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12.4: Defects in Crystals
SkillstoDevelop
Tounderstandtheoriginandnatureofdefectsincrystals.
The crystal lattices we have described represent an idealized, simplified system that can be used to understand many of the important principles
governingthebehaviorofsolids.Incontrast,realcrystalscontainlargenumbersofdefects(typicallymorethan104permilligram),rangingfrom
variableamountsofimpuritiestomissingormisplacedatomsorions.Thesedefectsoccurforthreemainreasons:
1. Itisimpossibletoobtainanysubstancein100%pureform.Someimpuritiesarealwayspresent.
2. Evenifasubstancewere100%pure,formingaperfectcrystalwouldrequirecoolingtheliquidphaseinfinitelyslowlytoallowallatoms,ions,
or molecules to find their proper positions. Cooling at more realistic rates usually results in one or more components being trapped in the
wrongplaceinalatticeorinareaswheretwolatticesthatgrewseparatelyintersect.
3. Applyinganexternalstresstoacrystal,suchasahammerblow,cancausemicroscopicregionsofthelatticetomovewithrespecttotherest,
thusresultinginimperfectalignment.
Inthissection,wediscusshowdefectsdeterminesomeofthepropertiesofsolids.Webeginwithsolidsthatconsistofneutralatoms,specifically
metals,andthenturntoioniccompounds.

Defects in Metals
Metalscanhavevarioustypesofdefects.Apointdefectisanydefectthatinvolvesonlyasingleparticle(alatticepoint)orsometimesaverysmall
setofpoints.Alinedefectisrestrictedtoarowoflatticepoints,andaplanedefectinvolvesanentireplaneoflatticepointsinacrystal.Avacancy
occurs where an atom is missing from the normal crystalline array it constitutes a tiny void in the middle of a solid (Figure 12.4.1). We focus
primarilyonpointandplanedefectsinourdiscussionbecausetheyareencounteredmostfrequently.

Figure12.4.1:CommonDefectsinCrystals.Inthistwodimensionalrepresentationofacrystallatticecontainingsubstitutionalandinterstitial
impurities,vacancies,andlinedefects,adashedlineandarrowsindicatethepositionofthelinedefect.

Impurities
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Impuritiescanbeclassifiedasinterstitialorsubstitutional.Aninterstitialimpurityisusuallyasmalleratom(typicallyabout45%smallerthanthe
host) that can fit into the octahedral or tetrahedral holes in the metal lattice (Figure 12.4.1). Steels consist of iron with carbon atoms added as
interstitialimpurities(Table12.4.1).Theinclusionofoneormoretransitionmetalsorsemimetalscanimprovethecorrosionresistanceofsteel.

Table12.4.1:Compositions,Properties,andUsesofSomeTypesofSteel
NameofSteel TypicalComposition* Properties Applications
lowcarbon <0.15%C softandductile wire
mildcarbon 0.15%0.25%C malleableandductile cables,chains,andnails
knives,cuttingtools,drill
highcarbon 0.60%1.5%C hardandbrittle
bits,andsprings
15%20%Cr,1%5%Mn,5%
cutlery,instruments,and
stainless 10%Ni,1%3%Si,1%C,0.05% corrosionresistant
marinefittings
P
lowcoefficientof measuringtapesand
invar 36%Ni
thermalexpansion metersticks
hardandwear armorplate,safes,and
manganese 10%20%Mn
resistant rails
retainshardnessat
highspeed 14%20%W highspeedcuttingtools
hightemperatures
hard,strong,and magnetsinelectric
silicon 1%5%Si
highlymagnetic motorsandtransformers
*Inadditiontoenoughirontobringthetotalpercentageupto100%,moststeelscontainsmall
amountsofcarbon(0.5%1.5%)andmanganese(<2%).
Incontrast,asubstitutionalimpurityisadifferentatomofaboutthesamesizethatsimplyreplacesoneoftheatomsthatcomposethehostlattice
(Figure12.4.1).Substitutionalimpuritiesareusuallychemicallysimilartothesubstancethatconstitutesthebulkofthesample,andtheygenerally
haveatomicradiithatarewithinabout15%oftheradiusofthehost.Forexample,strontiumandcalciumarechemicallysimilarandhavesimilar
radii,andasaresult,strontiumisacommonimpurityincrystallinecalcium,withtheSratomsrandomlyoccupyingsitesnormallyoccupiedbyCa.
Note
Interstitialimpuritiesaresmalleratomsthanthehostatom,whereassubstitutionalimpuritiesareusuallychemicallysimilarandaresimilarinsizeto
thehostatom.

