (D) NaWOo (A) NaWO, (B) NaWO, The Thedensityof CaF,(fluorite stucture)is 3.I 8 g/cm3. lengthofthe sideofthe unit cell is (D) 273ptn (C) 546pm (A) 253pm (B) 3aapm structure ofan ionic compounds? isconectinthe rock-salt Whichofthe following statements (A) coordination that numberof cationis fourwhereas of anionis six. (B) coordination that numberofcation is six whereas of anionis four. (C)coordination number each cation anionis four. and of (D) coordination numberofeachcationandanionis six. CaF,andCsClarerespectively numberofcation andanion Fluorite in Thecoordination (C)8:4and (D)4:2and2:4 (A) 8:4and6:3 8:8 and4:4 @)6:3 Theinterstitialholeis calledtetalredralbecause (A) It is formedby four spheres. (B) Partly same andpartly different. (C) It is formedby four spheres centres the ofwhich form a regulartetrahedron. Noneofthe abovethree. @) of Thetetahedralvoids formedby ccpanangement Cl- ionsin rock saltstructure are (B) Occupied Cl- ions (A) Occupied Na" ions by by (D)Vacant (C)OccupiedbyeitherNa*orClions particle a face-centred in each Thenumber around cubiclatticeis ofnearest neighbours (c) 8 (D) 12 (A)4 (8)6 (C) packing cations occupyonly 2/3octahedral (A) and voidsin it, If theanions form hexagonal closest is formulaofthe compound thenthegeneral (C) C2A3 (D) C3A2 (B) CA2 (A) CA withYatomsoccupying ithasthree typesofatomsX,Y,Z.XformsaFCClattice Asolid is formedand half voids.Theformulaofttre solid is: all thetetralredral occupying theocfrahedral voidsandZ atoms (C)X4Y2Z (D)X4YZ2 (A\\Y Z (B)XyYZ4

Q.4 Q.5

Q.6

Q.7 Q.8

Q.9

in LiAg crystallizes cubiclatticein which bothlithium andsilverhave compound Q.10 Theintermetallic is coordination numberofeight.Thecrystalclass (A) Simplecubic (B) Body centred cubic (C) Facecentredcubic @) None lenght of480 pm.If theradius XY in ofY- is. Q.I I A compound crystallizes BCC latticewith unitcelledge pm,thentheradius X* is of 225 (C1225 pm (A) 127.5 pm (B) 190.68 pm (D) 255pm to of Q.12 Themass a unit cell of CsClcorresponds (A) l Cs+and Cl- (B) I Cs+and6Cl- (C)4Cs*and4Cl- (D)8 Cs+and Cl l I packing atoms (radius ru), radius atomB thatcanbefitted of of A : the Q.I 3 In theclosest intotetahedralvoidsis (C)0.414 ru (D) 0.732 (B) 0.225 ru ru (A) 0.155 r, packed of closed sheets equalsizedspheres not of do Q.14 Whichoneofthe following schemes ordering generate closepackedlattice. (C)ABBAABBA (B)ABACABAC (D)ABCBCABCBC (A)ABCABC

EBansalClasses

Solid State

Ir2]

AB Ifthe radiusA+ is 22.5pm, thentheidealradiusof F Q. I 5 An ionic compound hasZnS tlpe structure. wouldbe (A) 54.35 pm (B)l00pm (C) la5.l6pm @)noneofthese 16 NH4CIcrystallizesin a body-centered cubictypelattice with a unit cell edgelengthof 387pm. The Q. distance betweenthe oppositively clrarged inthe latticeis ions (A)335.1pm (B)83.77pm (C\274.a6pm (D)t37.23pm Q.l7 rpu*= 95pm and ra,-=l8l pm in NaCl (rocksalt)structure. Whatis theshortest distance between Na*ions? (A)778.3pm Q.l8 (B)276pm (C) 195.7pm (D)390.3pm

In diamon4carbon atomoccupyFCClatticepointsaswell asaltemate tehahedral voids.Ifedgelength ofthe unit cellis 356pm,thenradius ofcarbonatomis (A)77.07pm (B )154.14pm (C)2 5 1 . 7 p m (D)89pm Whichofthe following will showschotrky defect (A) CaF2 (c)Agcl @)znS

