Chapter12:TheSolidState

12.1Solidsandtheirproperties
12.2AtomicSolids
12.3SomeSimpleIonicSolids
12.4OtherTypesofCrystallineSolids
12.5BondinginSolids
12.6PhaseDiagrams

ChapterinContext
Inthelastchapterwefocusedonthenonbondinginteractionsbetweencollectionsofatomsand
molecules,IMFs,andonhowtheseforcesmanifestthemselvesinthephysicalpropertiesofliquids.In
thischapterwecontinuethisexplorationwiththeadditionofsolids.Becausesolidshavealotof
structuraldetailthatismissinginliquidsandgases,wewillbeginbylookingatthestructuralfeaturesof
somerepresentative,althoughsimple,solids.Wewilllookbrieflyatbondinginsolids,andconcludethe
chapterbytyingthethreestatestogetherinwhatisknownasaphasediagram.

12.1Solidsandtheirproperties
Solidscanbepuresubstancesormixtures,crystallineoramorphous.Acrystallinesolidisoneinwhich
atomsarearrangedinaregularway.Thereislongrangeorderextendingovertheentirecrystal,which
canthereforebedescribedasbeingcomposedofatomic/molecularlevelbuildingblocksthatrepeat.
Theatomiclevelorderinacrystallinesolidisoftenreflectedinthewelldefinedfacesofthecrystal,but
manycrystallinesolidsexistasfusedpolycrystallinemassesinwhichtheorderisnotreadilyapparentat
themacroscopiclevel.Examplesofpuresubstancesthatarecrystallinesolidsatroomtemperatureand
pressureareironmetal,diamond,andtablesalt(NaCl)andsugar(C12H22O11).Inamorphoussolids
atomsarepositionedinanirregularmanorandthesolidslacklongrangeorder.Manyimportantsolid
materialsareamorphoussuchassyntheticfibers,plastics,andglasses,butpuresolidsubstancessuchas
elementalphosphorusorsulfurmayalsoexistinamorphousforms.

##Needaprettyphotographhereandmaybechangetheexamplesabovetomatchthepicture.

ClassificationofSolids

Thelackofawelldefinedrepeatingstructuremeansthatamorphousmaterialsaremoredifficultto
describesystematically,andwewillrestrictourdiscussionheretocrystallinesolids.Likeliquids,solids
arecondensedphasesinwhichtheconstituentparticlesareincontactandthepropertiesare
determinedbythenatureoftheinteractionsholdingtheparticlestogether.Solidscanbebroadly
classified,basedontheseinteractions,asvanderWaals,ionic,covalentormetallic.

VanderWaals(molecular)solidsarethoseinwhichtheparticlesareheldtogetherbytheIMFs
discussedinthepreviouschapter.TheseforcesarecollectivelyknownasVanderWaalsforces:dipole
dipoleincludinghydrogenbonding,dipoleinduceddipole,andLondondispersionforces.VanderWaals
solidsaretypicallymolecularanditisimportantheretodistinguishbetweenthestrengthsofthe
intramolecularcovalentbonds(200to600kJ/mol)andthestrengthsoftheintermolecularforces
holdingthesemoleculestogetherinthesolid(0.05to30kJ/mol).
Ionicsolidsarecomposedofoppositelychargedionscombinedtoproduceaneutralsolid.Theforces
holdingtheionstogetherarethecoulombforcesbetweentheoppositelychargedions.Sincethe
charges,inthiscase,arewholechargesratherthanthesmallpartialchargesfoundinvanderWaals
solids,theattractiveforcesbetweenionsinionicsolidsarestrongerthanthosebetweenthemolecules
invanderWaalssolids.

Incovalentsolids,theforcesholdingthesolidtogetherarecovalentbonds.Forexample,inadiamond
crystaleachcarbonatomiscovalentlybondedtoitsnearestneighbors,andtheentirecrystalcanbe
viewedasagiantmolecule.Thesesolidsarealsocallednetworkcovalentorcovalentnetworksolids.

Inmetallicsolids,positivelychargedsphericalmetalatomcoresareheldtogetherbyattractionstotheir
valenceelectronswhicharedelocalizedoverthewholecrystal.Thedetailsofthebondinginmetalswill
bediscussedlaterinthechapter.

SummaryofCrystallineSolids

Interaction Constituent MeltingPoint Attractive Schematic Examples

Type Particles Forces Diagram

VanderWaals Molecules Moderateto Dipole Iodine(I2)

low
Hbonds Sucrose
(C12H22O11)
Dispersion

Ionic Ions Hightovery Ionion NaCl

high
K2SO4

Covalent Covalent Veryhigh Covalent Diamond(C)

Network bonds
SiO2

Metallic Metalatoms Variable Metallicbonds Na

Type of Solid Melting Point Attractive Hardness Conductivity

Forces
Molecular Low Van der Waals Soft to Brittle Nonconducting
Ionic High to Very Ion-ion Hard and Brittle Nonconducting
High Solid,
Conducting
Liquid
Covalent Very High Covalent bonds Very Hard Usually
Network Nonconducting
Metallic Variable Metallic bonds Variable, Conducting
Malleable

CrystallineSolids:TheUnitCell

Crystallinesolidshavepatternsthatrepeat.Thisiscalledtranslationalsymmetrybecausebytranslating
anoriginalobjectyoucometoanidenticalobject.(Translatejustmeanstoslidetheobjectwithout
rotatingit).Inordertodescribetranslationalsymmetryyoudonthavetoknowwhattheobjectsare,
justwheretheyarelocated.Incrystallinesolids,theactualobjectthatisbeingtranslatedisrepresented
byapointcalledalatticepoint.Thelatticepointmightrepresentasingleatom,asinglemolecule,ora
collectionofatomsormoleculeswhateveritrepresentsrepeatsbytranslationalsymmetry.The
collectionoflatticepointsthatdescribesthecrystallinesoliddefinesacrystallattice.Thelatticepoints
canbeusedtodrawboxescalledunitcells,andanotherwayoflookingatthetranslationalsymmetryis
toimagineusingtheunitcellsasbuildingblockstoconstructthewholecrystal.

Intwodimensions,thisisillustratedinthefollowingfigure,wheretherepeatunitshownin(a)isasingle
foot.


Thereareonly12feetshowninthearray,butimaginethatthepatternrepeatstocoveraplanethat
containsAvogadro'snumberoffeet.Inordertorepresentthetranslationalsymmetry,thelatticepoints
musthaveidenticalenvironmentsinthepatternandthereforebeinthesameplacerelativetoeach
foot.In(b),alatticepointisarbitrarilyplacedoneachbigtoe.In(c),thelatticepointsareconnectedto
formunitcells.Becauseeachlatticepointissharedby4cellsandeachcellhasalatticepointineachof
its4corners,thereisonelatticepointperunitcell(4x=1).Thereisonefootperlatticepointandone
latticepointperunitcellsothereisonefootperunitcell,althoughtogetawholefootthepiecesofthe
threefeetthatenterasingleunitcellmustbeadded.In(d),thelatticepointsshowthetranslational
symmetrywithoutshowingtheobjectbeingtranslated.Noticethatwhiletherelativepositionsofthe
latticepointsareuniquelydeterminedbytheunderlyingtranslationalsymmetry,thereismorethanone
unitcellthatcanbedrawn.Adifferentchoiceoftheunitcellisoutlinedinblackin(d).Also,ifyou
imagineslidingthelatticein(d)overthefeetin(a),youcanseethatthelatticepointscouldhavebeen
choseninspacesbetweenthefeet,withonewholefootineachunitcell.

Foractualcrystals,weareinterestedinthreedimensions.Itturnsoutthatnaturedoesntusemany
differentkindsoftranslationalsymmetry,sothatinthreedimensionsthetranslationalsymmetryinall
crystallinesolidscanbedescribedforthe7existingcrystalsystemswithjust14patternscalledBravais
lattices.Withallofthecomplexityfoundincrystallinesolids,thisisprettyamazing.Butrememberthat
theobjectsrepresentedbythelatticepointscanbeverycomplexandcanhaveinternalsymmetry.