Dislocations, Deformations, and Work Hardening

Insertinganextraplaneofatomsintoacrystallatticeproducesanedgedislocation.Afamiliarexampleofanedgedislocationoccurswhenanearof
corncontainsanextrarowofkernelsbetweentheotherrows(Figure12.4.2).Anedgedislocationinacrystalcausestheplanesofatomsinthelattice
todeformwheretheextraplaneofatomsbegins(Figure12.4.2).Theedgedislocationfrequentlydetermineswhethertheentiresolidwilldeformand
failunderstress.

Figure12.4.2:EdgeDislocations.Shownaretwoexamplesofedgedislocations:(a)anedgedislocationinanearofcornand(b)athree
dimensionalrepresentationofanedgedislocationinasolid,illustratinghowanedgedislocationcanbeviewedasasimplelinedefectarisingfrom
theinsertionofanextrasetofatomsintothelattice.Inbothcases,theoriginoftheedgedislocationisindicatedbythesymbol.
Deformationoccurswhenadislocationmovesthroughacrystal.Toillustratetheprocess,supposeyouhaveaheavyrugthatislyingafewinches
offcenteronanonskidpad.Tomovetherugtoitsproperplace,youcouldpickuponeendandpullit.Becauseofthelargeareaofcontactbetween
therugandthepad,however,theywillprobablymoveasaunit.Alternatively,youcouldpickuptherugandtrytosetitbackdownexactlywhere

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youwantit,butthatrequiresagreatdealofeffort(andprobablyatleastoneextraperson).Aneasiersolutionistocreateasmallwrinkleatoneend
oftherug(anedgedislocation)andgraduallypushthewrinkleacross,resultinginanetmovementoftherugasawhole(part(a)inFigure12.4.3).
Movingthewrinklerequiresonlyasmallamountofenergybecauseonlyasmallpartoftherugisactuallymovingatanyonetime.Similarly,ina
solid,thecontactsbetweenlayersarebrokeninonlyoneplaceatatime,whichfacilitatesthedeformationprocess.

Figure12.4.3:TheRoleofDislocationintheMotionofOnePlanarObjectacrossAnother.(a)Pushingawrinkleacrosstherugresultsinanet
movementoftherugwithrelativelylittleexpenditureofenergybecauseatanygiventimeonlyaverysmallamountoftherugisnotincontactwith
thefloor.(b)Asecondintersectingwrinklepreventsmovementofthefirstbypinningit.
Iftherugwehavejustdescribedhasasecondwrinkleatadifferentangle,however,itisverydifficulttomovethefirstonewherethetwowrinkles
intersect(part(b)inFigure12.4.3)thisprocessiscalledpinning.Similarly,intersectingdislocationsinasolidpreventthemfrommoving,thereby
increasingthemechanicalstrengthofthematerial.Infact,oneofthemajorgoalsofmaterialsscienceistofindwaystopindislocationstostrengthen
orhardenamaterial.
Pinningcanalsobeachievedbyintroducingselectedimpuritiesinappropriateamounts.Substitutionalimpuritiesthatareamismatchinsizetothe
host prevent dislocations from migrating smoothly along a plane. Generally, the higher the concentration of impurities, the more effectively they
blockmigration,andthestrongerthematerial.Forexample,bronze,whichcontainsabout20%tinand80%copperbymass,producesamuchharder
andsharperweaponthandoeseitherpuretinorpurecopper.Similarly,puregoldistoosofttomakedurablejewelry,somostgoldjewelrycontains
75%(18carat)or58%(14carat)goldbymass,withtheremainderconsistingofcopper,silver,orboth.
Ifaninterstitialimpurityformspolarcovalentbondstothehostatoms,thelayersarepreventedfromslidingpastoneanother,evenwhenonlya
smallamountoftheimpurityispresent.Forexample,becauseironformspolarcovalentbondstocarbon,thestrongeststeelsneedtocontainonly
about1%carbonbymasstosubstantiallyincreasetheirstrength(Table12.4.1).
Mostmaterialsarepolycrystalline,whichmeanstheyconsistofmanymicroscopicindividualcrystalscalledgrainsthatarerandomlyorientedwith
respecttooneanother.Theplacewheretwograinsintersectiscalledagrainboundary.Themovementofadeformationthroughasolidtendstostop
atagrainboundary.Consequently,controllingthegrainsizeinsolidsiscriticalforobtainingdesirablemechanicalpropertiesfinegrainedmaterials
areusuallymuchstrongerthancoarsegrainedones.

