1.

1OrganicChemistry
Definition:
Thestudyofcarboncontainingmoleculesandtheirreactions

1.1OrganicChemistry
Whydowedistinguishbetweenorganicandinorganic
compounds?

Whathappenstoamoleculeduringareaction?
Acollision
Bondsbreak/form

Whyareorganiccompoundsimportant?

WHATisabond?

TheBIGquestion:WHYdoreactionsoccur?
Wewillneedatleast2semestersofyourtimetoanswerthis
question.
FOCUSontheelectrons.
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1.2StructuralTheory

1.2StructuralTheory

Inthemid1800s,itwasfirstsuggestedthatsubstances
aredefinedbyaspecificarrangementofatoms.

Atomsthataremostcommonlybondedtocarbon
includeN,O,H,andhalides(F,Cl,Br,I).
Withsomeexceptions,eachelementgenerallyformsa
specificnumberofbondswithotheratoms:

WhyisacompoundsformulaNOTadequatetodefineit?

Whattermdoweusetodescribedifferentsubstances
withthesameformula?

PracticewithSKILLBUILDER1.1.
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1.3CovalentBonding
AcovalentbondisaPAIRofelectronssharedbetween
twoatoms.Forexample:

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1.3CovalentBonding
Howdopotentialenergyandstabilityrelate?

Whatforceskeepthebondattheoptimal
length?
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1.3CovalentBonding Atomic
Structure
Areviewfromgeneralchemistry:
Protons(+1)andneutrons(neutral)resideinthenucleus.
Electrons(1)resideoutsidethenucleus.WHERE?

1.3CovalentBonding Counting
ValenceElectrons
Youcanalwayscalculatethenumberofvalenceelectronby
analyzingtheelectronicconfiguration.Lookatphosphorus.
Or,forGroupAelementsonly,justlookatthegroup
number(Romannumeral)ontheperiodictable.

Someelectronsareclosetothenucleusandothersarefar
away.WHY?
Lookatcarbonforexample.Whichelectronsarethevalence
electrons?
Whyarevalenceelectronsimportant?
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PracticewithSKILLBUILDER1.2.
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1.3CovalentBonding SimpleLewis
Structures

1.3CovalentBonding SimpleLewis
Structures

ForsimpleLewisstructures:

ForsimpleLewisstructures:

1. Drawtheindividualatomsusingdotstorepresentthe
valenceelectrons.
2. PuttheatomstogethersotheysharePAIRS ofelectronsto
makecompleteoctets.WHATisanoctet?

TakeNH3,forexample:

1. Drawtheindividualatomsusingdotstorepresentthe
valenceelectrons.
2. PuttheatomstogethersotheysharePAIRS ofelectronsto
makecompleteoctets.WHATisanoctet?

TrydrawingthestructureforC2H2.

PracticewithSKILLBUILDER1.3.
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1.4FormalCharge

1.4FormalCharge

Whattermdoweusetodescribeatomswithan
unbalancedorFORMALcharge?
Howdoesformalchargeaffectthestabilityofanatom?
Atomsinmolecules(sharingelectrons)canalsohave
unbalancedcharge,whichmustbeanalyzedbecauseit
affectsstability.
Tocalculateformalchargeforanatom:

Considertheformalchargeexamplebelow.Calculatetheformal
chargeoneachatom.

ComparethenumberofvalenceelectronsthatSHOULDbe
associatedwiththeatomtothenumberofvalenceelectrons
thatare ACTUALLYassociatedwithanatom.
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or

CarbonSHOULDhave4valenceelectronsbecauseitisinGroupIVAonthe
periodictable.
CarbonACTUALLYhas8valenceelectrons.Itneeds8foritsoctet,butonly
4counttowardsitscharge.WHY?
The4itACTUALLYhasbalanceoutthe4itSHOULDhave,soitdoesnot
haveaformalcharge.Itsneutral.
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1.4FormalCharge
Analyzetheformalchargeoftheoxygenatominthefollowing:

1.5PolarCovalentBonds
Covalentbondsareelectronpairsthatexistinanorbital
sharedbetweentwoatoms.Whatdoyouthinkthat
orbitallookslike?

or

OxygenSHOULDhave6valenceelectronsbecauseitisinGroupVIAonthe
periodictable.
ItACTUALLYhas8valenceelectrons.Itneeds8foritsoctet,butonly7
counttowardsitscharge.WHY?
IfitACTUALLYhas7,butitshouldonlyhave6,whatisitsformalcharge?