Theleastsymmetricalcrystalsystemistriclinic:allcelledgesunequalandallanglesbetweentheedges
notequaltoeachotherandnotequalto90.Themostsymmetricalcrystalsystemiscubic:allcelledges
equalandallanglesequalto90.Theremainingfivecrystalsystemsrunthegamutinbetween.


Sincecubesserveastheunitcellsinthesystemsthatwewillbeexamining,itisusefultovisualizetheir
featuresandwhathappenswhenidenticalcubespacktogethertofillspace.Anisolatedcubehas12
edges,6facesand8corners.Whenidenticalcubesarepackedtogether,eachfaceofacubeissharedby
twocubes,eachedgeofacubeissharedby4cubes,andeachcornerofacubeissharedby8cubes.
Alsonoticethatsixcubeedgescometogetherateachcorner.

TherearethreepossibleBravaislatticesforthecubicsystem.Theseareshowninthefollowingfigure,
wherethespheresrepresentlatticepoints:simpleorprimitivecubic(P),bodycenteredcubic(BCC)and
facecenteredcubic(FCC).Thedifferencebetweentheseisinthenumberoflatticepointsperunitcell.

Inthesimplecubiclattice,eachoftheeightcornersoftheunitcellcontainsalatticepointwhichis
sharedbythe8unitcellsthatmeetateachcorner.Therefore,the8cornerlatticepointsaccountfor
only1wholelatticepointforeachunitcell(8x1/8=1).Inthebodycenteredcubiccell,inadditionto
theonelatticepointfromthecorners,thereisalatticepointinthecenterofthecubetogiveatotalof
twolatticepointsperunitcell.Thismeansthatwhateverisrepresentedbythelatticepointatthe
cornerofthecubeisalsofoundatitscenter.Inafacecenteredcubiccell,inadditiontothelatticepoint
associatedwiththecorners,thereisalatticepointinthecenterofeachofthe6faces.Sinceeachfaceis
sharedbytwocells,ofeachfacelatticepointisassignedtoeachcell,andthesixfacescontribute3
latticepoints(6x=3)percellforatotaloffourlatticepointsperunitcell.Inafacecenteredcubic
cell,whatevermotifisassociatedwiththelatticepointsatthecornersoftheunitcellalsoappearsin
thecenterofeachface.

12.2AtomicSolids
Metals

Becausemanymetalscrystallizeinacubicunitcellwithonlyoneatomperlatticepoint,someofthe
simplestcrystalstructurestovisualizearethosefoundformetals.

Whenthereisoneatomperlatticepoint,youcanimaginethateachatomlieswithalatticepointatits
center,andthattheatomextendsoutfromitscenterformingaspherethatmakescontactwithits
nearestneighbors.Thenumberofnearestneighborsiscalledthecoordinationnumber.Thelattice
points,andthecontentsoftheunitcellwhenthereisonlyoneatomperlatticepoint,arecomparedin
thefollowingfigureforthethreetypes.Inthesecases,alloftheatomsinthecellareidenticalandthe
differentcolorsareonlytomakethegeometryeasiertovisualize.Authors:ThefollowingisaKotz7e
figure.Shouldweredoonewithalltheatomsthesamecolor?

Inasimplecubicarrangement,nearestneighborsmakecontactalongthecelledges.Eachatomhassix
nearestneighbors,becausesixcelledgescometogetherineachcorner.Inthebodycenteredcasethe
atominthecentermakescontactwiththe8corneratoms,andcontactisalongthebodydiagonal.Ina
facecenteredcell,contactisalongthefacediagonal.Althoughitisdifficulttovisualizehere,inaface
centeredcelleachatomhas12nearestneighbors.Thiswillbecomeeasiertovisualizewhenweconsider
closepackingbelow.Authors:Simplify?Dowecareaboutcoordinationnumbers?

Todocalculationsbasedonexperimentaldata,itisoftennecessarytoknowtherelationshipbetween
theedgelengthoftheunitcell,a,andtheradiusoftheatoms,r,thatcompriseit.Becausethecontact
betweenatomsisdifferentforeachofthethreetypes,therelationshipbetweentheedgelengthand
theatomradiusisalsodifferentforeach.

Inthesimplecubiccell,wheretheatomsmeetalongtheedgeofthecell,theedgeofeachcellistwice
theradiusoftheatom:a=2r.


Inthefacecenteredcell,thecontactisalongthefacediagonal.Afacediagonalpassesthroughthe
diameteroftheatominitsface(adistanceof2r)andhalfwaythrougheachoftwocorneratomsfora
distanceofrfromeach.Thetotaldistancealongthefacediagonalistherefore4randeachedgehasa
lengthofa.FromthePythagoreantheorem,a2+a2=(facediagonal)2orfacediagonal=a 2 =4r.

Inthebodycenteredcell,theatomsmeetalongthebodydiagonal.Thediagonalpassesthroughthe
diameteroftheatominthecenterofthecell,butalsopasseshalfwaythrougheachofthecorner
atoms.Thecontributionfromeachofthetwocorneratomsisr,andthecontributionfromthecenter
atomis2r,sothattheentirebodydiagonalhasalengthof4r.Inthiscasetherighttriangleforthe
calculationiscomposedofthebodydiagonal(4r),anedge(a)andafacediagonal(a 2 ),outlinedinred
inthefigureabove,togivea2+(a 2 )2=(4r)2ora 3 =4r.

Theresultsforallthreearesummarizedinthefollowingtableandarevalidforatomicsubstancesthat
crystallizeincubiclatticeswithoneatomperlatticepoint,whereaistheedgelengthoftheunitcell
andristheradiusoftheatom.

Lattice Atomsper rtoa rtoafactor Coordination %Volume

cell relationship number Occupied

SimpleCubic 1 2r=a r=0.5a 6 52.4

Bodycentered 2 4r=a 3 r=0.43301a 8 68.0

Cubic

Facecentered 4 4r=a 2 r=0.35355a 12 74.0

Cubic

EXAMPLEPROBLEM:AtomicSolids1.RelationshipbetweenEdgeLengthandAtomicRadius

Metallicuraniumcrystallizesinabodycenteredcubiclattice,withoneUatomperlatticepoint.How
manyatomsarethereperunitcell?Iftheedgelengthoftheunitcellisfoundtobe343pm,whatisthe
metallicradiusofUinpm?
Solution:Forabodycenteredcubiclatticewithoneatomperlatticepoint,thereare2atomsperunit
cell.Forthistypeoflatticetheatomsareincontactalongabodydiagonaland4r=a 2 ,whereristhe
metallicradiusandaistheedgelengthofthecell.

Thus,r=0.433a=0.433x343pm=149pm

EXAMPLEPROBLEM:AtomicSolids2.RelationshipbetweenDensityandUnitCellParameters.

Theelementsiliconisfoundtocrystallizeinafacecenteredcubiclattice,withanedgelengthof541.7
pm.Ifthedensityofsolidsiliconis2.348g/cm3,howmanySiatomsarethereperunitcell?

Solution:

Step1.Sincethedensityisgivening/cm3,usetheedgelengthtocalculatethevolumeofthecellincm3.
Thenusethedensitytocalculatethemassinoneunitcell.

Foracubiccellthevolumeistheedgelengthcubed.1pm=1012m=1010cm

Vcell=(541.7pm)3=(541.7x1010cm)3=1.590x1022cm3

M=DxV

Mcell=2.348g/cm3x1.590x1022cm3=3.732x1022g

Step2.UsethemolarmassofsiliconandAvogadrosnumbertocalculatethemassof1Siatom.Then
dividethemassoftheunitcellbythemassof1atomtogetthenumberofatomsinthecell.

28.09g 1mol
Matom = =4.66510 23 g/atom
mol 6.02210 atoms
23

3.78210 22 g 1atom
numberofatoms= =8atoms/cell
cell 4.66510 23 g

Sinceyouweretoldthattheunitcellwasfacecenteredcubic,areyousurprisedtosee8atomspercell?
Siliconcrystallizeswiththediamondstructureinwhicheachatomiscovalentlybondedto4othersto
giveanetworkcovalentsolid.Itdoeshaveafacecenteredcubiccell,butithas2atomsperlatticepoint
foratotalof8atomspercell.

ActivefigureplusOWLhomework.