Grainboundaries.Asapolycrystallinematerialsolidifies,grainswithirregularshapesform.Theinterfacesbetweengrainsconstitutegrain
boundaries.(Squaresrepresentunitcellswithingrains.)
Workhardeningistheintroductionofadensenetworkofdislocationsthroughoutasolid,whichmakesitverytoughandhard.Ifallthedefectsina
single1cm3sampleofaworkhardenedmaterialwerelaidendtoend,theirtotallengthcouldbe106km!ThelegendarybladesoftheJapaneseand
Moorishswordsmithsowedmuchoftheirstrengthtorepeatedworkhardeningofthesteel.Asthedensityofdefectsincreases,however,themetal
becomesmorebrittle(lessmalleable).Forexample,bendingapaperclipbackandforthseveraltimesincreasesitsbrittlenessfromworkhardening
andcausesthewiretobreak.

Memory Metal
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Memory Metal
ThecompoundNiTi,popularlyknownasmemorymetalornitinol(nickeltitaniumNavalOrdinanceLaboratory,afterthesitewhereitwasfirst
prepared), illustrates the importance of deformations. If a straight piece of NiTi wire is wound into a spiral, it will remain in the spiral shape
indefinitely, unless it is warmed to 50C60C, at which point it will spontaneously straighten out again. The chemistry behind the temperature
inducedchangeinshapeismoderatelycomplex,butforourpurposesitissufficienttoknowthatNiTicanexistintwodifferentsolidphases.
Thehightemperaturephasehasthecubiccesiumchloridestructure,inwhichaTiatomisembeddedinthecenterofacubeofNiatoms(orvice
versa).Thelowtemperaturephasehasarelatedbutkinkedstructure,inwhichoneoftheanglesoftheunitcellisnolonger90.Bendinganobject
made of the lowtemperature (kinked) phase creates defects that change the pattern of kinks within the structure. If the object is heated to a
temperature greater than about 50C, the material undergoes a transition to the cubic hightemperature phase, causing the object to return to its
originalshape.Theshapeoftheobjectabove50Ciscontrolledbyacomplexsetofdefectsanddislocationsthatcanberelaxedorchangedonlyby
thethermalmotionoftheatoms.

