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electronegativity

ELECTRONEGATIVITY
Thispageexplainswhatelectronegativityis,andhowandwhyit
variesaroundthePeriodicTable.Itlooksatthewaythat
electronegativitydifferencesaffectbondtypeandexplainswhat
ismeantbypolarbondsandpolarmolecules.
Ifyouareinterestedinelectronegativityinanorganicchemistry
context,youwillfindalinkatthebottomofthispage.

Whatiselectronegativity
Definition
Electronegativityisameasureofthetendencyofanatomto
attractabondingpairofelectrons.
ThePaulingscaleisthemostcommonlyused.Fluorine(the
mostelectronegativeelement)isassignedavalueof4.0,and
valuesrangedowntocaesiumandfranciumwhicharetheleast
electronegativeat0.7.

Whathappensiftwoatomsofequalelectronegativitybond
together?
Considerabondbetweentwoatoms,AandB.Eachatommay
beformingotherbondsaswellastheoneshownbuttheseare
irrelevanttotheargument.

Iftheatomsareequallyelectronegative,bothhavethesame
tendencytoattractthebondingpairofelectrons,andsoitwillbe
foundonaveragehalfwaybetweenthetwoatoms.Togeta
bondlikethis,AandBwouldusuallyhavetobethesameatom.
Youwillfindthissortofbondin,forexample,H2orCl2
molecules.
Note:It'simportanttorealisethatthisisanaveragepicture.
Theelectronsareactuallyinamolecularorbital,andare
movingaroundallthetimewithinthatorbital.

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Thissortofbondcouldbethoughtofasbeinga"pure"covalent
bondwheretheelectronsaresharedevenlybetweenthetwo
atoms.

WhathappensifBisslightlymoreelectronegativethanA?
BwillattracttheelectronpairrathermorethanAdoes.

ThatmeansthattheBendofthebondhasmorethanitsfair
shareofelectrondensityandsobecomesslightlynegative.At
thesametime,theAend(rathershortofelectrons)becomes
slightlypositive.Inthediagram," "(readas"delta")means
"slightly"so +means"slightlypositive".
Definingpolarbonds
Thisisdescribedasapolarbond.Apolarbondisacovalent
bondinwhichthereisaseparationofchargebetweenoneend
andtheotherinotherwordsinwhichoneendisslightly
positiveandtheotherslightlynegative.Examplesincludemost
covalentbonds.ThehydrogenchlorinebondinHClorthe
hydrogenoxygenbondsinwateraretypical.

WhathappensifBisalotmoreelectronegativethanA?
Inthiscase,theelectronpairisdraggedrightovertoB'sendof
thebond.Toallintentsandpurposes,Ahaslostcontrolofits
electron,andBhascompletecontroloverbothelectrons.Ions
havebeenformed.

A"spectrum"ofbonds
Theimplicationofallthisisthatthereisnoclearcutdivision
betweencovalentandionicbonds.Inapurecovalentbond,the
electronsareheldonaverageexactlyhalfwaybetweenthe
atoms.Inapolarbond,theelectronshavebeendraggedslightly
towardsoneend.
Howfardoesthisdragginghavetogobeforethebondcounts
asionic?Thereisnorealanswertothat.Younormallythinkof
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sodiumchlorideasbeingatypicallyionicsolid,butevenhere
thesodiumhasn'tcompletelylostcontrolofitselectron.
Becauseofthepropertiesofsodiumchloride,however,wetend
tocountitasifitwerepurelyionic.

Note:Don'tworrytoomuchabouttheexactcutoffpoint
betweenpolarcovalentbondsandionicbonds.AtA'level,
exampleswilltendtoavoidthegreyareastheywillbe
obviouslycovalentorobviouslyionic.Youwill,however,be
expectedtorealisethatthosegreyareasexist.

Lithiumiodide,ontheotherhand,wouldbedescribedasbeing
"ionicwithsomecovalentcharacter".Inthiscase,thepairof
electronshasn'tmovedentirelyovertotheiodineendofthe
bond.Lithiumiodide,forexample,dissolvesinorganicsolvents
likeethanolnotsomethingwhichionicsubstancesnormallydo.

Summary
Noelectronegativitydifferencebetweentwoatomsleadsto
apurenonpolarcovalentbond.
Asmallelectronegativitydifferenceleadstoapolar
covalentbond.
Alargeelectronegativitydifferenceleadstoanionicbond.

Polarbondsandpolarmolecules
InasimplemoleculelikeHCl,ifthebondispolar,soalsoisthe
wholemolecule.Whataboutmorecomplicatedmolecules?
InCCl4,eachbondispolar.