XrayDiffraction
MuchofourknowledgeofthestructuresofmoleculesandmaterialscomesfromtheXraydiffraction
analysisofcrystallinesolids.Inthesinglecrystalexperiment,abeamofmonochromaticXraysstrikesa
smallsinglecrystalandthepositionsandtheintensitiesofhundredstothousandsofdiffractedbeams
aremeasured.BecauseitistheelectronsintheatomsthatscatterXrays,theexperimentgives
informationabouttheelectrondensityinthecrystal,whichinturnshowshowtheatomsarearranged
intheunitcell.Analternativeexperimentisneutrondiffraction,wheretheneutronbeamisscatteredby
thenucleioftheatoms.Xraysaremorecommonlyusedbecausetheyareeasilygeneratedinsealed
tubesinthelaboratorybybombardingametaltargetwithelectrons,whereastheproductionofa
neutronbeamrequiresanuclearreactor.

Figure12.XXXrayphotographofamyoglobincrystaltakenbytheprecessionmethod.Aspotappearswherevera
diffractedbeamhitsthefilm.Darkerspotscorrespondtomoreintensediffractedbeams.Thepositionsofthe
spotsreflectthesizeandshapeoftheunitcell.Theintensitiesofthespotsreflectthearrangementoftheatomsin
theunitcell.

Thesizeandshapeoftheunitcellcanbedeterminedfromthepositionsofthediffractedbeams,while
theintensitiesgiveinformationaboutwhatkindsofatomsareintheunitcellandwheretheyare
located.BecauseXraysareelectromagneticradiationwithwavelengthscomparabletoatomic
dimensions,diffractioncanbedescribedintermsofthereflectionoftheXraybeamoffofsetsof
parallelplanesinthecrystal.Theseplanesaredrawnthroughlatticepointsandsoreflecttheperiodicity
ofthescatteringmotifs.Adiffractedbeamistobeexpectedwheneverthescatteredradiationfromthe
arrayofidenticalmotifsisinphase.Theconditionforobservingareflectionbydiffractionfromacrystal
isknownasBraggsLawandcanbestated

n=2dsin

whereisthewavelengthoftheXradiation,nisanintegercalledtheorderofthereflection,disthe
spacingbetweenthesetofplanesforthereflection,andistheanglethattheincidentXraybeam
makeswiththeplanes.Areflectionwithn=1iscalledafirstorderreflection,n=2asecondorder
reflection,andsoforth.

Figure12.?xxBraggsLaw:Inordertohaveconstructiveinterference,thedifferenceinpathlengthofthebeam
reflectedfromparallelplanes,separatedbyadistanced,mustbeanintegralnumberofwavelengths,n.The
differenceinpathlengthisab+cd.

Becausetheplanesaredrawnthroughthelatticepoints,theyreflectthesizeandshapeoftheunitcell.
Therefore,thescatteringanglefromanappropriatesetofplanescanbeusedtodeterminetheunitcell
edgelength,andthisinturncanbeusedtodeterminetheradiusofanatom.

EXAMPLEPROBLEM:Determiningadspacingandaradiusfromascatteringangle.

Silvermetalcrystallizesinafacecenteredlatticewith1atomperlatticepoint.MonochromatedX
radiationfromacoppertargethasawavelengthof154pm.Ifthisradiationisusedinadiffraction
experimentwithasilvercrystal,afirstorderdiffractedbeamisobservedatathetavalueof10.91.
Whatisthedspacingbetweentheplanesthatgaverisetothisreflection?Ifthisisthespacingbetween
parallelplanesthatdelimittheunitcell,whatisthemetallicradiusofasilveratom?

SOLUTION

Step1.Solvefordusingtherelationshipn=2dsin,wheren=1,and=10.91:

n (1)(154pm)
d= = =407pm
2sin 2sin(10.91)

Step2.Determinethemetallicradiusofasilveratom.

Thedspacingcorrespondstotheedgelengthofthecubiccellandis407pm.Becausethestructureis
cubicclosepacked(facecenteredcubic)therelationshipbetweentheedgelengthofthecell,a,andthe
radiusoftheatom,r,is4r=a 2 .

407 2
r= =144pm
4


Closepackingofspheresandpercentofoccupiedspace

Inametalcrystal,themetalatomscanbeviewedasspheresthatarepackedtogetherandonemight
expectthattherewouldbemanyexamplesofmetalsthatadopteachofthethreestructuresdescribed
above.Infact,whilemanymetalsadoptthebodycenteredcubicstructure(examplesarebarium,
chromium,iron,lithium,manganese,molybdenum,tungstenandvanadium),andevenmoreadoptthe
facecenteredcubicstructure(examplesarealuminum,calcium,copper,gold,lead,nickel,silverand
strontium),thesimplecubicstructureisrarelyfoundformetals(poloniumisareportedexample).Asa
generalrule,crystallinesolidsminimizetheirenergiesbypackingatomsascloselytogetheraspossible,
andthistendencyisobservedunlessdirectionalforces(suchascovalentorhydrogenbonds)lowerthe
energyenoughtoovercomeit.Thelackofmetalsfoundwiththesimplecubicstructuresuggeststhat
thisarrangementisnotagoodoneforpacking.Toseeifthisiscorrect,letscalculatethepercentofthe
volumeoccupiedinthethreestructures.

Thevolumeofacubicunitcelliseasilycalculatedintermsofitsedgelengtha,andforeachofthethree
types,theunitcellvolumeissimplya3.Thevolumeoccupiedbyasphericalatomiseasilycalculatedin
termsoftheradiusras4/3r3andthenumberofatomsineachunitcellisknown.Theratioofthe
volumeoccupiedbyatomsinthecelltothetotalvolumeofthecellcanbecalculatedwithoutknowing
thevalueofeitheraorr,becausetheratiobetweenthemisknownforeachstructuraltype.Puttingthis
togethergivestheformula

3
4 a
%volumeoccupied=n 100
3 r

wherenisthenumberofatomsperunitcell.Applyingthistoeachstructuraltypegives52.4%,68.0%
and74.0%forsimplecubic,bodycenteredcubicandfacecenteredcubic,respectively.Thelowpercent
ofvolumeoccupiedforthesimplecubicstructureisconsistentwiththelackofmetalsthatadoptthis
structure,whilethemostefficientpackingarrangementisthefacecenteredcubicone.Istheface
centeredcubicstructurethemostefficientpackingarrangementpossible?

Itturnsoutthattherearetwowaystopackspheresthemostefficiently,andthatoneofthese
correspondstothefacecenteredcubicstructure.Asaresult,thefacecenteredcubicstructureisalso
calledthecubicclosepackedstructure.Theotherwayresultsinanhexagonallatticeandthestructure
iscalledthehexagonalclosepackedstructure.Inbothofthesestructures,thepercentvolumeoccupied
isidenticalat74.0%.

Whenyoupackspheres,thereisalwayssomespaceleftopen.Itisusefultotrytovisualizetheclose
packingofspheres,becausemanyioniccrystalsconsistofalatticeofnearlyclosepackedionswith
smallercounterionsintheholesbetweenthem.Visualizationofthepackingisoftendonebystacking
layersofspheresthatarethemselvespackedasefficientlyaspossible.


Thefirstlayerofsphereshasanarrangementwhereeachsphereissurroundedbysixspheresthatform
ahexagon.Whereverthreespheresmeetinalayer,atriangulardepressionisformedthatcouldactasa
seatforasphereinthenextlayer,buttheseseatsaresoclosetogetherthatadjacentonescantbe
occupied.Inplacingthesecondlayer,wheneveranatomoccupiesoneoftheseseatsatetrahedralhole
isformedinthecenterofthetetrahedralarrangementofthefouratoms.Atthesametime,asetof
octahedralholesiscreatedwiththevacanttriangularseatsattheircenters.Heresixatoms,threefrom
eachlayer,cometogether.Inaninfinitearray,therearetwotetrahedralholesandoneoctahedralhole
foreachsphere.