Memorymetal.FlexonisafatigueresistantalloyofTiandNithatisusedasaframeforglassesbecauseofitsdurabilityandcorrosionresistance.
Memory metal has many other practical applications, such as its use in temperaturesensitive springs that open and close valves in the automatic
transmissionsofcars.BecauseNiTicanalsoundergopressureortensioninducedphasetransitions,itisusedtomakewiresforstraighteningteethin
orthodonticbracesandinsurgicalstaplesthatchangeshapeatbodytemperaturetoholdbrokenbonestogether.
Another flexible, fatigueresistant alloy composed of titanium and nickel is Flexon. Originally discovered by metallurgists who were creating
titaniumbasedalloysforuseinmissileheatshields,Flexonisnowusedasadurable,corrosionresistantframeforglasses,amongotheruses.
Example12.4.1
Becausesteelswithatleast4%chromiumaremuchmorecorrosionresistantthaniron,theyarecollectivelysoldasstainlesssteel.Referringtothe
compositionofstainlesssteelinTable12.4.1and,ifneeded,theatomicradiiinFigure7.7,predictwhichtypeofimpurityisrepresentedbyeach
elementinstainlesssteel,excludingiron,thatarepresentinatleast0.05%bymass.
Given:compositionofstainlesssteelandatomicradii
Askedfor:typeofimpurity
Strategy:
UsingthedatainTable12.4.1andtheatomicradiiinFigure7.7,determinewhethertheimpuritieslistedaresimilarinsizetoanironatom.Then
determine whether each impurity is chemically similar to Fe. If similar in both size and chemistry, the impurity is likely to be a substitutional
impurity.Ifnot,itislikelytobeaninterstitialimpurity.
Solution:
According to Table 12.4.1, stainless steel typically contains about 1% carbon, 1%5% manganese, 0.05% phosphorus, 1%3% silicon, 5%10%
nickel,and15%20%chromium.Thethreetransitionelements(Mn,Ni,andCr)lienearFeintheperiodictable,sotheyshouldbesimilartoFein
chemical properties and atomic size (atomic radius = 125 pm). Hence they almost certainly will substitute for iron in the Fe lattice. Carbon is a
secondperiodelementthatisnonmetallicandmuchsmaller(atomicradius=77pm)thaniron.Carbonwillthereforetendtooccupyinterstitialsites
in the iron lattice. Phosphorus and silicon are chemically quite different from iron (phosphorus is a nonmetal, and silicon is a semimetal), even
thoughtheyaresimilarinsize(atomicradiiof106and111pm,respectively).Thustheyareunlikelytobesubstitutionalimpuritiesintheironlattice
orfitintointerstitialsites,buttheycouldaggregateintolayersthatwouldconstituteplanedefects.
Exercise12.4.1
Considernitrogen,vanadium,zirconium,anduraniumimpuritiesinasampleoftitaniummetal.Whichismostlikelytoformaninterstitialimpurity?
asubstitutionalimpurity?
Answer:nitrogenvanadium

Defects in Ionic and Molecular Crystals

All the defects and impurities described for metals are seen in ionic and molecular compounds as well. Because ionic compounds contain both
cationsandanionsratherthanonlyneutralatoms,however,theyexhibitadditionaltypesofdefectsthatarenotpossibleinmetals.
The most straightforward variant is a substitutional impurity in which a cation or an anion is replaced by another of similar charge and size. For
example, Br can substitute for Cl , so tiny amounts of Br are usually present in a chloride salt such as CaCl2 or BaCl2. If the substitutional
impurityandthehosthavedifferentcharges,however,thesituationbecomesmorecomplicated.Suppose,forexample,thatSr2+ (ionicradius=118
pm)substitutesforK+ (ionicradius=138pm)inKCl.Becausetheionsareapproximatelythesamesize,Sr2+ shouldfitnicelyintothefacecentered
cubic (fcc) lattice of KCl. The difference in charge, however, must somehow be compensated for so that electrical neutrality is preserved. The
simplestwayisforasecondK+ iontobelostelsewhereinthecrystal,producingavacancy.ThussubstitutionofK+bySr2+ inKClresultsinthe
introductionoftwodefects:asiteinwhichanSr2+ ionoccupiesaK+ positionandavacantcationsite.Substitutionalimpuritieswhosechargesdo
notmatchthehostsareoftenintroducedintentionallytoproducecompoundswithspecificproperties.
Virtuallyallthecoloredgemsusedinjewelryareduetosubstitutionalimpuritiesinsimpleoxidestructures.Forexample,Al2O3, a hard white
solidcalledcorundumthatisusedasanabrasiveinfinesandpaper,istheprimarycomponent,ormatrix,ofawidevarietyofgems.Becausemany
trivalent transition metal ions have ionic radii only a little larger than the radius of Al3+ (ionic radius = 53.5 pm), they can replace Al3+ in the
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octahedralholesoftheoxidelattice.SubstitutingsmallamountsofCr3+ions(ionicradius=75pm)forAl3+ givesthedeepredcolorofruby,anda
mixture of impurities (Fe2+ ,Fe3+ ,andTi4+ ) gives the deep blue of sapphire. True amethyst contains small amounts of Fe3+ in an SiO2 (quartz)
matrix.Thesamemetalionsubstitutedintodifferentminerallatticescanproduceverydifferentcolors.Forexample,Fe3+ ionsareresponsiblefor
theyellowcoloroftopazandthevioletcolorofamethyst.Thedistinctenvironmentscausedifferencesindorbitalenergies,enablingtheFe3+ ionsto
absorblightofdifferentfrequencies,atopicdiscussedlater.