PracticewithSKILLBUILDER1.4.
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1.5PolarCovalentBonds
Covalentbondsareeitherpolarornonpolar:
Nonpolarcovalentbonds:bondedatomsshareelectronsevenly
Polarcovalentbonds:oneoftheatomsattractselectronsmorethanthe
other

Justlikeanatomicorbital,theelectronscouldbe
anywherewithinthatorbitalregion.
Whatfactorsdeterminewhichatominthebondwill
attractthesharedelectronsmore?
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1.5PolarCovalentBonds
Electronstendtoshiftawayfromlower
electronegativityatomstohigherelectronegativity
atoms.

Electronegativity:
Howstronglyanatomattractssharedelectrons

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Thegreaterthedifferenceinelectronegativity,the
morepolarthebond.

Klein, Organic Chemistry 1e

1.5PolarCovalentBonds
Canabondhavebothcovalentandioniccharacter?

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1.6AtomicOrbitals
Generalchemistryreview:
Inthe1920s,quantummechanicswasestablishedasa
theorytoexplainthewavepropertiesofelectrons.
Thesolutiontowaveequationsforelectronsprovides
uswithvisualpicturescalledorbitals.

PracticewithSKILLBUILDER1.5.

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1.6AtomicOrbitals
Generalchemistryreview:
Thetypeoforbitalcanbeidentifiedbyitsshape.
Anorbitalisaregionwherethereisacalculated90%
probabilityoffindinganelectron.Theremaining10%
probabilitytapersoffasyoumoveawayfromthe
nucleus.

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1.6AtomicOrbitals
ElectronsbehaveasBOTHparticlesandwaves.Howcantheybe
both?
Maybethetheoryisnotyetcomplete.

Thetheorydoesmatchexperimentaldata,andithaspredictive
capability.
Likeawaveonalake,anelectronswavefunctioncanbe(+),(),orZERO.

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1.6AtomicOrbitals
Becausetheyaregenerated
mathematicallyfromwavefunctions,
orbitalregionscanalsobe(),(+),or
ZERO.

Whycantitfitmore?

Klein, Organic Chemistry 1e

1.6AtomicOrbitals
Oncethe2sisfull,electronsfillintothethree
DEGENERATE2porbitals.
Wherearethenodesineachofthe2porbitals?

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1.6AtomicOrbitals

The2sorbitalisfillednext.The2sorbitalhasanode.

Inthisporbital,thereisanodalplane.
Thesignofthewavefunctionwillbe
importantwhenwelookatorbital
overlappinginbonds.
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Electronsaremoststable(lowestinenergy)iftheyare
inthe1sorbital?
The1sorbitalisfulloncetherearetwoelectronsinit.

Thesignofthewavefunctionhasnothing
todowithelectricalcharge.

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WHERE?

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1.6AtomicOrbitals
Commonelementsandtheirelectronconfigurations:

PracticewithSKILLBUILDER1.6.
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1.6AtomicOrbitals

1.7ValenceBondTheory

Whataretherulesthatgovernourplacementofelectrons?

Abondoccurswhenatomicorbitalsoverlap.Overlapping
orbitalsarelikeoverlappingwaves.

Onlyconstructiveinterferenceresultsinabond.
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1.7ValenceBondTheory
ThebondforanH2 moleculeresultsfromconstructive
interference.

Wheredothebondedelectronsspendmostoftheir
time?
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1.8MolecularOrbitalTheory
Whyistheantibondingorbital
higherinenergy?
Whentheatomicorbitals
overlap,whydotheelectrons
gointothebondingMOrather
thantheantibonding
MO?

H2 MOs
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1.8MolecularOrbitalTheory
Atomicorbitalwavefunctions
overlaptoformmolecular
orbitals(MOs)thatextend
overtheentiremolecule.
MOsareamorecomplete
analysisofbondsbecausethey
includebothconstructiveand
destructiveinterference.
ThenumberofMOscreated
mustbeequaltothenumber
ofatomicorbitalsthatwere
used.
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H2 MOs

Klein, Organic Chemistry 1e

1.8MolecularOrbitalTheory
ImagineaHe2 molecule.
HowwoulditsMOs
comparetothoseforH2?
Howwouldtheenergyof
theHe2 compareto2He?
Whydoesheliumexistinits
atomicformratherthanin
molecularform?
Ingeneral,ifamoleculehas
allofitMOsoccupied,willit
bestableorunstable?
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H2 MOs

Klein, Organic Chemistry 1e

1.8MolecularOrbitalTheory
ConsidertheMOsforCHBr3:

Howmanyelectronscanfitintotheareasrepresented
in(b)?