Thesecondlayerisidenticaltothefirstone,butisshiftedrelativetoit.Becausethefirstandsecond
layersarenotdirectlyovereachothertheyarecalledAandB.Whenitcomestoplacingthethirdlayer,
therearetwowaystodoit,eachonecorrespondingtooneofthetwopossibleclosepackedstructures.
Thethirdlayercanbepositionedsothatthespheresaredirectlyabovethespheresinthefirstlayer.
ThisarrangementiscalledABABandcreatesthehexagonalclosepackedstructure.Alternatively,the
thirdlayercanoccupythesetofpositionsthatarenotdirectlyabovethespheresinthefirstlayer.This
arrangementiscalledABCABCandleadstothecubicclosepackedstructure.Itsabittrickytosee
thattheABCthreelayerstackisidenticaltothefacecenteredcubiclatticebecausethestacking
directionisalongthebodydiagonalofthecube.Itis,however,easiertoseeherethatthecoordination
numberofthespheresinaclosepackedstructureis12.Eachspheremakescontactwith6spheresin
thesamelayer,and3sphereseachinthelayeraboveandthelayerbelow,foratotalof12.

12.3SomeSimpleIonicSolids
Inanionicsolid,bothcationsandanionsarepresent,sothatthepreviousstructurescomposedof
identicalspherescannotbeusedtodescribethemexactly.However,manyioniccrystalscanbe
visualizedintermsofthesestructures.Ofteninionicstructures,onetypeofionwilloccupyasetof
positionsthatcorrespondstoeitherthesimplecubicstructureoroneoftheclosepackedstructures,
withthecounterionsoccupyingpositionsdefinedbytheholesinthelatticeformedbythefirstion.
Sinceanionstendtobelargerthancations,itisofteneasiertovisualizethattheanionsformthebasic
frameworkandthecationssitintheholes,butthisneednotbethecase.Regardlessofhowtheions
packintotheunitcell,theratiosofthenumbersofionsofeachtypemustmatchthestoichiometryof
thecompound.

TheCsClStructure.

Oneofthesimpleststructuraltypesfor1:1salts,whichisobservedwhenthecationandtheanionare
closetothesamesize,isthecesiumchloridestructure.Cesiumchloridecrystallizesinasimplecubicunit
cellwithonecesiuimionandonechlorideion,perlatticepoint.Sincethereis1latticepointperunit
cell,thereisoneCsClformulaunitperunitcell.Thecesiumchlorideunitcellisshownschematicallyin
thefollowingfigure:

Atfirstglancethecelllooksbodycentered,butitisnotbecausethesphereatthecenterisnotthesame
astheonesatthecorners.The8redspheresatthecornerseachbelongto8unitcellsandtherefore
contributeonlyoneredspheretotheunitcell(1/8x8=1).Thecellalsocontainsawholepurplesphere
initsinterior,sothereisoneredsphereandonepurplesphereperunitcell.Thisgivesa1to1ratioof
redtopurple,whichisthecorrectratioforCsCl.Sowhichisthecesiumionandwhichisthechloride
ion?Theanswerisitdoesntmatter.Youcanviewthelatticeasasimplecubicarrayofchlorideions
withacesiumioninthecenterofeachunitcell,orasasimplecubicarrayofcesiumionswithachloride
ioninthecenterofeachunitcell.Alternatively,thestructurehasbeendescribedasinterlockingsimple
cubiclatticesofanionsandcations.

Whenanionliesinthecenterofacubeinwhichthecounterionsoccupythecorners,theioninthe
centerissaidtobeinacubichole.Inthecesiumchloridestructure,boththecesiumionandthe
chlorideionhavecoordinationnumbersof8.Someothercompoundsthatadoptthecesiumchloride
structurearecesiumbromideandthalliumchloride.

OctahedralandTetrahedralHolesintheCubicClosepackedLattice.

Beforelookingatmorestructures,itisusefultovisualizethepositionsoftheoctahedralandtetrahedral
holesinacubicclosepackedarrayofions.Inthediagramsbelow,thegrayspheresshowthepositions
ofacubicclosepacked(facecenteredcubic)arrayofionsintheunitcell.Thepositionsofthe
octahedralholesareshowninthecellontheleft.Thereisanoctahedralholeoneachcelledgeandin
thecenterofthecell.Acubehas12edges,andeachedgeissharedby4cells,sothereare4octahedral
holesperunitcell,3fromtheedges(1/4x12=3)plus1inthecenter.

Thepositionsofthetetrahedralholesareshowninthediagramtotheright.Thereare8oftheseina
cubicarrangementintheinteriorofthecell.Pointsintheinteriorofthecellbelongentirelytotheunit
cell,sothereare8tetrahedralholesperunitcell.

TheNaClStructure.

Thesodiumchloridestructureisanothercubicstructurecommonlyadoptedby1to1salts.Amodelof
thesodiumchlorideunitcellisshowntotheleftbelow,wherethesodiumionsarerepresentedby
whitespheresandthechlorideionsbygoldspheres.Thestructureisfacecenteredcubic,withone
sodiumionandonechlorideionperlatticepoint.Sincethereare4latticepointsperunitcellthisgivesa
totalof4NaClmoietiesperunitcell.Youcancometothesameconclusionbycountingspheresinthe
unitcell.Noticethatthegoldcoloredchlorideionshavethesamearrangementasinafacecentered
metalwithacubicclosepackedstructure.Thereforethereareatotalof4chlorideionspercell(1from
the8cornersplus3fromthe6faces).Thesodiumions(whitespheres)occupytheoctahedralholes
createdbythechlorideions.Thisalonetellsyouthereare4percell.Oryoucancount:thereisasodium
iononeachofthecelledgesandoneinthecenterofthecell,foratotalof4sodiumionsperunitcell.
NoticethattheratioofNa+toClis4:4or1:1.

NaClUnitCell ExtendedStructure
Ifthepositionsofthesodiumionsandthechlorideionswereinterchanged,thesameextended
structurewouldresult,andthesodiumchloridestructureissometimesdescribedastwo
interpenetratingfacecenteredcubiclattices.Thiscanbeseenbyinspectingtheextendedstructureto
therightoftheunitcell.Finally,boththecationandtheanionhaveacoordinationnumberof6,aseach
issurroundedbyanoctahedronofcounterions.

TheZnSStructure.

TheZnS(zincblende)structurecanbedescribedasacubicclosepackedarraysofanionswithcationsin
halfofthetetrahedralholes.Inthediagrambelow,sulfideionsarerepresentedbygoldspheresandzinc
ionsarerepresentedbybluespheres.Thereare4zincionsintheinterioroftheunitcelland4sulfide
ionsperunitcell,(1/8x8)+(1/2x6),whichgivesthecorrectstoichiometryfora1:1salt.Eachzincion
makescontactwiththe4sulfideionscomprisingthetetrahedralhole,andhasacoordinationnumberof
4.

EXAMPLEPROBLEM:Determiningachemicalformulafromtheunitcellcontents.

Theunitcellofacompoundofuraniumandoxygenthatcrystallizesinacubicunitcellisshowninthe
diagrambelow,wherethegrayspheresrepresenturaniumionsandtheredspheresrepresentoxide
ions.Whatisthechemicalformulaofthecompound?Whatisthecoordinationnumberoftheuranium
ionsinthecrystal?

SOLUTION:Youmayrecognisethatthelatticecanbeviewedasacubicclosepackedarrayofuranium
ionswithoxideionsinallofthetetrahedralholes.Thisgives4uraniumionsand8oxideionsperunit
cell,andaU:Oratioof4:8.ThechemicalformulaisthereforeUO2.

Alternatively,theionscansimplybecountedbasedontheirpositionsinacubicunitcell:
Uraniumions:corners=8x1/8=1;faces=6x=3;total=1+3=4.
Oxideions:8intheinteriorofthecell=8

Tovisualizethecoordinationnumberoftheuraniumions,focusontheuraniumiononthetopfaceof
thecell.Thisionhasthefouroxygenionsinthecelldirectlybeneathitasnearestneighbors.But
becauseofthetranslationalsymmetry,theuraniumiononthebottomfaceofthecellisidenticaltothe
oneonthetopfaceofthecell.Thisuraniumionisclosesttothefouroxygenionsdirectlyaboveitinthe
cell.Therefore,intheextendedstructure,eachuraniumionliesatthecenterofacubeofoxygenions
andhasacoordinationnumberof8.

Nearestneighborsinsimpleionicsolidsandthesizesofions.