Thesamecationindifferentenvironments.AnFe3+substitutionalimpurityproducessubstanceswithstrikinglydifferentcolors.
Substitutionalimpuritiesarealsoobservedinmolecularcrystalsifthestructureoftheimpurityissimilartothehost,andtheycanhavemajoreffects
onthepropertiesofthecrystal.Pureanthracene,forexample,isanelectricalconductor,butthetransferofelectronsthroughthemoleculeismuch
sloweriftheanthracenecrystalcontainsevenverysmallamountsoftetracenedespitetheirstrongstructuralsimilarities.

If a cation or an anion is simply missing, leaving a vacant site in an ionic crystal, then for the crystal to be electrically neutral, there must be a
correspondingvacancyoftheionwiththeoppositechargesomewhereinthecrystal.IncompoundssuchasKCl,thechargesareequalbutopposite,
sooneanionvacancyissufficienttocompensateforeachcationvacancy.IncompoundssuchasCaCl2,however,twoCl anionsitesmustbevacant
tocompensateforeachmissingCa2+ cation.Thesepairs(orsets)ofvacanciesarecalledSchottkydefectsandareparticularlycommoninsimple
alkali metal halides such as KCl (part (a) in Figure 12.4.4). Many microwave diodes, which are devices that allow a current to flow in a single
direction,arecomposedofmaterialswithSchottkydefects.