Therearemanyareasofatomicorbitaloverlap.
NoticehowtheMOsextendovertheentiremolecule.
EachpicturerepresentsONEorbital.
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1.8MolecularOrbitalTheory

Klein, Organic Chemistry 1e

1.9HybridizedAtomicOrbitals

Dependingonthecircumstances,wewillusebothMO
andvalencebondtheorytoexplainphenomena.
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1.9HybridizedAtomicOrbitals
Tomakemethane,theCatommusthave4atomicorbitals
availableforoverlapping.

Giventheelectron
configurationforCand
H,imaginehowtheir
atomicorbitalsmight
overlap.

Ifanelectronisexcitedfromthe2stothe2p,willthatmakeitsuitablefor
makingmethane?

Wouldsuchorbital
overlapyieldmethane?
IffourHatomsweretocomeinandoverlapwiththe2sand2p
orbitals,whatgeometrywouldtheresultingmethanehave?
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1.9HybridizedAtomicOrbitals
Thecarbonmustundergohybridizationtoformfour
equalATOMICorbitals

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1.9HybridizedAtomicOrbitals
Shouldtheshapeofansp3 orbitallookmorelikeansor
morelikeporbital?

Theatomic orbitalsmustbeequalinenergytoform
fourequalenergysymmetricalCHbonds.
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1.9HybridizedAtomicOrbitals

1.9HybridizedAtomicOrbitals

TomakeCH4,the1satomicorbitalsoftheHatomswill
overlapwiththefoursp3 hybridatomicorbitalsofC.

Drawapicturethatshowsthenecessaryatomicorbitals
andtheiroverlaptoformethane(C2H6).

Drawapicturethatshowsthenecessaryatomicorbitals
andtheiroverlaptoformwater.

PracticewithCONCEPTUALCHECKPOINT1.19.
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1.9HybridizedAtomicOrbitals

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1.9HybridizedAtomicOrbitals
Ansp2 hybridizedcarbonwillhavethreeequalenergy
sp2 orbitalsandoneunhybridizedporbital.

Considerethene(ethylene).

EachcarboninethenemustbondtoTHREEother
atoms,soonlyTHREEhybridizedatomicorbitalsare
needed.

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1.9HybridizedAtomicOrbitals

1.9HybridizedAtomicOrbitals

Thesp2 atomicorbitalsoverlaptoformsigma()bonds.

Theunhybridizedporbitalsinetheneformpi()bonds,
createdbySIDEBYSIDEorbitaloverlap.

Sigma bondsprovidemaximumHEADON
overlap.
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PracticewithCONCEPTUALCHECKPOINT1.20.
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1.9HybridizedAtomicOrbitals
MOtheoryprovidesasimilarpicture:
Remember,redandblueregionsareallpartofthesame
orbital.

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1.9HybridizedAtomicOrbitals
Considerethyne(acetylene).
EachcarboninethynemustbondtoTWOotheratoms,
soonlyTWOhybridizedatomicorbitalsareneeded

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1.9HybridizedAtomicOrbitals
Whichshouldbestronger,apibondorasigmabond?
WHY?

1.9HybridizedAtomicOrbitals
Whyissp2 hybridizationnotappropriateformethane
(CH4)?

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1.9HybridizedAtomicOrbitals
ThespatomicorbitalsoverlapHEADONtoformsigma
()bondswhiletheunhybridizedporbitalsoverlap
SIDEBYSIDEtoformpi()bonds.

PracticewithSKILLBUILDER1.7.
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1.9HybridizedAtomicOrbitals
Explainthedifferentstrengthsandlengthsbelow.

Whichshouldbestronger,ansp3sp3 sigmabond
overlaporanspspsigmabondoverlap?

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PracticewithCONCEPTUALCHECKPOINT1.24.
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1.10MolecularGeometry
Valenceshellelectronpairrepulsion(VSEPRtheory):

1.10MolecularGeometry
Todeterminemoleculargeometry:

Valenceelectrons(bondedandlonepairs)repeleachother.

2. Predictthehybridizationofthecentralatom:

Todeterminemoleculargeometry:
1. Determinethestericnumber.

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1.10MolecularGeometry
sp3 Geometry
Foranysp3 hybridizedatom,thefourvalenceelectronpairs
willformaTETRAHEDRALELECTRONGROUPgeometry:
Methanehasfour HOWdoesthe
Thebondanglesin
equalbonds,sothe lonepairofammonia oxygenareeven
bondanglesare
affectitsgeometry? smaller.WHY?
equal.

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1.10MolecularGeometry
sp2 Geometry
CalculatethestericnumberforBF3.
Electronpairsthatarelocatedinsp2 hybridizedorbitals
willformatrigonalplanarELECTRONGROUP geometry.
Whatwillbethemoleculargeometry?