Youhaveseenthatdifferentcrystallineformsareobservedforcompoundsthathavethesame
stoichiometry.Youmightbewonderingwhythisisthecase.Ifionsaretreatedashardspheres,to
minimizeenergywewouldexpectthationsofoppositechargewouldbeincontactandthatthere
wouldbeasmanysuchinteractionsaspossible.Atthesametime,ionsofthesamechargeshouldrepel
oneanother,andwouldnotbeexpectedtobeinclosecontact.Becauseatetrahedralholeissmaller
thananoctahedralhole,whichinturnissmallerthanacubichole,relativesizecandictatethetypeof
vacanciesthatarefilledinalatticeandthiscandictatethetypeoflatticeformed.Supposeacation(red)
ispackedwithanions(gray)asinthefollowingdiagrams.Letthesquarearrangementsof4anions
representthefouratomplaneinanoctahedralhole,whilethetriangulararrangementofthree
representsthreeofthefouranionscomprisingatetrahedralhole.

Anunfavorablesituationisdepictedinthemiddlediagram.Herethecation(red)isinaholeformedby
theanions(gray),butistoosmalltotouchallofthemsimultaneously.Acombinationlikethiswouldnot
minimizeenergy,andthesubstancecouldbetterminimizeitsenergybyhavingitscationsinthesmaller
tetrahedralholes,wherecontactcanbemadewithalloftheanions.Inthesituationonthefarright,a
largercation(green)placedintheoctahedralholedrivestheanionsapartabitandcreatesafavorable
situationforionicbonding.Ifastilllargercationwascombinedwiththesameanion,thecubichole
couldbecomeabetteralternativethantheoctahedralhole,becauseasufficientlylargercationcould
accommodatemoreanionsandwouldpermit8interactionspercationinsteadof6.Thusforagiven
anion,arelativelysmallcationmightresultinaclosepackedstructureinwhichthecationsoccupied
tetrahedralholes,asomewhatlargercationmightfavoroccupationoftheoctahedralholes,whileastill
largercationmightresultinastructureinwhichthecationoccupiescubicholes.
Regardlessofthepackingarrangement,ionsofoppositechargeareassumedtobeincontact,andthe
distancebetweentheircentersistakentobethesumoftheirionicradii.Manyionicradiihavebeen
obtainedfromthedistancesbetweenioncentersobtainedfromcrystallographicdata.Sincethe
distancegivesasumratherthananindividualionicradius,oneofthevaluesmustbeknowninorderto
determinetheothervalue.Bylookingatvaluesfrommanydifferentstructures,setsofselfconsistent
experimentalionicradiicanbedetermined.

EXAMPLEPROBLEM:Densityfromunitcelldataandionicradii

Magnesiumsulfidecrystallizeswiththesodiumchloridestructureandisrepresentedinthefollowing
modelwithS2showningreenandMg2+showninred.IftheradiusoftheMg2+ionis72pmandthe
radiusoftheS2ionis184pm,whatisthedensityofcrystallineMgSing/cm3?

SOLUTION:ThemassoftheunitcellcanbecalculatedbecausetherearefourMgSformulaunitsper
unitcellandthemolarmassisknown.Thevolumeoftheunitcellcanbecalculatedasitsedgelength
cubed.Becausetheionsareincontactalonganedge,thelengthoftheedgeistwicethesumofthe
ionicradii,whichweregiven.Thedensityistheratioofthemassofthecelltothevolumeofthecell.

Step1.Calculatethemassoftheunitcellwhichcontains4formulaunitsofMgS(Molarmass=56.37
g/mol).

4molecules 56.37g 1mol

=3.74x10 22 g/cell
cell mol 6.022x10 23 molecules

Step2.Calculatetheedgelengthoftheunitcell,andfromthisitsvolume.

Edgelength=2(72.0pm)+2(184pm)=512pm

10 12 m 100cm
512pm =5.12x10 8 cm
pm m

Vcell=(5.12x108cm)3=1.34x1022cm3

Step3.Calculatethedensityfromthemassandthevolumeofthecell.

3.74x10 22 g
D= =2.79g/cm3
1.34x10 22 cm3

 DoionradiianddensityOWLshere.

12.4OtherTypesofCrystallineSolids.
Itwouldbewrongtoleaveyouwiththeimpressionthatallionicsolidsaresimple,andthatonlyionic
compoundsformcrystalswithlatticepointsallinarow.Letstakeaquicklookatafewsolidsthatare
morecomplicated.

Ceramicsaresolidinorganicmaterialsthataretypicallypreparedbyheatingatelevatedtemperatures.
Ingeneral,theyareinsulators,butin1986alanthanumbariumcopperoxideceramicwasdiscoveredto
beahightemperaturesuperconductor.Hightemperatureinthiscontextwasonly30K,butsubsequent
investigationshaveleadtotemperaturesabovethatofliquidnitrogen(77K)whichiseasilyattained.
Theseceramicsconsistoflayersofcopperoxidespacedbylayerscontainingotheratoms.Onesuch
hightemperaturesuperconductorisayttriumbariumcopperoxideceramic,withtheunitcellshownin
thefollowingdiagram.Thespheresinthemodelontherightrepresentionicradii.

Theunitcellinthiscaseisprimitiveorthorhombic(onelatticepointperunitcell,allcelledgesdifferent
lengths,allangles=90).Youcanseethat,inthiscase,asinglelatticepointcorrespondstoafairly
complicatedmotif.Canyoufigureouttheformulaofthecompoundbylookingattheunitcell?Hint:its
sometimescalleda123superconductor.Didyougetit?TheformulaisYBa2Cu3O7.

Zeolitesaresolidinorganicmaterialsthathaveanaluminosilicateframeworkthatresultsinaporous
structure.Theyarenetworkcovalentstructureswithadditionalmaterialshousedinthepores.These
substancescanactasmolecularsievesbecausetheirporestructureshavemoleculardimensionsof
variablesizesthatcanholdsomemoleculesorions,butnotothers.Forexample,zeolitesarewidely
usedforionexchangeinwaterpurificationandsoftening,andinchemistryasdryingagents.

Faujasiteisanaturallyoccurringzeolitewithacompositiongivenby(Ca,Na2,Mg)3.5[Al7Si17O48]32H2O.It
crystallizesinafacecenteredcubiclattice,whichmeansthatithas4latticepointsperunitcell,butit
hasacomplicatedstructurewithalotofsymmetry.Theunitcellofasyntheticcalciumfaujasiteis
showninthefollowingdiagram,vieweddownabodydiagonalofthecube.Alotofatomsare

superimposedintheviewshown,sodonttrytocountthem,butnotethesiliconaluminumoxygen
covalentframeworkthatextendsthroughoutthecrystalandthelargecagesandchannelsthatare
formed.Thissyntheticversionhasbeendehydrated,andthereareonlycalciumions(green)presentto
maintainelectricalneutrality.

Organicmoleculesdontlookmuchliketheyshouldformcrystals,buttheydo(checkoutyoursugar
bowlsometime).Acetamide,CH3CONH2,isasmallorganicmoleculethatexistsasacrystallinesolidat
roomtemperature.(Oddlyenoughitisconsideredtobeamineral).Modelsofitsunitcellareshown
below.

Acetamidehasaunitcellwithsymmetrythatishardtovisualize,soletsnotworryaboutthat.Just
focusonthefactsthatthecrystalismadeupofmoleculesthatarepackedtogether,andthattheunit
celldoesrepeattofillspace.Therearenoionsandnocovalentnetworkssothemoleculesareheld
togetherinthecrystalonlybyvanderWaalsforces.Inadditiontodispersionforces,thereisextensive
intermolecularhydrogenbondingbetweenthehydrogenatomsoftheNH2groupsandtheoxygen
atomsoftheCOgroups.Ifyoulookcloselyatthespacefillingmodel,youcanseeplaceswheretheH
atomsoftheNH2groupsarecozyinguptooxygenatoms.Acetamidemeltsataround80Candboilsat
222C.ComparethistoN,Ndimethylacetamide,CH3CON(CH3)2,whichisaliquidatroomtemperature,
boilsat165C,andcannotformhydrogenbonds.

12.5BondinginSolids
IonicBonding:LatticeEnergy

Wehavesaidthationicsolidsareheldtogetherbythestrongattractiveforcesbetweenoppositely
chargedions.Coulombslawinthiscontextcanbewritten:

q1 q2
E=a
r

whereaisaconstant,q1andq2arethechargesontheionsandristhedistancebetweentheircenters.