Figure12.4.4:TheTwoMostCommonDefectsinIonicSolids.(a)ASchottkydefectinKClshowsthemissingcation/anionpair.(b)AFrenkeldefect
inAgIshowsamisplacedAg+cation.
Occasionallyoneoftheionsinanioniclatticeissimplyinthewrongposition.Anexampleofthisphenomenon,calledaFrenkeldefect,isacation
thatoccupiesatetrahedralholeratherthananoctahedralholeintheanionlattice(part(b)inFigure12.4.4).Frenkeldefectsaremostcommoninsalts
that have a large anion and a relatively small cation. To preserve electrical neutrality, one of the normal cation sites, usually octahedral, must be
vacant.
FrenkeldefectsareparticularlycommoninthesilverhalidesAgCl,AgBr,andAgI,whichcombinearathersmallcation(Ag+ ,ionicradius=115
pm)withlarge,polarizableanions.CertainmorecomplexsaltswithasecondcationinadditiontoAg+ andBr orI have so many Ag+ ions in
tetrahedralholesthattheyaregoodelectricalconductorsinthesolidstatehencetheyarecalledsolidelectrolytes.Sincemostioniccompoundsdo
notconductelectricityinthesolidstate,howevertheydoconductelectricitywhenmoltenordissolvedinasolventthatseparatestheions,allowing
themtomigrateinresponsetoanappliedelectricfield.)Inresponsetoanappliedvoltage,thecationsinsolidelectrolytescandiffuserapidlythrough
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the lattice via octahedral holes, creating Frenkel defects as the cations migrate. Sodiumsulfur batteries use a solid Al2O3 electrolyte with small
amountsofsolidNa2O.Becausetheelectrolytecannotleak,itcannotcausecorrosion,whichgivesabatterythatusesasolidelectrolyteasignificant
advantageoveronewithaliquidelectrolyte.
Example12.4.2
InasampleofNaCl,oneofevery10,000sitesnormallyoccupiedbyNa+ isoccupiedinsteadbyCa2+ .AssumingthatalloftheCl sitesarefully
occupied,whatisthestoichiometryofthesample?
Given:ionicsolidandnumberandtypeofdefect
Askedfor:stoichiometry
Strategy:
A. Identifytheunitcellofthehostcompound.Computethestoichiometryif0.01%oftheNa+ sitesareoccupiedbyCa2+ .Iftheoverallchargeis
greaterthan0,thenthestoichiometrymustbeincorrect.
B. Ifincorrect,adjustthestoichiometryoftheNa+ iontocompensatefortheadditionalcharge.
Solution:
APureNaClhasa1:1ratioofNa+ andCl ionsarrangedinanfcclattice(thesodiumchloridestructure).IfalltheanionsitesareoccupiedbyCl ,
thenegativechargeis1.00performulaunit.If0.01%oftheNa+ sitesareoccupiedbyCa2+ ions,thecationstoichiometryisNa0.99Ca0.01.This
resultsinapositivechargeof(0.99)(+1)+(0.01)(+2)=+1.01performulaunit,foranetchargeinthecrystalof+1.01+(1.00)=+0.01performula
unit.Becausetheoverallchargeisgreaterthan0,thisstoichiometrymustbeincorrect.
BThemostplausiblewayforthesolidtoadjustitscompositiontobecomeelectricallyneutralisforsomeoftheNa+ sitestobevacant.IfoneNa+
site is vacant for each site that has a Ca2+ cation, then the cation stoichiometry is Na0.98Ca0.01. This results in a positive charge of (0.98)
(+1)+(0.01)(+2)=+1.00performulaunit,whichexactlyneutralizesthenegativecharge.ThestoichiometryofthesolidisthusNa0.98Ca0.01Cl1.00.
Exercise12.4.2
InasampleofMgOthathasthesodiumchloridestructure,0.02%oftheMg2+ ionsarereplacedbyNa+ ions.Assumingthatallofthecationsitesare
fullyoccupied,whatisthestoichiometryofthesample?
Answer: If the formula of the compound is Mg0.98Na0.02O1x, then x must equal 0.01 to preserve electrical neutrality. The formula is thus
Mg0.98Na0.02O0.99.

Nonstoichiometric Compounds
Thelawofmultipleproportions,statesthatchemicalcompoundscontainfixedintegralratiosofatoms.Infact,nonstoichiometriccompoundscontain
large numbers of defects, usually vacancies, which give rise to stoichiometries that can depart significantly from simple integral ratios without
affectingthefundamentalstructureofthecrystal.Nonstoichiometriccompoundsfrequentlyconsistoftransitionmetals,lanthanides,andactinides,
withpolarizableanionssuchasoxide(O2 )andsulfide(S2 ).SomecommonexamplesarelistedinTable12.4.2,alongwiththeirbasicstructure
type. These compounds are nonstoichiometric because their constituent metals can exist in multiple oxidation states in the solid, which in
combinationpreserveelectricalneutrality.

Table12.4.2:SomeNonstoichiometricCompounds
Compound ObservedRangeofx
Oxides*
FexO 0.850.95
NixO 0.971.00
TiOx 0.751.45
VOx 0.91.20
NbOx 0.91.04
Sulfides
CuxS 1.772.0
FexS 0.800.99
ZrSx 0.91.0
*Alltheoxideslistedhavethesodiumchloridestructure.
One example is iron(II) oxide (ferrous oxide), which produces the black color in clays and is used as an abrasive. Its stoichiometry is not FeO
becauseitalwayscontainslessthan1.00FeperO2 (typically0.900.95).ThisispossiblebecauseFecanexistinboththe+2and+3oxidation
states. Thus the difference in charge created by a vacant Fe2+ site can be balanced by two Fe2+ sites that have Fe3+ ions instead [+2
vacancy=(32)+(32)].Thecrystallatticeisabletoaccommodatethisrelativelyhighfractionofsubstitutionsandvacancieswithnosignificant
changeinstructure.
Note
Becauseacrystalmustbeelectricallyneutral,anydefectthataffectsthenumberorchargeofthecationsmustbecompensatedbyacorresponding
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defectinthenumberorchargeoftheanions.

