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Chapter2.AtomicStructureandBonding

Chapter2.AtomicStructureandBonding
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[Chapter11.ThermalProcessingofMetalAlloys][Chapter13.CeramicsStructuresandProperties]
[Chapter14.CeramicsApplicationsandProcessing][Chapter15.PolymerStructures]
[Chapter16.Polymers.Characteristics,ApplicationsandProcessing][Chapter17.Composites]
[Chapter19.ElectricalProperties]

2.2FundamentalConcepts
Atomsarecomposedofelectrons,protons,andneutrons.Electronandprotonsarenegativeandpositive
chargesofthesamemagnitude,1.61019Coulombs.
Themassoftheelectronisnegligiblewithrespecttothoseoftheprotonandtheneutron,whichformthe
nucleusoftheatom.Theunitofmassisanatomicmassunit(amu)=1.661027kg,andequals1/12the
massofacarbonatom.TheCarbonnucleushasZ=6,andA=6,whereZisthenumberofprotons,andA
thenumberofneutrons.Neutronsandprotonshaveverysimilarmasses,roughlyequalto1amu.A
neutralatomhasthesamenumberofelectronsandprotons,Z.
Amoleistheamountofmatterthathasamassingramsequaltotheatomicmassinamuoftheatoms.
Thus,amoleofcarbonhasamassof12grams.ThenumberofatomsinamoleiscalledtheAvogadro
number,Nav=6.0231023.NotethatNav=1gram/1amu.
Calculatingn,thenumberofatomspercm3inapieceofmaterialofdensity(g/cm3).
n=Nav/M
whereMistheatomicmassinamu(gramspermol).Thus,forgraphite(carbon)withadensity=1.8
g/cm3,M=12,weget61023atoms/mol1.8g/cm3/12g/mol)=91022C/cm3.
Foramolecularsolidlikeice,oneusesthemolecularmass,M(H2O)=18.Withadensityof1g/cm3,
oneobtainsn=3.31022H2O/cm3.Notethatsincethewatermoleculecontains3atoms,thisis
equivalentto9.91022atoms/cm3.
Mostsolidshaveatomicdensitiesaround61022atoms/cm3.Thecuberootofthatnumbergivesthe
numberofatomspercentimeter,about39million.Themeandistancebetweenatomsistheinverseof
that,or0.25nm.Thisisanimportantnumberthatgivesthescaleofatomicstructuresinsolids.

2.3ElectronsinAtoms
Theforcesintheatomarerepulsionsbetweenelectronsandattractionbetweenelectronsandprotons.
Theneutronsplaynosignificantrole.Thus,Ziswhatcharacterizestheatom.
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Theelectronsformacloudaroundtheneutron,ofradiusof0.052nanometers.Electronsdonotmove
incircularorbits,asinpopulardrawings,butin'fuzzy'orbits.Wecannottellhowitmoves,butonlysay
whatistheprobabilityoffindingitatsomedistancefromthenucleus.Accordingtoquantummechanics,
onlycertainorbitsareallowed(thus,theideaofaminiplanetarysystemisnotcorrect).Theorbitsare
identifiedbyaprincipalquantumnumbern,whichcanberelatedtothesize,n=0isthesmallestn=1,
2..arelarger.(Theyare"quantized"ordiscrete,beingspecifiedbyintegers).Theangularmomentumlis
quantized,andsoistheprojectioninaspecificdirectionm.Thestructureoftheatomisdeterminedby
thePauliexclusionprinciple,onlytwoelectronscanbeplacedinanorbitwithagivenn,l,monefor
eachspin.Table2.1inthetextbookgivesthenumberofelectronsineachshell(givenbyn)and
subshells(givenbyl).
2.4ThePeriodicTable
Elementsarecategorizedbyplacingthemintheperiodictable.Elementsinacolumnsharesimilar
properties.Thenoblegaseshaveclosedshells,andsotheydonotgainorloseelectronsnearanother
atom.Alkaliscaneasilyloseanelectronandbecomeaclosedshellhalogenscaneasilygainonetoform
anegativeion,againwithaclosedshell.Thepropensitytoformclosedshellsoccursinmolecules,when
theyshareelectronstocloseamolecularshell.ExamplesareH2,N2,andNaCl.
Theabilitytogainorloseelectronsistermedelectronegativityorelectropositivity,animportantfactorin
ionicbonds.