Ifthedetailsofhowtheionsarepackedtogetherinthesolidareknown,itoughttobepossibletouse
Coulombslawtocalculatetheenergyreleasedwhenmolarquantitiesoftheisolatedionsinthegas
phase(zerointeractionenergy)cometogethertoformamoleofcrystallinesolid.Insuchacalculation
thestrongestattractiveforceswouldbebetweennearestneighborsofoppositecharge,butitwouldbe
necessarytosumupalloftheattractiveandrepulsiveforces,includingthoseoperatingatadistance.
Summationslikethisaredone,andgivecalculatedvaluesofthebindingenergyincrystals.Thesevalues
canalsobedeterminedexperimentally.

Letsseeifwecanusesomeoftheexperimentalresultsthatyouhavealreadyseentogetamore
quantitativeideaofwhatthismeans.Thebindingenergyinacrystallinelatticeiscalledthelattice
energyandisgiventhesymbolU.Itistheenergyrequiredtoseparateonemoleofacrystallineionic
solidintoitsgaseousions.Alternativelyitcanbedefinedastheenergyreleasedwhenonemoleofa
crystallineionicsolidformsfromitsgaseousions.Forexample,forNaCl:

NaCl(s)Na+(g)+Cl(g) U=H=latticeenergy(kJ/mol)

Notethatseparatingtheionsisanendothermicprocess,whilethereversereactionisexothermic.

RecallHesssLaw(Chapter5)thatsaysthatifaprocesscanbeexpressedasthesumofotherprocesses,
thenHfortheoverallprocessisthesumoftheHsfortheindividualsteps.Thesumoftheequations
forthefollowing5stepsgivestheequationforthelatticeenergyofsodiumchloride.


(1)Thevaporization(sublimation)ofsolidsodiummetal

Na(s)Na(g) Hosublimation=107kJ

(2)Thefirstionizationenergyofsodium:(Chapter7)

Na(g)Na+(g)+e IE=496kJ

(3)ThedissociationofmolofCl2(g)thisishalfoftheClClbondenergy=242kJ/mol:(Chapter8)

Cl2(g)Cl(g) BE=121kJ

(4)Theelectronaffinityofchlorine:(Chapter7)

Cl(g)+eCl(g) EA=349kJ

(5)ThereverseoftheenthalpyofformationofNaCl(s):(Chapter5)

NaCl(s)Na(s)+Cl2(g) Hfo=(411kJ)=411kJ

Takingthesumof(1)through(5)gives:

NaCl(s)Na+(g)+Cl(g) U=107+496+121349+411=786kJ

So,thelatticeenergyofNaCl(s)is786kJ/mol.Thisprocesscanalsobedescribedintermsofacyclethat
iscalledaBornHabercycle.Authors:dowewantafigure?

AccordingtoCoulombslaw,theenergyofinteractionbetweenionsofoppositechargeincreaseswith
themagnitudeofthechargesanddecreaseswiththedistancebetweenthem.Youcanseetheseeffects
inthefollowingtableoflatticeenergies,whereallofthecompoundshavethesodiumchloride
structure.Noticethatforionsofthesamecharge,themagnitudesofthelatticeenergiesdecreaseas
thesizeoftheions(Chapter7)increases,asthiscausesanincreaseinthedistancebetweentheir
centers.AlsocompareMgOwithNaF,wheretheionshavecomparablesizes,butwherethehigher
chargeonthedivalentionsleadstoamuchlargerlatticeenergy.

Compound LiF LiCl LiBr NaF NaCl NaBr MgO

U(kJ/mol) 1037 852 815 926 786 752 3850

EXAMPLEPROBLEM:Calculatingalatticeenergyfromthermodynamicdata.

CalculatethelatticeenergyofKCl(s)usingthefollowingthermodynamicdata(alldatagivenisin
kJ/mol).WouldyouexpectthistobelargerorsmallerthanthevalueforNaCl(s)?

K(s) Hsublimation=+89.6
K(g) IE=419
ClCl BE=242
Cl(g) EA=349
KCl(s) Hof=437
SOLUTION

ThelatticeenergyisHforthereaction:KCl(s)K+(g)+Cl(g)

Usethedatagiventowritefiveequationsthatwillsumtogivethisreaction,andthensumtheirHsto
gettheHvalue.

(1) K(s)K(g) Hsublimation=89.6kJ

(2) K(g)K+(g)+e Ionizationenergy=419kJ

(3) Cl2(g)Cl(g) Bondenergy=121kJ

(4) Cl(g)+eCl(g) Electronaffinity=349

(5) KCl(s)K(s)+Cl2(g) Hfo=(438kJ)=437kJ

Sum(1)(5):

KCl(s)K+(g)+Cl(g) U=89.6+419+121349+437=718kJ

ThelatticeenergyofKClis718kJ/mol.ThisvalueissmallerthanthatforNaCl(786kJ/mol),asexpected
becauseofthelargersizeofK+comparedtoNa+.Notethatthestandardheatofformationvaluefor
KCl(s)isfortheformationofthesaltfromitselements,sothatforthereverseequationthevaluehas
theoppositesign.

DolatticeenergyOWLhereifitisdecidedtokeepthis.Needtowrite.

MetallicBonding:BandTheory

Mostmetalsaresolidcrystallinematerialsthataremalleableandductileandgoodconductorsofheat
andelectricity.Inthesimplestbondingmodel,themetalatomcoresareimaginedtobeheldtogether
bydelocalizedvalenceelectronsthataccountforthelackofdirectionalpreferenceinthebonding,and
arefreetomoveaboutthecrystaltoconductelectricity.

Thereisamoreformalapproachtothebondingincrystallinemetallicsolidsthatissimilartothe
molecularorbitaltheorythatyousawinChapter9,exceptthatthevalencemolecularorbitalsincrystals
involvealloftheatomsinthecrystalandsoextendoverthewholething.Inmolecularorbitaltheory,
whentwoidenticalorbitalsfromtwoidenticalatomscombine,twomolecularorbitals,oneoflower
energyandoneofhigherenergy,areproduced.Inacrystalthatcontainsamoleofatoms,amoleof
suchorbitalswillcombinetoproduceamoleofmolecularorbitalsthatextendoverthecrystalandare
verycloselyspacedinenergy,someoflowerenergywhichconferstabilityandsomeofhigherenergy
whichdonot.Agroupofsuchorbitalsiscalledabandbecausetheorbitalsarenearlycontinuousin
energy.Theorbitalsinthevalenceshellsoftheatomscombinetogiveaseriesofbands,someofwhich
areseparatedbyenergygaps.

Intheisolatedmetalcrystal,valenceelectronsoccupythelowestenergyorbitalspossibleinwhatis
calledthevalencebandtoaccountforbonding.Thenextlowestenergyorbitalsavailableactasthe
conductionband.Inorderforamaterialtobeaconductor,electronsinthetopofthevalenceband
mustbeabletomoveintotheconductionbandwhenanelectricfieldisapplied.Forthistohappen,the
differenceinenergybetweenthevalencebandandtheconductionbandmustbesufficientlysmall.Ina
materialthatactsasaconductor,eitherthevalencebandandtheconductionbandarecontiguous,or
thevalencebandandtheconductionbandoverlap,sothereisnoenergygap.Metalsfallintothis
categoryandsoareconductors.

Inaninstrinsicsemiconductor,thevalencebandisfullandtheenergygapissmallenoughthatifthe
solidisheated,thermalenergybecomessufficienttopromoteelectronsfromthevalencebandintothe
emptyconductionband.Siliconisanexampleofasemiconductor.Inaninsulator,thevalencebandis
fullandtheenergygapissolargethatmotionofelectronsfromittotheemptyconductionbandis
prohibited.Diamondisanexampleofaninsulator.