Summary
Defectsdeterminethebehaviorofsolids,butbecauseioniccompoundscontainbothcationsandanions,theyexhibitadditionaltypesofdefects
thatarenotfoundinmetals.
Realcrystalscontainlargenumbersofdefects.Defectsmayaffectonlyasinglepointinthelattice(apointdefect),arowoflatticepoints(aline
defect),oraplaneofatoms(aplanedefect).Apointdefectcanbeanatommissingfromasiteinthecrystal(avacancy)oranimpurityatomthat
occupieseitheranormallatticesite(asubstitutionalimpurity)oraholeinthelatticebetweenatoms(aninterstitialimpurity).Inanedgedislocation,
anextraplaneofatomsisinsertedintopartofthecrystallattice.Multipledefectscanbeintroducedintomaterialssothatthepresenceofonedefect
preventsthemotionofanother,inaprocesscalledpinning.Becausedefectmotiontendstostopatgrainboundaries,controllingthesizeofthegrains
inamaterialcontrolsitsmechanicalproperties.Inaddition,aprocesscalledworkhardeningintroducesdefectstotoughenmetals.Schottkydefects
areacoupledpairofvacanciesonecationandoneanionthatmaintainselectricalneutrality.AFrenkeldefectisanionthatoccupiesanincorrect
site in the lattice. Cations in such compounds are often able to move rapidly from one site in the crystal to another, resulting in high electrical
conductivityinthesolidmaterial.Suchcompoundsarecalledsolidelectrolytes.Nonstoichiometriccompoundshavevariablestoichiometriesovera
givenrangewithnodramaticchangeincrystalstructure.Thisbehaviorisduetoalargenumberofvacanciesorsubstitutionsofoneionbyanother
ionwithadifferentcharge.

Conceptual Problems
1.Howaredefectsandimpuritiesinasolidrelated?Canapure,crystallinecompoundbefreeofdefects?Howcanasubstitutionalimpurityproduce
avacancy?
2.Whydoesapplyingamechanicalstresstoacovalentsolidcauseittofracture?Useanatomicleveldescriptiontoexplainwhyametalisductile
underconditionsthatcauseacovalentsolidtofracture.
3.Howdoesworkhardeningincreasethestrengthofametal?Howdoesworkhardeningaffectthephysicalpropertiesofametal?
4.Workhardenedmetalsandcovalentsolidssuchasdiamondsarebothsusceptibletocrackingwhenstressed.Explainhowsuchdifferentmaterials
canbothexhibitthisproperty.
5.Supposeyouwanttoproduceaductilematerialwithimprovedproperties.Wouldimpurityatomsofsimilarordissimilaratomicsizebebetterat
maintaining the ductility of a metal? Why? How would introducing an impurity that forms polar covalent bonds with the metal atoms affect the
ductilityofthemetal?Explainyourreasoning.
6. Substitutional impurities are often used to tune the properties of material. Why are substitutional impurities generally more effective at high
concentrations,whereasinterstitialimpuritiesareusuallyeffectiveatlowconcentrations?
7.IfanO2 ion(ionicradius=132pm)issubstitutedforanF ion(ionicradius=133pm)inanioniccrystal,whatstructuralchangesintheionic
latticewillresult?
8.Howwilltheintroductionofametalionwithadifferentchargeasanimpurityinducetheformationofoxygenvacanciesinanionicmetaloxide
crystal?
9. Many nonstoichiometric compounds are transition metal compounds. How can such compounds exist, given that their nonintegral cation:anion
ratiosapparentlycontradictoneofthebasictenetsofDaltonsatomictheoryofmatter?
10.Ifyouwantedtoinducetheformationofoxygenvacanciesinanioniccrystal,whichwouldyouintroduceassubstitutionalimpuritiescations
withahigherpositivechargeoralowerpositivechargethanthecationsintheparentstructure?Explainyourreasoning.

