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ValenceBondTheoryandHybridAtomicOrbitals

representedbyTeCl4E,whereErepresentsalonepairofelectrons.Twolonepairsoccupytwosuch
orbitalsinthemoleculeBrF3,orBrF3E2.ThesestructuresaregiveninaVSEPRtableof5and6
coordinations.

ThecompoundSF4isanotherAX4Etype,andmanyinterhalogencompoundsClF3andIF3areAX3E2
type.TheionI3isofthetypeAX2E3.

Thed2sp3hybridorbitals
Thesixd2sp3hybridorbitalsresultedwhentwo3d,one3s,and
three3patomicorbitalsaremixed.Whenanatommakesuseof
sixd2sp3hybridorbitalstobondtosixotheratoms,themolecule
takestheshapeofanoctahedron,intermsofmoleculargeometry.
ThegascompoundSF6isatypicalsuchstructure.Thislink
providesothershapesaswell.
Therearealsocasesthatsomeofthed2sp3hybridorbitalsare
occupiedbylonepairelectronsleadingtothestructuresofthe
followingtypes:
AX6,AX5E,AX4E2AX3E3andAX2E4
IOF5,IF5E,XeF4E2
NoknowncompoundsofAX3E3andAX2E4areknownor
recognized,becausetheyarepredictedtohaveaTshapeandlinearshaperespectivelywhenthelonepairs
ofelectronsareignored.

Molecularshapesofcompounds
Whilethehybridizedorbitalswereintroduced,intheforegoingdiscussion,ValenceshellElectronpair
Repulsion(VSEPR)Modelwereincludedtosuggesttheshapesofvariousmolecules.Specifically,theVSEPR
modelcountsunsharedelectronpairsandthebondedatomsastheVSEPRnumber.Asingle,doubleand
tripplebondisconsideredas1.AfterhavingconsideredthehybridizedorbitalsandtheVSEPRmodel,wecan
nottakeasystematicapproachtorationalizetheshapesofmanymoleculesbasedonthenumberofvalence
electrons.
Asummaryintheformofatableisgivenheretoaccountfortheconceptsofhybridorbitals,valencebond
theory,VSEPR,resonancestructures,andoctetrule.Inthistable,thegeometricshapesofthemoleculesare
describedbylinear,trigonalplanar,tetrahedral,trigonalbypyramidal,andoctahedral.Thehybridorbitals
usearesp,sp2,sp3,dsp3,andd2sp3.
TheVSEPRnumberisthesameforallmoleculesofeachgroup.InsteadofusingNH3E,andOH2E2,weuse
:NH3,::OH2toemphasizetheunshared(orlone)electronpairs.
Asummaryofhybridorbitals,valencebondtheory,VSEPR,
resonancestructures,andoctetrule.
Trigonal
Trigonal
Linear
Tetrahedral
Octahedral
planar
bipyramidal
sp
BeH2
BeF2
CO2
HCN
HCCH

sp2
BH3
BF3
CH2O
(>C=O)
>C=C<
CO32

sp3
CH4
CF4
CCl4
CH3Cl
NH4

http://www.science.uwaterloo.ca/~cchieh/cact/c120/hybrid.html

dsp3
PF5
PCl5
PFCl4
:SF4
:TeF4
::ClF3

d2sp3
SF6
IOF5
PF6
SiF62
:BrF5
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ValenceBondTheoryandHybridAtomicOrbitals

benzene
graphite
fullerenes
NO2
N3
:OO2(O3)
:SO2
SO3

:NH3
:PF3
:SOF2
::OH2
::SF2

::BrF3
:::XeF2

:IF5
::XeF4

:::I3
(:::II2)
:::ICl2

SiO44
PO43
SO42
ClO4

aloneoddelectron:aloneelectronpair
Thistablecorrelatesalotofinterestingchemicalconceptsinordertounderstandthemolecularstructuresof
thesecompoundsorions.Therearesomeintriqueingchemicalrelationshipsamongthemoleculesineach
columnforyoutoponder.
OnlyBeandCatomsareinvolvedinlinearmolecules.Ingasphase,BeH2andBeF2arestable,andthese
moleculesdonotsatisfytheoctetrule.TheelementCmakesuseofsphybridizedorbitalsandithastheability
toformdoubleandtriplebondsintheselinearmolecules.
Carboncompoundsarepresentintrigonalplanarandtetrahedralmolecules,usingdifferenthybridorbitals.The
extraelectroninnitrogenforitscompoundsinthesegroupsappearasloneunpairedelectronorloneelectron
pairs.MoreelectronsinOandSleadtocompoundswithloneelectronpairs.Thefiveatomanionsare
tetrahedral,andmanyresonancestructurescanbewrittenforthem.
Trigonalbipyramidalandoctahedralmoleculeshave5and6VSEPRpairs.Whenthecentralatomscontain
morethan5or6electrons,theextraelectronsformlonepairs.Thenumberoflonepairscaneasilybederived
usingLewisdotstructuresforthevalenceelectrons.
Indescribingtheshapesofthesemolecules,weoftenignorethelonepairs.Thus,NO2,N3,:OO2(O3),and
:SO2arebentmoleculeswhereas:NH3,:PF3,and:SOF2arepyramidal.Youalreadyknowthat::OH2(water)
and::SF2arebentmolecules.
Theloneelectronpairtakesuptheequatoriallocationin:SF4,whichhasthesamestructureas:TeF4described
earlier.Ifyoulayamodelofthismoleculeontheside,itlookslikeabutterfly.Bythesamereason,::ClF3and
::BrF3haveaTshape,and:::XeF2,:::I3,and:::ICl2arelinear.
Similarly,:BrF5and:IF5aresquarepyramidalwhereas::XeF4issquareplanar.

TheCenterAtom
Anicestudentaskedabrilliantquestion.
Whichatomintheformulaisusuallythecenteratom?
Usually,theatominthecenterismoreelectropositivethantheterminalatoms.However,theHandhalogen
atomsareusuallyattheterminalpositionsbecausetheyformonlyonebond.
Takealookatthechemicalformulasinthetable,andseeiftheabovestatementistrue.
However,theapplicationofVSEPRtheorycanbeexpandedtocomplicatedmoleculessuchas
HHHO
|||//
HCC=C=CC=CCC
||\
HNOH
/\
HH

ByapplyingtheVSEPRtheory,onededucesthefollowingresults:
HCCbondangle=109o
HC=Cbondangle=120o,geometryaroundCtrigonalplanar
C=C=Cbondangle=180o,inotherwordslinear
HNCbondangle=109o,tetrahedralaroundN
COHbondangle=105or109o,2loneelectronpairsaroundO
http://www.science.uwaterloo.ca/~cchieh/cact/c120/hybrid.html

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