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Ifthestericnumberis4,thenitissp3.
Ifthestericnumberis3,thenitissp2.
Ifthestericnumberis2,thenitissp.

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1.10MolecularGeometry
sp3 Geometry
TheMOLECULARgeometryisdifferentfromthe
ELECTRONGROUP geometry.HOW?
Example

Arrangement
Steric
Hybridization ofelectron
number
pairs

CH4

sp3

Tetrahedral

Tetrahedral

NH3

sp3

Tetrahedral

Trigonalpyramidal

H2O

sp3

Tetrahedral

Bent

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Arrangementof
atoms
(geometry)

Klein, Organic Chemistry 1e

1.10MolecularGeometry
sp2 Geometry
Howmanyelectronsareinboronsunhybridizedp
orbital?
DoesthisgeometryfollowVSEPRtheory?

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1.10MolecularGeometry
sp2 Geometry
Analyzethestericnumber,hybridization,electron
groupgeometry,andmoleculargeometryforthis
imine?

1.10MolecularGeometry
spGeometry
Analyzethestericnumber,hybridization,electron
groupgeometry,andthemoleculargeometryforthe
followingmolecules:
BeH2

CO2

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1.10MolecularGeometry
Summary

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1.11MolecularPolarity
Electronegativitydifferencescauseinduction.
Induction(shiftingofelectronsWITHINtheirorbitals)
resultsinadipolemoment.
Dipolemoment=(theamountofpartialcharge)x(the
distancethe+and areseparated)
Dipolemomentsarereportedinunitsofdebye(D)
1debye=1018esu cm
Anelectrostaticunitofcharge(esu)isaunitofcharge.Oneelectron
hasachargeof4.80x1010 esu.
Centimeters(cm)areincludedintheunitbecausethedistance
betweenthecentersof+and chargesaffectsthedipole.

PracticewithSKILLBUILDER1.8.
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1.11MolecularPolarity
ConsiderthedipoleforCH3Cl
Dipolemoment()=charge(e)xdistance
(d)
=(1.056x1010esu)x(1.772x108cm)
Notethattheamountofchargeseparationis
lessthanwhatitwouldbeifitwereafull
chargeseparation(4.80x1010 esu).

=1.87x1018esu cm
Converttodebye
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1.11MolecularPolarity
WhatwouldthedipolemomentbeifCH3Clwere100%
ionic?
=charge(e)xdistance(d)
Pluginthechargeanddistance

Pluginthechargeanddistance

=1.87D

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Klein, Organic Chemistry 1e

=(4.80x1010esu)x(1.772x108cm)
Thefullchargeofanelectronispluggedin

=8.51x1018esu cm=8.51D

What%oftheCClbondisionic?
IstheCClbondmostlyionicormostlycovalent?
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1.11MolecularPolarity
Checkoutthepolarityofcomeothercommonbonds:

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1.11MolecularPolarity
Formoleculeswithmultiplepolarbonds,thedipole
momentisthevectorsumofalloftheindividualbond
dipoles.

1.11MolecularPolarity
WhyistheC=Odoublebondsomuchmorepolarthan
theCOsinglebond?

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1.11MolecularPolarity
Itisimportanttodetermineamoleculesgeometry
FIRSTbeforeanalyzingitspolarity.
Ifyouhavenotdrawnamoleculewiththepropergeometry,
youmaynotassessthepolaritycorrectly.

Wouldthedipoleforwaterbedifferentifitwerelinear
ratherthanangular?

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1.11MolecularPolarity

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1.11MolecularPolarity

Electrostaticpotentialmapsareoftenusedtogivea
visualdepictionofpolarity.

PracticewithSKILLBUILDER1.9.
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1.11MolecularPolarity

1.12IntermolecularForces
Manypropertiessuchassolubility,boilingpoint,
density,stateofmatter,meltingpoint,etc.areaffected
bytheattractionsBETWEENmolecules.
Neutralmolecules(polarandnonpolar)areattractedto
oneanotherthrough:
Dipoledipoleinteractions
Hydrogenbonding
Dispersionforces(a.k.a.Londonforcesorfleetingdipole
dipoleforces)

Explainwhythedipolemomentforpentane
equal0D.
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1.12IntermolecularForces
Dipoledipole
Dipoledipoleforcesresultwhenpolarmoleculesline
uptheirOPPOSITEcharges.
Notethatacetonespermanentdipoleresultsfromthe
differenceinelectronegativitybetweenCandO.
ThedipoledipoleattractionsBETWEENacetone
moleculesaffectsacetonesboilingpoint(BP)and
meltingpoint(MP).HOW?