Theconductingpropertiesofasemiconductorcanbeimprovedbydopingwithanotherelement.For
example,inpuresiliconthevalencebandisfullandtheconductionbandisempty.Ifsomeofthesilicon
atomsarereplacedbyagroup5atomsuchasarsenic,foreachSiatomreplacedanextraelectronis
introducedintothelattice.Theseelectronsoccupylevelsjustbelowtheconductionbandandareeasily
promotedintotheconductionband,increasingtheconductivityofthesiliconwhenapotential
differenceisapplied.Becausethedopantintroducesnegativeelectrons,thisiscalledanntype
semiconductor.However,ifsomeofthesiliconatomsarereplacedbygroup3atomssuchasgallium,
thereisonefewerelectroninthevalencebandforeachSiatomreplaced.Thiscreatespositiveholes
intowhichelectronscanmovewhenapotentialdifferenceisapplied,againsupportingacurrent.Thisis
calledaptypesemiconductorbecauseitisthepresenceofpositiveholesthatpromotesthecurrent.

SimulationMetalBonding:BandTheory

12.6PhaseDiagrams
Phasechangesinvolvingsolids.

Inasolidtheparticlesareheldinplacerelativetooneanotherbecausetheydonothaveenoughenergy
toovercometheforcesthatholdtheminplace.Asthetemperatureofthesolidisincreased,the
averageenergyoftheparticlesincreases.Whenatemperatureisreachedwheresomeofthesurface
particleshaveenoughenergytomoveawayfromtheirneighbors,adynamicequilibriumisestablished
betweenthesolidandtheliquid.Foraslongasthereissomesolidpresenttheadditionofenergywill
notresultinanincreaseintemperature,butwillconvertmoresolidtoliquid.Thestrongertheattractive
forcesbetweentheparticles,thehigherthetemperatureatwhichthiswilloccur.Atemperatureat
whichasolidandaliquidareinequilibriumatagivenpressureiscalledameltingpoint.Becausesolids
andliquidsarenotverycompressibleandhavecomparabledensities,themeltingtemperatureofasolid
doesnotchangemuchwithpressure.However,thereissomepressuredependence,sothattospecifya
meltingtemperaturepreciselyitisalsonecessarytospecifythepressure.Becauseacrystaliscomposed
ofobjectsthatrepeat,theforcesholdingthemtogetheralsorepeatthroughoutthelattice.Apure
crystallinesolidischaracterizedbyasharpmeltingpoint,ratherthanthegradualsofteningseenin
amorphousmaterials.

Becausethemeltingpointofasolidreflectsthestrengthoftheforcesholdingtheparticlesinthesolid
together,ingeneral,substanceswithrelativelyhighmeltingpointsalsohaverelativelyhighboiling
points.However,theefficiencywithwhichtheparticlesinasolidpacktogethervarieswiththeirshape
andwiththegeometricdetailsoftheirinteractions.Thiscausesthevariationofmeltingpointswith
strengthofattractiveforcestobelessregularthanwhatisfoundforboilingpoints.

AsyousawinChapter5,theconversionofasolidtoaliquidiscalledmeltingorfusionandtheenergy
requiredtoeffecttheconversioniscalledtheheatoffusion,Hfusion.Fusionisalwaysanendothermic
process,becauseitalwaystakesenergytoovercometheforcesholdingtheparticlesinasolidinplace.
Thereverseprocess,freezing,isalwaysexothermic.Someheatsoffusionatthenormalmeltingpoint
andheatsofvaporizationatthenormalboilingpointaregiveninthefollowingtable.

Table12.XXSelectedHeatsofFusionandVaporizationattheTemperatureoftheNormalPhase
Transition.

Melting Heat of Boiling

Heat of fusion
Substance Point C vaporization Point C
(kJ/mol)
(kJ/mol)
methane 0.94 -182.5 8.2 -161.6
ethane 2.86 -182.8 14.7 -88.6
propane 3.53 -187.6 19.0 -42.1
methanol 3.16 -97.0 35.3 64.7
ethanol 5.02 -114.3 38.6 78.4
1-propanol 5.20 -127 41.4 97.2
water 6.01 0.0 40.7 100.0
Na 2.60 97.82 97.42 881.4
NaBr 26.11 755 160.7 1390

Notethattheheatoffusionisalwayssmallerthantheheatofvaporizationforagivensubstance.This
reflectsthefactthatthesolidandliquidarebothcondensedphasesinwhichtheparticlesarefairly
closetogether,whiletogotothegasphasealloftheattractiveforcesmustbeovercome.

Manysolidsarevolatileenoughtohaveappreciablevaporpressures,evenattemperaturesbelowtheir
meltingpoints.Thedirectconversionofasolidtoagasiscalledsublimation.Likefusionand
vaporization,andforthesamereasons,sublimationisanendothermicprocess.Thereverseprocess,
deposition,isthereforeexothermic.Theenergyrequiredtosublimeasolidiscalleditsheatof
sublimation,Hsublimation.Howdoyouthinkthemagnitudeoftheheatofsublimationofasubstance
comparestoitsheatofvaporization?Sincemelting(s)followedbyvaporization(g)resultsin
thesameoverallchangeassublimation(sg),accordingtoHessslaw,theheatofsublimationshould
beequaltothesumoftheheatoffusionandtheheatofvaporization.Thereforetheheatof
sublimationshouldbethelargestofthethree.

Hsub=Hfus+Hvap


POSSIBLEEXAMPLEPROBLEMAu:couldusejust(a)tokeepitsimple,orcouldgiveallvaluesat298K.

(a)UsethedatainTable12.XXtoapproximatetheheatofsublimationforwater.Whyisthisjustan
approximation?

(b)At298K,thestandardheatofformationofH2O(g)is241.8kJ/molwhilethestandardheatof
formationofH2O()is285.8kJ/mol.Usethistocalculatetheheatofvaporizationofwaterand
compareyourresulttothevalueintable12.XX.

SOLUTION

(a)Hsub=Hfus+Hvap=6.01kJ/mol+40.7kJ/mol=46.7kJ/mol

Forwater,theheatoffusionisgivenat0Candtheheatofvaporizationisgivenat100C.SinceHdoes
varysomewhatwithtemperature,thecalculatedvalueforHsubisonlyanapproximation.

(b)H2O()H2O(g)H=241.8kJ/mol(285.8)kJ/mol=44.0kJ/mol

Thevalueat25Cislargerthanthevalueat100C(40.7kJ/mol).Atthehighertemperature,the
moleculesintheliquidhaveahigheraverageenergyandaremoregaslike(furtherapartandlessshort
rangeorder),solessenergyshouldbeneededfortheconversion.

CouldhavesomeOWLhereifwedecidetodoanexampleproblem.

PhaseDiagrams

Aphasediagramsummarizestheconditionsatwhichphasesareinequilibriumwitheachotherorat
whichonlyasinglephaseisstable.Foraonecomponentsystem,thephasesaresolid,liquidandgas,
althoughsomesubstanceshavemorethanonesolidphase.Theindependentvariablesaretemperature
andpressure,andtheseareplottedonthexandyaxes,respectively.Thephasediagramforwater,not
toscale,isshownbelow.


Eachpointonthediagramrepresentsaspecifictemperatureandpressure.Areasonthediagram
correspondtoregionswhereonlyonephaseisstable.Notethatthegaseousphaseisfavoredatlower
pressuresandhighertemperatures(lowerandtotheright)whilethesolidphaseisfavoredathigher
pressuresandlowertemperatures(upperleft).Alsonoticethattheliquidphaseoccupiesaregion
betweenthesolidandthegaseousphasesandisnotstablebelowacertainpressure,regardlessofthe
temperature.

Separatinganytwoareasarelineswherethetwophasesareinequilibrium.Youhavealreadyseenpart
ofthelineTC.Thisisidenticaltothecurvethatshowshowthevaporpressurevarieswithtemperature.
Sincetheboilingpointisthetemperatureatwhichthevaporpressureequalstheexternalpressure,this
curvealsoshowshowtheboilingtemperaturevarieswithpressure.Analogoustothis,thecurveTA
showshowthevaporpressureofthesolidvarieswithtemperature,whilethelineTBrepresents
equilibriumbetweenthesolidandliquidphasesandshowshowthemeltingtemperaturevarieswith
pressure.Thenormalmeltingpointandthenormalboilingpointarethemeltingandboiling
temperaturesatapressureof1atm,andareseenonthediagramwherethelineP=1atmintersects
thesolidliquidandtheliquidvaporlines.Forwaterthetemperaturescorrespondingto1atmarethe
familiar0Cand100Cformeltingandboiling,respectively.