2.5BondingForcesandEnergies
TheCoulombforcesaresimple:attractivebetweenelectronsandnuclei,repulsivebetweenelectronsand
betweennuclei.Theforcebetweenatomsisgivenbyasumofalltheindividualforces,andthefactthat
theelectronsarelocatedoutsidetheatomandthenucleusinthecenter.
Whentwoatomscomeveryclose,theforcebetweenthemisalwaysrepulsive,becausetheelectronsstay
outsideandthenucleirepeleachother.Unlessbothatomsareionsofthesamecharge(e.g.,both
negative)theforcesbetweenatomsisalwaysattractiveatlargeinternucleardistancesr.Sincetheforceis
repulsiveatsmallr,andattractiveatsmallr,thereisadistanceatwhichtheforceiszero.Thisisthe
equilibriumdistanceatwhichtheatomsprefertostay.
Theinteractionenergyisthepotentialenergybetweentheatoms.Itisnegativeiftheatomsarebound
andpositiveiftheycanmoveawayfromeachother.Theinteractionenergyistheintegraloftheforce
overtheseparationdistance,sothesetwoquantitiesaredirectlyrelated.Theinteractionenergyisa
minimumattheequilibriumposition.Thisvalueoftheenergyiscalledthebondenergy,andisthe
energyneededtoseparatecompletelytoinfinity(theworkthatneedstobedonetoovercomethe
attractiveforce.)Thestrongestthebondenergy,thehardestistomovetheatoms,forinstancethehardest
itistomeltthesolid,ortoevaporateitsatoms.

2.6PrimaryInteratomicBonds
IonicBonding
Thisisthebondwhenoneoftheatomsisnegative(hasanextraelectron)andanotherispositive(has
lostanelectron).Thenthereisastrong,directCoulombattraction.AnexampleisNaCl.Inthemolecule,
therearemoreelectronsaroundCl,formingClandlessaroundNa,formingNa+ .Ionicbondsarethe
strongestbonds.Inrealsolids,ionicbondingisusuallycombinedwithcovalentbonding.Inthiscase,the
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fractionalionicbondingisdefinedas%ionic=100[1exp(0.25(XAXB)2],whereXAandXBare
theelectronegativitiesofthetwoatoms,AandB,formingthemolecule.
CovalentBonding
Incovalentbonding,electronsaresharedbetweenthemolecules,tosaturatethevalency.Thesimplest
exampleistheH2molecule,wheretheelectronsspendmoretimeinbetweenthenucleithanoutside,
thusproducingbonding.
MetallicBonding
Inmetals,theatomsareionized,loosingsomeelectronsfromthevalenceband.Thoseelectronsforma
electronsea,whichbindsthechargednucleiinplace,inasimilarwaythattheelectronsinbetweentheH
atomsintheH2moleculebindtheprotons.

2.7SecondaryBonding(VanderWaals)
FluctuatingInducedDipoleBonds
Sincetheelectronsmaybeononesideoftheatomortheother,adipoleisformed:the+nucleusatthe
center,andtheelectronoutside.Sincetheelectronmoves,thedipolefluctuates.Thisfluctuationinatom
Aproducesafluctuatingelectricfieldthatisfeltbytheelectronsofanadjacentatom,B.AtomBthen
polarizessothatitsouterelectronsareonthesideoftheatomclosesttothe+side(oroppositetothe
side)ofthedipoleinA.ThisbondiscalledvanderWaalsbonding.
PolarMoleculeInducedDipoleBonds
ApolarmoleculelikeH2O(Hsarepartially+,Oispartially),willinduceadipoleinanearbyatom,
leadingtobonding.
PermanentDipoleBonds
Thisisthecaseofthehydrogenbondinice.TheHendofthemoleculeispositivelychargedandcan
bondtothenegativesideofanotherdipolarmolecule,liketheOsideoftheH2Odipole.

2.8Molecules
Ifmoleculesformedaclosedshellduetocovalentbonding(likeH2,N2)thentheinteractionbetween
moleculesisweak,ofthevanderWaalstype.Thus,molecularsolidsusuallyhaveverylowmelting
points.

ReviewClassificationofmaterials
Seetablechapter2.gif

Terms:
Atomicmassunit(amu)
Atomicnumber
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Chapter2.AtomicStructureandBonding

Atomicweight
Bondingenergy
Coulombicforce
Covalentbond
Dipole(electric)
Electronstate
Electronegative
Electropositive
Hydrogenbond
Ionicbond
Metallicbond
Mole
Molecule
Periodictable
Polarmolecule
Primarybonding
Secondarybonding
Valenceelectron

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