Note:Ordinarylinesrepresentbondsintheplaneofthe
screenorpaper.Dottedlinesrepresentbondsgoingaway
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fromyouintothescreenorpaper.Wedgedlinesrepresent
bondscomingoutofthescreenorpapertowardsyou.

Themoleculeasawhole,however,isn'tpolarinthesensethat
itdoesn'thaveanend(oraside)whichisslightlynegativeand
onewhichisslightlypositive.Thewholeoftheoutsideofthe
moleculeissomewhatnegative,butthereisnooverall
separationofchargefromtoptobottom,orfromlefttoright.
Bycontrast,CHCl3ispolar.

Thehydrogenatthetopofthemoleculeislesselectronegative
thancarbonandsoisslightlypositive.Thismeansthatthe
moleculenowhasaslightlypositive"top"andaslightlynegative
"bottom",andsoisoverallapolarmolecule.
Apolarmoleculewillneedtobe"lopsided"insomeway.

PatternsofelectronegativityinthePeriodicTable
Themostelectronegativeelementisfluorine.Ifyouremember
thatfact,everythingbecomeseasy,becauseelectronegativity
mustalwaysincreasetowardsfluorineinthePeriodicTable.
Note:Thissimplificationignoresthenoblegases.
Historicallythisisbecausetheywerebelievednottoform
bondsandiftheydon'tformbonds,theycan'thavean
electronegativityvalue.Evennowthatweknowthatsomeof
themdoformbonds,datasourcesstilldon'tquote
electronegativityvaluesforthem.

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Trendsinelectronegativityacrossaperiod
Asyougoacrossaperiodtheelectronegativityincreases.The
chartshowselectronegativitiesfromsodiumtochlorineyou
havetoignoreargon.Itdoesn'thaveanelectronegativity,
becauseitdoesn'tformbonds.

Trendsinelectronegativitydownagroup
Asyougodownagroup,electronegativitydecreases.(Ifit
increasesuptofluorine,itmustdecreaseasyougodown.)The
chartshowsthepatternsofelectronegativityinGroups1and7.

Explainingthepatternsinelectronegativity
Theattractionthatabondingpairofelectronsfeelsfora
particularnucleusdependson:
thenumberofprotonsinthenucleus
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thedistancefromthenucleus
theamountofscreeningbyinnerelectrons.

Note:Ifyouaren'thappyabouttheconceptofscreeningor
shielding,itwouldpayyoutoreadthepageonionisation
energiesbeforeyougoon.Thefactorsinfluencingionisation
energiesarejustthesameasthoseinfluencing
electronegativities.
UsetheBACKbuttononyourbrowsertoreturntothispage.

Whydoeselectronegativityincreaseacrossaperiod?
Considersodiumatthebeginningofperiod3andchlorineatthe
end(ignoringthenoblegas,argon).Thinkofsodiumchlorideas
ifitwerecovalentlybonded.

Bothsodiumandchlorinehavetheirbondingelectronsinthe3
level.Theelectronpairisscreenedfrombothnucleibythe1s,
2sand2pelectrons,butthechlorinenucleushas6more
protonsinit.Itisnowondertheelectronpairgetsdraggedsofar
towardsthechlorinethationsareformed.
Electronegativityincreasesacrossaperiodbecausethenumber
ofchargesonthenucleusincreases.Thatattractsthebonding
pairofelectronsmorestrongly.
Whydoeselectronegativityfallasyougodownagroup?
Thinkofhydrogenfluorideandhydrogenchloride.

Thebondingpairisshieldedfromthefluorine'snucleusonlyby
the1s2electrons.Inthechlorinecaseitisshieldedbyallthe
1s22s22p6electrons.
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Ineachcasethereisanetpullfromthecentreofthefluorineor
chlorineof+7.Butfluorinehasthebondingpairinthe2level
ratherthanthe3levelasitisinchlorine.Ifitisclosertothe
nucleus,theattractionisgreater.
Asyougodownagroup,electronegativitydecreasesbecause
thebondingpairofelectronsisincreasinglydistantfromthe
attractionofthenucleus.

DiagonalrelationshipsinthePeriodicTable
Whatisadiagonalrelationship?
Atthebeginningofperiods2and3ofthePeriodicTable,there
areseveralcaseswhereanelementatthetopofonegrouphas
somesimilaritieswithanelementinthenextgroup.
Threeexamplesareshowninthediagrambelow.Noticethatthe
similaritiesoccurinelementswhicharediagonaltoeachother
notsidebyside.