ItisinstructivetorelatetheheatingcurvesthatweredescribedinChapter5tothelineP=1atmonthe
phasediagram.ImaginestartingwiththesolidatP=1atmandsometemperaturebelow0C.Also
imaginethatthesampleisinacylinderfittedwithafrictionlesspistonthatmovestoadjustthevolume
sothatthepressureonbothsidesofthepistonisequalto1atm.Asyouheatthesolidatconstant
pressure,itstemperatureincreasesuntilthesolidliquidequilibriumisreached.Atthispoint,further
heatingcausesthesampletomeltat0C.Additionalheatingthenincreasesthetemperatureofthe
liquidandmovesyouacrosstheliquidregionuntiltheliquidvaporlineisreachedandthesample
vaporizesat100C.Finally,additionalheatingraisesthetemperatureofthegasandmovesyouintothe
regionwherethegasisthestablephase.

TheliquidvaporcurveTCbeginsandendsintwopointsthatyoumaynothaveseenbefore.PointTis
calledthetriplepoint.Thisistheuniquepointonthediagramwhereallthreephasesmeetand
correspondstotheonetemperatureandpressurewhereallthreephasesareinequilibrium.Onthehigh
temperatureend,thecurvedoesnotextendbeyondpointC,whichiscalledthecriticalpoint.The
temperatureandpressureatthispointarecalledthecriticaltemperatureandthecriticalpressure,
respectively.Analogoustootherpointsdefiningequilibriumbetweengasandliquid,thecriticalpressure
isthepressurerequiredtoliquefythegasatthecriticaltemperature.Beyondthecriticaltemperatureit
isnotpossibletoliquefythegas,regardlessofthepressure.Somecriticaltemperaturesandpressures
aregivenbelow:

Critical temperature (C) Critical pressure (atm)

Ammonia, NH3 132.5 111.5
Argon 122.4 48.1
Bromine 310.8 102
Chlorine 143.8 76.0
Fluorine 128.85 51.5
Helium 267.96 2.24
Hydrogen 239.95 12.8
Krypton 63.8 54.3
Methane, CH4 -82.1 45.8
Neon 228.75 27.2
Nitrogen 146.9 33.5
Oxygen 118.6 49.8
Sulfur dioxide, SO2 157.8 77.7
Water, H2O 373.936 217.7
Xenon 16.6 57.6

Substancesinwhichtheintermolecularforcesarerelativelystrong,suchasthepolarmolecules
ammonia,sulfurdioxideandwater,haverelativelyhighcriticaltemperatures.Substancesinwhichthe
intermolecularforcesareweak,suchasargon,hydrogen,nitrogenandoxygenhavelowcritical
temperatures.Permanentgasesaregaseswhosecriticaltemperaturesarebelowroomtemperature,
sotheycannotbeliquefiedatroomtemperature,regardlessofthepressure.Ifyourethinkingwaita
minute,Iveseenliquidnitrogenrememberthatitsverycold!

Attemperaturesandpressuresabovethecriticaltemperatureandpressure,substancesareknownas
supercriticalfluids.Supercriticalfluidscanhavepropertiesthatmakethemofpracticalimportance.For
example,supercriticalcarbondioxideisusedinoneoftheprocessesfordecaffeinatingcoffeebeans,
replacingpotentiallycarcinogenicsolventsthatwereformallyused.Itisalsousedasasolventfor
extractingcompoundsthatareusedasfragrances,permittingthistobedoneattemperaturesthatare
lowenoughtoavoiddecompositionofthecompounds.

Sincethemeltingtemperatureisnotverysensitivetopressure,theslopeofthesolidliquidlineonthe
phasediagramforwaterisgreatlyexaggerated.Thenegativeslopeforwaterisunusualandoccurs
becauseforwaterthedensityofthesolidislessthanthedensityoftheliquid,duetotheopenstructure
ofthehydrogenbondedicelattice.AccordingtoLeChatelierifyouincreasethepressureonan
equilibriumsystemitwillrespondtodecreasethepressure.Apressureincreasewillcausethesolid
liquidequilibriumtoshifttofavorthemoredensephasebecausethiswillalleviatepressureby
decreasingvolume.Forwater,theliquidisthemoredensephase,andraisingthepressurecausesthe
meltingpointtodecrease(negativeslope).Thismeansthatatagiventemperatureincreasingthe
pressureenoughwillmeltthesolid.Noticethatasyoumovetohigherpressures,theliquidoccupies
moreareaonthephasediagramforwater.

Contrastthistothebehaviorofcarbondioxideshownonthefollowingphasediagram.

Carbondioxideisamoretypicalsubstanceinthatthedensityofthesolidisgreaterthanthedensityof
theliquid.Therefore,itsmeltingpointincreasesasthepressureincreases,thesolidliquidlinehasa
positiveslope,andathigherpressuresthesolidoccupiesmoreareaonthediagram.Carbondioxidehas
anunusualfeatureinthatithasneitheranormalmeltingpointnoranormalboilingpoint.Thisis
becauseitstriplepointpressureisabove1atm.Becausetheliquiddoesnotexistasastablephase
belowthetriplepointpressureof5.19atm,at1atmthesolidsublimestogivethegasratherthan
melting.Sincethishappensatatemperatureof78C,solidcarbondioxideisusedforcoolingandis
calleddryicebecauseitdoesntmelt.

EXAMPLEPROBLEM:PhaseDigrams

Answerthefollowingquestionsbasedonthephasediagramforammonia,NH3,andonthefollowing
data:Hfusion=331J/g,Hvap=1371J/g,specificheatliquid=4.75J/gK,specificheatgas=0.037J/gK


(a)Whatisthenormalmeltingpoint?Thenormalboilingpoint?
(b)Atwhattemperatureandpressuredothethreephasescoexistinequilibrium?
(c)Isammoniaasolid,aliquidoragasatroomtemperatureandpressure?Ifagas,isitapermanent
gas?
(d)Whichisthemoredensephase,theliquidorthesolid?
(e)A10.0gsampleofammoniaisheatedataconstantpressureof1atmfromatemperatureof200.0K
toatemperatureof400.0K.HowmuchenergyinkJisrequired?

SOLUTION:

(a)Normalreferstoapressureof1atm.Thepointontheliquidsolidlinewithapressureof1atmhasa
temperatureof195.4K.Thisisthenormalmeltingpoint.Thepointontheliquidvaporcurvewitha
pressureofoneatmoccursatatemperatureof239.8K.Thisisthenormalboilingpoint.

(b)Lookfortheonepointthatallthreephaseshaveincommon(T).Thisisthetriplepointat195.3K
and0.059atm.
(c)Takeroomtemperatureandpressuretobe298Kand1atm.Thiscorrespondstothepointindicated
bytheletterXonthediagramwhichisinthegaseousregion.Ammoniaisagasatroomtemperature,
butitisnotapermanentgas.Becausethetemperatureisbelowthecriticaltemperature(405.5K),itcan
beliquefiedbyincreasingthepressuretoabout11atmat298K..

(d)Theliquidsolidequilibriumlinehasapositiveslope.Therefore,thesolidismoredensethanthe
liquid.

(e)ThisprocessisliketheheatingcurvesdescribedinChapter5.Thesubstancestartsasaliquidat1
atmand200.0K.Theliquidisheatedatconstantpressureuntilitstemperaturereachesthenormal
boilingtemperatureof239.8K.Anyattempttoheattheliquidfurtherwillcauseliquidtovaporizeat
constanttemperature.Notethatastheliquidvaporizes,thevolumemustincreaseinordertomaintain
constantpressure.Whenalloftheliquidhasvaporized,furtherheatingwillraisethetemperatureofthe
gastothefinaltemperatureof400.0K.

Energyrequiredtoraisethetemperatureoftheliquidfrom200Kto239.8K:
Q=(10.0g)(4.75J/gK)(239.8200.0)=1891J

Energyrequiredtovaporizetheliquidat239.8K
Q=(10.0g)(1371J/g)=13710J

Energyrequiredtoheatthegasfrom239.8Kto400.0K
Q=(10.0g)(0.037J/gK)(400.0239.8)=59.3J

Totalenergyrequired=1891J+13710J+59.3J=15660J=15.7kJ

PhaseDiagrams.