Q. l9

(D)CsCl

orderofinitialsT (true) tr'(false) followingstatements. or for Q.20 Givethecorrect I. In ananti-fluoritestrucflre anions form FCClatticeandcations occupyall tetrahedral voids. tr. Iftheradius ofcations anions 0.2A and0.95A thencoordinate and are numberofcationintbe crystalis 4. III An atom/ionis tansferredfrom a latticesiteto anintentitial positionin Frenkeldefect. ry. Densityofcrystalalwaysinueasesduetosubstitutinalimpuitydefect. (A)TFFF (B)FTTF (c)TFFr (D)]TTF

IV EXERCISry
No. Paragraphfor Question I to 3 arrangement atomsis described a of a encountered as In hexagonal systems crystals, frequently of prism.Here, topandbottom hexagons three and atoms sandwiched ofthecellareregular are hexagonal the (HCP),is calledhexagonal modelof thisstructure, close-packed in between them. space-filling A planeby six identicalspheres closely in surrounded thesame as constituted sphere a flat surface ofa on possible. placed first layersothattheytoucheach overthe otherandrepresent as Threespheres then are threespheres touches ofthe bottomlayer.Finally,the layer.Eachoneofthesetlueespheres thesecond to Assume layeriscovered second with athird layerthatis identical thebottomlayerin relativeposition. radius ofeverysphere be'r'. to Q. I Q.2 Thenumber atoms this HCPunit cellsis of in

(A)4

(B)6

(c) 12

(D)17

Thevolumeofthis HCPunitcellis

6) z+Jir3
Q.3

(B)rcJir3
(B )47.6%

(c)tzJif
(c)32 %

(D) 1 tE'
(D)26%

64

Theempty inthis HCPunitcellis space

(A)74%
Q.4

IJEE-20081 g/molis 5 Awhichcrystallizesin 75 Theedgelength ofunitcellofametalhavingmolecularweight cubic (NA:6 I G3).Givetheanswer pm. lattice.Ifthe ofmetalatom. density 2 g/ccthenfrndtheradius is in "

pEE2006l

Q.5 Q.6

length400pm. Calculate maximumdiameter An element crystallises FCClatticehaving in edge the the whichcanbeplaced interstital siteswithoutdisturbing structure. in UEE 20051 in contains cations altemate Whichofthe following FCC structure tetrahedral voids? (c)Nqo (D) CaF2 (A)NaCI (B)ZnS

UEE200sl

I : is Q.7(i) ABcrystallizesinarocksaltstructurewithA:B= l.TheshortestdistancebetweenAandB YIBnm.TheformulamassofAB is6.023Yamuu,{roeYisanya$itaryconstant. FindthedensrtyinkgmJ. (ii) Ifmeasured density 20kgm-3.Identiffthetypeofpoint defect. is UEE*20041 Q.8 on Marblesof diameterI 0 mm eachareto be ananged a flat surface thattheir centres within the so lie the enclosed four linesof lengtheach40 mm.Sketch arrangement will givethemaximum area by that per in of that and number marbles unit area, canbeenclosed thismanner deduce expression the to it calculate UEE-20031 in A substance crystallises a FCClattice whichatorns occupy in "An' AB, each corner thecubeand" of ooB" Identifytheconectcomposition atoms occupy centesofeachfaceofthe cube. ttre ofthe substance

Q.9

Apy
(A)AB3
(B)A4Bl

(D) composition cannot specified [JEn-20021 be planes FCClattice. givenbelowshowthelocation atoms three in crystallographic of in Draw Q. I 0 Thefigures planes yourdiagram. theunitcell for theconesponding and in structure identifythese

(c)A.B

Eff i
Solid State

ooo
aY-\a\

pEE-20001

bBansatClasses

II4]

Q.I I

[n a solid"AB" havingNaCl structure atoms occupy comers thecubicunit cell. If all the the "A" of face-centred atomsalongoneofthe axesareremoved, thentheresultant stoichiomety ofthe solid is (A)s' (B)A,B (c)A1Br (D)484 IJf,E-20001 In anyionicsolid[\D(] with schottkydefects, number ofpositive negative arcsame,[T@ *rc and ions

Q.l2

number ametalcrystallising a hcpstructure of in is Q.13 Thecoordination (A) l2 (B )4 (c)8