Forexample,boronisanonmetalwithsomepropertiesrather
likesilicon.UnliketherestofGroup2,berylliumhassome
propertiesresemblingaluminium.Andlithiumhassome
propertieswhichdifferfromtheotherelementsinGroup1,and
insomewaysresemblesmagnesium.
Thereissaidtobeadiagonalrelationshipbetweenthese
elements.
Thereareseveralreasonsforthis,buteachdependsontheway
atomicpropertieslikeelectronegativityvaryaroundthePeriodic
Table.
Sowewillhaveaquicklookatthiswithregardto
electronegativitywhichisprobablythesimplesttoexplain.

Explainingthediagonalrelationshipwithregardto
electronegativity
ElectronegativityincreasesacrossthePeriodicTable.So,for
example,theelectronegativitiesofberylliumandboronare:
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Be 1.5
B

2.0

ElectronegativityfallsasyougodownthePeriodicTable.So,for
example,theelectronegativitiesofboronandaluminiumare:
B 2.0
Al 1.5
So,comparingBeandAl,youfindthevaluesare(bychance)
exactlythesame.
TheincreasefromGroup2toGroup3isoffsetbythefallasyou
godownGroup3fromborontoaluminium.
Somethingsimilarhappensfromlithium(1.0)tomagnesium
(1.2),andfromboron(2.0)tosilicon(1.8).
Inthesecases,theelectronegativitiesaren'texactlythesame,
butareveryclose.
Similarelectronegativitiesbetweenthemembersofthese
diagonalpairsmeansthattheyarelikelytoformsimilartypesof
bonds,andthatwillaffecttheirchemistry.Youmaywellcome
acrossexamplesofthislateroninyourcourse.

Questionstotestyourunderstanding
Ifthisisthefirstsetofquestionsyouhavedone,pleasereadthe
introductorypagebeforeyoustart.YouwillneedtousetheBACKBUTTON
onyourbrowsertocomebackhereafterwards.
questionsonelectronegativity
answers
Therearenoquestionsontherestofthispage.

Warning!AsfarasIamaware,noneoftheUKbasedA
level(orequivalent)syllabusesanylongerwantthenextbit.
ItusedtobeontheAQAsyllabus,buthasbeenremoved
fromtheirnewsyllabus.Atthetimeofwriting,itdoes,
however,stillappearonatleastoneoverseasAlevel
syllabus(Malta,buttheremaybeothersthatI'mnotaware
of).Ifindoubt,checkyoursyllabus.
Otherwise,ignoretherestofthispage.Itisanalternative
(and,tomymind,moreawkward)wayoflookingatthe
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formationofapolarbond.Readingitunnecessarilyjustrisks
confusingyou.

Thepolarisingabilityofpositiveions
Whatdowemeanby"polarisingability"?
Inthediscussionsofar,we'velookedattheformationofpolar
bondsfromthepointofviewofthedistortionswhichoccurina
covalentbondifoneatomismoreelectronegativethanthe
other.Butyoucanalsolookattheformationofpolarcovalent
bondsbyimaginingthatyoustartfromions.
Solidaluminiumchlorideiscovalent.Imagineinsteadthatitwas
ionic.ItwouldcontainAl3+andClions.
Thealuminiumionisverysmallandispackedwiththree
positivechargesthe"chargedensity"isthereforeveryhigh.
Thatwillhaveaconsiderableeffectonanynearbyelectrons.

Wesaythatthealuminiumionspolarisethechlorideions.
Inthecaseofaluminiumchloride,theelectronpairsaredragged
backtowardsthealuminiumtosuchanextentthatthebonds
becomecovalent.Butbecausethechlorineismore
electronegativethanaluminium,theelectronpairswon'tbe
pulledhalfwaybetweenthetwoatoms,andsothebondformed
willbepolar.

Factorsaffectingpolarisingability
Positiveionscanhavetheeffectofpolarising(electrically
distorting)nearbynegativeions.Thepolarisingabilitydepends
onthechargedensityinthepositiveion.
Polarisingabilityincreasesasthepositiveiongetssmallerand
thenumberofchargesgetslarger.
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Asanegativeiongetsbigger,itbecomeseasiertopolarise.For
example,inaniodideion,I,theouterelectronsareinthe5
levelrelativelydistantfromthenucleus.
Apositiveionwouldbemoreeffectiveinattractingapairof
electronsfromaniodideionthanthecorrespondingelectronsin,
say,afluorideionwheretheyaremuchclosertothenucleus.
Aluminiumiodideiscovalentbecausetheelectronpairiseasily
draggedawayfromtheiodideion.Ontheotherhand,aluminium
fluorideisionicbecausethealuminiumioncan'tpolarisethe
smallfluorideionsufficientlytoformacovalentbond.

Wherewouldyouliketogonow?
Tolookatelectronegativityinanorganicchemistry
context...
Tothebondingmenu...
Totheatomicstructureandbondingmenu...
ToMainMenu...

JimClark2000(lastmodifiedMarch2013)

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