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1.12IntermolecularForces
Dipoledipole
Whydoisobutyleneandacetonehavesuchdifferent
MPsandBPs?

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1.12IntermolecularForces
HydrogenBonding

1.12IntermolecularForces
HydrogenBonding

Hydrogenbonds(Hbonds)areanespeciallystrongtype
ofdipoledipoleattraction.
Hydrogenbondsarestrongbecausethepartial+and
chargesarerelativelylarge.
WhyarethepartialchargesintheHbondingexamples
belowrelativelylarge?

Onlywhenahydrogenshareselectronswithahighly
electronegativeatom(O,N,F,orCl)willitcarryalarge
partialpositivecharge.

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Thelarge+ontheHatomcanattractlarge chargeson
othermolecules.

Evenwiththelargepartialcharges,Hbondsarestill
about20timesweakerthancovalentbonds.
CompoundswithHatomsthatarecapableofforming
HbondsarecalledPROTIC.

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1.12IntermolecularForces
HydrogenBonding

1.12IntermolecularForces
HydrogenBonding

WhichofthefollowingsolventsarePROTIC(capableof
Hbonding),andwhicharenot?

Explainwhythefollowingisomershavedifferentboiling
points.

Aceticacid

Methylenechloride

Diethylether

Dimethylsulfoxide

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1.12IntermolecularForces
LondonDispersionForces
Iftwomoleculesarenonpolar(dipole=0D),willthey
attractoneanother?
YES.HOW?

Nonpolarmoleculesnormallyhavetheirelectrons()
spreadoutevenlyaroundthenuclei(+),completely
balancingthecharge.

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1.12IntermolecularForces
LondonDispersionForces
Theconstantrandommotionoftheelectronsinthe
moleculewillsometimesproduceanelectron
distributionthatisNOTevenlybalancedwiththe
positivechargeofthenuclei.
Suchunevendistributionproducesatemporarydipole,
whichcaninduceatemporarydipoleinaneighboring
molecule.

However,theelectronsareinconstantrandommotion
withintheirMOs.
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1.12IntermolecularForces
LondonDispersionForces
Theresultisafleetingattractionbetweenthetwo
molecules.

Suchfleetingattractionsaregenerallyweak.
However,likeanyweakattraction,ifthereareenough
ofthem,theycanadduptoalot.
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1.12IntermolecularForces
LondonDispersionForces
Thegreaterthesurfaceareaofamolecule,themore
temporarydipoleattractionsarepossible.
Considerthefeetofagecko:
Theyhavemanyflexiblehairsontheirfeetthat
maximizesurfacecontact.
TheresultingLondondispersionforcesare
strongenoughtosupporttheweightofthe
gecko.

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1.12IntermolecularForces
LondonDispersionForces

1.12IntermolecularForces
LondonDispersionForces

Explainwhymoleculeswithmoremassgenerallyhave
higherboilingpoints.

Explainwhymorehighlybranchedmoleculesgenerally
havelowerboilingpoints.

PracticewithSKILLBUILDER1.10.
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1.13Solubility

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1.13Solubility

Weusetheprinciplethatlikedissolveslike.
PolarcompoundsGENERALLYmixwellwithotherpolar
compounds:
IfthecompoundsmixingareallcapableofHbondingand/or
strongdipoledipoleinteractions,thenthereisnoreasonwhy
theyshouldntmix.

Weknowitisdifficulttogetapolarcompound(like
water)tomixwithanonpolarcompound(likeoil):
Wecantusejustwatertowashoiloffourdirtycloths.

Toremovenonpolaroils,grease,anddirt,weneed
soap.

NonpolarcompoundsGENERALLYmixwellwithother
nonpolarcompounds:
Ifnoneofthecompoundsarecapableofformingstrong
attractions,thennostrongattractionswouldhavetobe
brokentoallowthemtomix.
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1.13Solubility

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1.13Solubility

Soapmoleculesorganizeintomicellesinwater,which
formanonpolarinteriortocarryawaydirt.

Whichattractionisgenerallystronger?
Theattractionbetweenapermanentdipoleandaninduced
orfleetingdipole,
or
Theattractionbetweenatemporarydipoleandaninduced
dipole(2fleetingdipoles).

Whichattractionisgenerallystronger?
Theattractionbetweenapolarmoleculeandanonpolar
molecule,
or
Theattractionbetweentwononpolarmolecules?
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1.13Solubility
Whywontanonpolarcompoundreadilydissolvein
water?
Isitbecausethewatermoleculesrepelthenonpolar
molecules?

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