Onthestabilitiesoffullandhalffullshells,andothermyths.

RichardHartshorn
Dept.ofChemistry
UniversityofCanterbury
AndChemistryHotlinecontact
RichardRendle
FoundationStudies
UniversityofCanterbury
TeacherManagerMindspringScholarshipChemistryProgramme.
ThisarticlewastriggeredbyarecentstudentdiscussionthatoccurredontheMindspringScholarship
ChemistrydiscussionpagesandalsorelatestoquestionssentintotheChemistryhotline.
TheChemistryHotlineisafacilityforteacherstoemailDr.RichardHartshornwith
questionsrelatingtochemistry.hotline@chem.canterbury.ac.nz.Questionsandresponses
havefeaturedinanumberofissuesofChemNZ.
Mindspringisawebbasedonlineenvironment.ItincludesNZTeachercurriculumshare
areas,documentmanagementsystemsforschooladministrationanddepartments,and
classwebsitesandassignments.Thechemistryscholarshipprogrammeispartofthelast
item.Itaimstoprovideassignmentsanddiscussionpagesforstudentsdoingselected
scholarshipsubjects(For2006theseareChemistry,Physicswhichwastrialedin2005
BiologyandEconomics).Eachsubjecthasateachermanagerandastudenttutor(a
universitypostgradstudent).
Mindspringdiscussionpagesgeneratedpostingsonionisationenergyandperiodicity,twoofwhich
arereproducedbelow.
Iunderstandthatthegeneraltrendsofionisationenergyareadecreasedownagroup
duetodistancefromnucleusandincreasedshieldingmakingeffectivenuclearchargeon
electronssolessenergyisrequiredfortheremovalofelectronsandanincreaseacrossa
periodduetostrongernuclearchargeandelectronsbeingaddedtothesameenergy
levelsoelectronsrequiremoreenergytoremove,butIdon'treallygrasptheanomaly
thing,likehowaluminiumhasalowerIEthanmagnesiumandsulfurhasalowerIEthan
phosphoruswhichdifferfromthegeneraltrendofanincreaseacrossaperiod.Could
anybodyhelpmewiththis?
Thanks
Thishasmestumpedtoo!I'vetriedlookingitup,butIgetdifferentandopposing
answers!Mychemteacherandtextbooktellmethatfull/halffullorbitalsaremore
stableanditisthereforehardertoremoveelectronsfromthem,BUTAbritishchemhelp
siteIfoundsays:

2
"Warning!Youmightpossiblycomeacrossatextbookwhichdescribesthedrop
betweengroup2andgroup3bysayingthatafulls2orbitalisinsomewayespecially
stableandthatmakestheelectronmoredifficulttoremove.
Inotherwords,thatthefluctuationisbecausethegroup2valueforionisationenergyis
abnormallyhigh.Thisisquitesimplywrong!Thereasonforthefluctuationisbecause
thegroup3valueislowerthanyoumightexpectforthereasonswe'velookedat."
(http://www.chemguide.co.uk/atoms/properties/ies.html#top,abouthalfwaydownthe
page)
I'mveryconfused
Traditionallytheaddedstabilityofhalffullandfullelectronshellshasbeenusedexplainavariety
ofpropertiesofatomsandions.Itisconvenientbecauseitcanbeapplied,apparentlyplausibly,toa
numberofsituationsandisareasonablystraightforwardconceptforstudentstoacceptanduse.
Therealityisthathalffullandfullshellsdonothaveanyspecialaddedstabilityandthereisa
perfectlyrationalandlessmysteriousexplanationforeachsituationwherethisaddedstabilityis
usuallyinvoked.Aslightlydifferentoneisrequiredforeachcase,andperhapsthisiswhytheadded
stabilitymythissopervasivetheonemagicstatementcanbeusedinanumberofdifferent
situations.Shouldthisalterthewayweteachatomicstructureandelectronconfigurations?Fullshell
stabilityisingrainedfromYear9and10upandisusedinmosttextbooks.Itisprobablycounter
productivetotryandoverturnthis.Howeverfromthediscussionpostingsaboveitisclearthatsome
ofourbetterstudentsarenotconvincedaboutstabilityofhalffullshellsandteachersneedtobe
awareofmoreaccurateexplanationsforthosethatneedthem.