(D) 6

UEE-20001 UEE-20001

lengthsare3.5and3.0A Q.14 Ametalcryatallisesintotwocubicphases,FCCandBCCwhoseunitcell respectively. Calculate ratioofdensities the ofFCC andBCC. UEE-Ieeel are Q. 15 Whichofthe following statements conect: (A) Thecoordinationnumberofeachtype inCsCl is 8, ofion Ametal thatcrystallises BCC structure a coordination in has number12. @) (C)Aunit cellofan ioniccrystal shares some ofits ionswith otherunitcells (D) Thelength theunitcellin NaCl is 552pm. of I hu. :95 pm ; 1.'- : l8l pm ] UEE-19981 each Na* ion is sunounded six Cl- nearest by neighbours _ and Q.16 In thesodiumchloridestrucrure, Na*ionsnextnearest neighbours. [.rEE-1ee1 has The length units. edge ofthe unitcellis 0.564 Whc nm. Q.17 A unitcellofsodiumchloride fourformula isthedensitv sod.chloride. of UEE-lee7l with atomicrad.Whatwould Q.l 8 Ctromiumcrystallises bcclattice.Theunitcell lengthis 287pm. Calculate bethedensity ofcluomium. UEE-leel

SBansal Classes

Solid&ate

Fsl

ANSWERKEY
EXERCISE I Q.l Q.5 Q.8 Q.l I A-B ZnAlzOA 3.5g cm-3 0.24% Q.2 Q.6 Q.9 AuCq Q.3 A4B2C2 Q.4 Q.7 Q.l0 5g.g5o ,+4 267pm,231.2pm,188.8 pm FCC

267pm,534pm,378 pm 3.472x 102a atoms

pm,219.25 pm Q.l2 438.5 Q.l5 19.4glcm3.l43.9pm

e.l 3 6 e.t7 4l .67gcm-3

Q.l4 346.4pm Q.l8 5.74gcma

srn-1q.20 l.ilA Q.19 a :5.94x10-8cm,Y=2.096'19*zz

PBOFICIENCYTEST
l.F 5.F 2. 6.

T3.F T7.T
ll. 14.

4.7 8.F

9. 13.

10.

Ji a:4r

12.

Ji a= 4rl

cubic close, FCC c : +r ,/,

close, hexagonal HP

t 5.

16.

leastorminimum

t7.

t2

18.

0.732

19.

,ftu 2

20.

remains decreases, constant

EXERCISE II Q.I Q.5 Q.8 Q.9 pm 123.84 x 6.01 102i Q.2 Q.6 pm 175.8 4, 6, I Q.3 Q.7 AB2O4 Q.4 pm,No 103.4

7.887glcc,8,59gm/cm3

(a) 1.143, 1.172 (b) gm/cm3,6.023"1022 5.188 atomsofA, 3.0ll5xl022unit cells

A Q.1l 2.l6grn/cm3Q.l2 3.57 Q.l5 (a)octahedral,(b) li4

A Q.13 2.68s A Q.16 4.34

Q . 1 4 ls . 0 s 3

Q.l7 6.Q!x lSrr*o1-t (b)6,(c)4.02A Q.l9 (a)MnFr,

Q.l8 0.414r,79.3% r.:z Q.20 (a)l.4eA, 1U; glcm: Solid &ate

Bansal Classes

{I6l

A, Q.2l (a)2.8S 1U;t Z , (c) I 9.4g/cc centered Q.23 forFeisbcc,forV isbcc.for Pdis face Q.24 (a)4.5A, (b)5.2A, 1c;8,(d)6, (e)0.92glcm3 Q.27 (n)3.52A,0)t.Z+A (ii) e/cc Q.29 (i)3.90, 0.120 EXERCISEIII Q.l B Q.2 C Q.e A Q.16 A Q.3 D Q.4 C

ofHrO Q'22 4 molecules

g/cm3 Q.26 XYr.4.38 Q28 MgrSiOo,FerSiOo,59% Q'30 2'376%

Q.s

Q.6

Q.7

Q.S C Q.ls B

Q.lO B Q.17 D

Q.ll B Q.lS A EXERCISEIV

Q'12 A Q'19 D

Q . l3 B Q'20 D

Q'14 C

Q.lB Q.6 B

Q2A

D Q.3

Q.4

p 216'5m

Q's

117'1pm

Q . 7 ( i) :5 kem { if It density. isonlypossible and density observed calculated in is difference theoretically (d There huge defect. space interstitial i.e.substitution occupies species foreign some Q.S Discuss Q.13 A Q.9 A Q'll D Q.10 Dscuss Q.l5 A. C' D Q'1612 Q'12 True glcmj Q 17 2'165

Q,14 | .259

pm,(ii) glcm3 7.30 Q.1S (i)124.27

,1