Conceptual Answers
5.Impurityatomsofsimilarsizeandwithsimilarchemicalpropertieswouldbemostlikelytomaintaintheductilityofthemetal,becausetheyare
unlikelytohavealargeeffectontheeasewithwhichonelayerofatomscanmovepastanotherundermechanicalstress.Largerimpurityatomsare
likelytoformbumpsorkinksthatwillmakeitharderforlayersofatomstomoveacrossoneanother.Interstitialatomsthatformpolarcovalent
bondswiththemetalatomstendtooccupyspacesbetweenthelayerstheyactasagluethatholdslayersofmetalatomstogether,whichgreatly
decreasestheductility.
7.SinceO2 andF arebothverysimilarinsize,substitutionispossiblewithoutdisruptionoftheionicpacking.Thedifferenceincharge,however,
requirestheformationofavacancyonanotherF sitetomaintainchargeneutrality.
9.Mosttransitionmetalsformatleasttwocationsthatdifferbyonlyoneelectron.Consequently,nonstoichiometriccompoundscontainingtransition
metals can maintain electrical neutrality by gaining electrons to compensate for the absence of anions or the presence of additional metal ions.
Conversely,suchcompoundscanloseelectronstocompensateforthepresenceofadditionalanionsortheabsenceofmetalions.Inbothcases,the
positivechargeonthetransitionmetalisadjustedtomaintainelectricalneutrality.

Numerical Problems
1. The ionic radius of K+ is 133 pm, whereas that of Na+ is 98 pm. Do you expect K+ to be a common substitutional impurity in compounds
containingNa+ ?Whyorwhynot?
2.GivenCs(262pm),Tl(171pm),andB(88pm)withtheirnotedatomicradii,whichatomismostlikelytoactasaninterstitialimpurityinanSn
lattice(Snatomicradius=141pm)?Why?
3.Afteraluminum,ironisthesecondmostabundantmetalinEarthscrust.Thesilverywhite,ductilemetalhasabodycenteredcubic(bcc)unitcell
withanedgelengthof286.65pm.
a.Usethisinformationtocalculatethedensityofiron.

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b.Whatwouldthedensityofironbeif0.15%oftheironsiteswerevacant?
c.Howdoesthemassof1.00cm3ofironwithoutdefectscomparewiththemassof1.00cm3ofironwith0.15%vacancies?
4. Certain ceramic materials are good electrical conductors due to high mobility of oxide ions resulting from the presence of oxygen vacancies.
Zirconia (ZrO2) can be doped with yttrium by adding Y2O3. If 0.35 g of Y2O3 can be incorporated into 25.0 g of ZrO2 while maintaining the
zirconiastructure,whatisthepercentageofoxygenvacanciesinthestructure?
5.WhichofthefollowingionsismosteffectiveatinducinganO2 vacancyincrystalofCaO?TheionicradiiareO2 ,132pmCa2+ ,100pmSr2+ ,
127pmF ,133pmLa3+ ,104pmandK+ ,133pm.Explainyourreasoning.

Numerical Answers
1.No.Thepotassiumismuchlargerthanthesodiumion.
3.
a.7.8744g/cm3
b.7.86g/cm3
c.Withoutdefects,themassis0.15%greater.
5.ThelowerchargeofK+ makesitthebestcandidateforinducinganoxidevacancy,eventhoughitsionicradiusissubstantiallylargerthanthatof
Ca2+ . Substituting two K+ ions for two Ca2+ ions will decrease the total positive charge by two, and an oxide vacancy will maintain electrical
neutrality.Forexample,if10%oftheCa2+ ionsarereplacedbyK+ ,wecanrepresentthechangeasgoingfromCa20O20toK2Ca18O20,whichhasa
netchargeof+2.LossofoneoxideionwouldgiveacompositionofK2Ca18O19,whichiselectricallyneutral.
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