1
First
kJ
mol
2400

He
2200
Ne

2000
1800

F
Ar
1600

1400

Cl
H
O
1200
P

C
1000
Be

S
Mg
800

Si
B

600

Li
Na
Al
Ca
400
K
200
0

Agraphoffirstionisationenergiesisshownbelow(thedottedlinesinthegrapharethetrendlines
thatarereferredtobelow).

Themythoftheaddedstabilityofhalffullsubshells

Nitrogenandphosphorushavehalffullpsubshells,(2p3and3p3respectively),yettheylieontheir
respectivetrendlinesthatareestablishedonlookingatvaluesfortheprevioustwoelements.Thereis
noaddedstabilityoftheseelectronconfigurationstoputthemoutofline.Theelementsthatarethe

3
anomaliesarethesubsequentelementsoxygenandsulfurwithap4configuration.Itisnotthatthe
halffullp3configurationsaremorestablewithrespecttothetrendbutthatthep4configurationsare
lessstable(oratleastanelectronisremovedmoreeasily)!
Thereasonforthisisthatthelastelectronaddedingoingfromp3top4ispairingwithapelectronin
thesameorbital(2p4foroxygenand3p4forsulfur)theelectrostaticinteractionsbetweenthepaired
electronsmakeiteasiertoremovethatelectron,i.e.amuchlowerionisationenergyresults.
2

Themythoftheaddedstabilityoffullshellsandsubshells

Thetrendlinesfortheionisationenergiesoftheelementsprecedingthenoblegasesneonandargon
areshownandextensionsofthoselinesfitwellwiththeexperimentallyobservedvaluesforneonand
argon.Thereisnoaddedstabilityofthefullshell.Themorecorrectinterpretationisthattheelements
aroundthemareunusually,butpredictably,reactive.Group17elementshaveaveryhighelectron
affinitybecauseoftheirhigheffectivenuclearchargeand,sincetheyhaveavacancyinalowenergy
orbitalthatcanhostanelectron,theydosoeasily.Group1elementshaveanelectronthatisvery
easilyremovedbecauseitisbothfurtherfromthenucleus(beinginthenextshell)andverywell
shieldedfromthenuclearchargebytheotherelectrons.
Berylliumwith2s2andmagnesiumwith3s2havefullssubshells.Thefollowingelements(boron
with2s2,2p1andaluminiumwith3s23p1)haveanelectroninanewsubshell.Itistheseelementsthat
showadropinionisationenergynotberylliumandmagnesiumshowinganaddedstability.Inthe
caseofboron(andsimilarlyforaluminium)thelastandouterelectronisapelectron,whichis
slightlyfurtheroutfromthenucleusthantheselectrons,whichmeansthatitisbothbettershielded
fromthenucleusandexperienceslesselectrostaticattractionduetotheincreaseddistance.
3

Themythinrelationtotransitionmetalelectronconfigurationspart1.

Theideaoftheaddedstabilityofhalffullandfullsubshellsisalsousedtoexplaintheoutoforder
electronconfigurationsofchromiumandcopper;chromiumbeing4s13d5insteadof4s23d4andCu
being4s13d10insteadof4s23d9.
Thefirstimportantpointtonoteinexplainingtheseisthattheenergiesofthe4sand3dorbitalsare
veryclose.
Inthecaseofchromium,thismeansthat4s13d5willbelowerinenergythan4s23d4,becauseinthe
secondcaseyouhaveto"pay"theelectronpairingenergy.Sincethispairingenergyislargerthan
anydifferenceintheenergiesofthe4sand3dorbitals,thelowestenergyelectronconfigurationwill
betheonewhichhasoneelectronineachofthesixorbitalsthatareavailable.Effectivelythisis
Hund'sruleapplyingnotjusttostrictlydegenerateorbitals(orbitalswiththesameenergy),buttoall
orbitalsthatare(significantly)closerinenergythantheelectronpairingenergy.
Inthecaseofcopper,the3dorbitalhasdroppedinenergybelowthatofthe4s,sothatitisbetterto
havethepairedelectronsinthedandtheunpairedoneinthes.Thereasonwhythe3dislowerthan
4sistiedtothehigheffectivenuclearcharge.Thehigheffectivenuclearchargegivesrisetothe
smallsizeofCucomparedwiththeearliertransitionmetals,andalsomeansthatorbitalsininner
shellsaremorestabilisedwithrespecttothosefurtheroutforcopperthanforearlierelements.

Themythinrelationtotransitionmetalelectronconfigurationspart2.

QuestiontoChemistryHotline.
Inarecentexaminationquestion,studentswereaskedtogiveareasonwhytheFe3+ionwasmore
common/stablethantheFe2+ion.Thereasoningoftheanswerwasasfollows:
Theelectronconfigurationofthe+3ionis[Ar]3d5
Theelectronconfigurationofthe+2ionis[Ar]3d6
Sinceallthe3dorbitalsarehalffilledintheFe3+ionandthusmakingthe3dsublevelalsohalffilled
this(andimplicitlyafull3dsublevel)ismorestablethanfullandpartiallyfilledorbitalsinthe
3dsublevelintheFe2+ion.
Hmmm!saidonestudent.Isthisthesameforcopper?
Theelectronconfigurationofthe+2ionis[Ar]3d9
Theelectronconfigurationofthe+1ionis[Ar]3d10
ThiswouldmeantheCu+ionismorestable/commonthantheCu2+
Thisisnotso.Soeitherthereasoningiswrongfortheexamquestionorthereareotherreasonsat
playincopperions.
ChemistryHotlineanswer(slightlymodified).
Thisisnotaverygoodquestion.Thefirstpointisthatquestionsaboutrelativestabilitymustalways
givedetailsaboutconditions.Iftheydon'tthentheyhavenomeaning...
Second,theconditions(e.g.whatligandsarepresent)canaffecttheenergiesoforbitalsandremove
thedegeneracyofdorbitalssothatargumentsabouthalffullnessorotherwisebecomemeaningless
(oratleastmorecomplicated!).Theelectronicpropertiesofligandscanalsoaffecttherelative
stabilitiesofoxidationstates.
Third,therelativestabilityofhalffullandfullsubshellsismoreabouttheinstabilityof
configurationswithonemoreoronelesselectrons.Sodium'sconfigurationisveryunstableduetothe
easeofremovingthenextshellelectronandisnothingtodowithanyspecialstabilityoftheresulting
configuration.Equallyfluorinewantstopickupanelectronasithasaveryhigheffectivenuclear
chargethatisnotshieldedbytheothervalenceelectrons.Itisnotthestabilityoftheresulting
configurationthatdoesit(howwouldthefluorineatomknowitcouldgettoastableconfiguration
byaddinganelectron?).
Finally,agoodreasonwhyFe3+isoftenmorestablethanFe2+isbecauseweareusuallydealingwith
anoxygenatedsystem(i.e.stronglyoxidising)andtheironisabletoreacteasilywiththeoxygen...
Comparingtherelativestabilityoftheoxidationstatesofironandcopperisnotstraightforward,
evenwhentheconditionsarespecified.Thenumber,geometricarrangement,andkindsofligands
canbeveryimportantindeterminingthestabilityoftheresultingcomplex.Thelevelofbonding
theoryrequiredtosupporttheseargumentsiswellbeyondthatdealtwithinschools.

6
Summary
Ineachofthecaseswehavelookedat,thereareperfectlyreasonable,detailedexplanationsforthe
observedexperimentalfactsandthesedontinvolveanyspecialstabilitybeingassociatedwith
halffullorfullsubshells.Thespecialstabilityideaisausefuloneinthatitprovidesoneexplanation
foraseriesofdifferentobservations(andtiesinnicelywithotherconceptslikeuseoftheoctetrule),
butweshouldbeawarethatanystudentscratchingbeneaththesurfaceoftheexplanationwillbe
justifiablydissatisfiedwithit,andwemustbepreparedtoprovidethemorecompletepicture.
Asanadditionalnote,weaddthattheideaofelectronspairingupistaughtthroughalllevelsof
secondaryschool.Onefeaturethatisapparentintheexplanationsaboveandwhichisnotemphasised
inteachingisthatthereisanenergycostassociatedwithelectronspairing(atleastincomparisonto
theelectronsoccupyingseparateorbitals),becausewhenelectronsarepairedinanorbitaltheyare
occupyingthesameregionofspaceandthereforeexperienceelectrostaticrepulsionsfromeachother
(inadditiontotheelectrostaticattractiontothenucleus).Thisisareasonableandsatisfying
explanationthatgoessomewaytoexplainingwhyHundsruleworks!Perhapsweshouldmakemore
ofit.