Sections3.3&3.

4 CovalentBondingandLewis
Structures
Learninggoals:
WritingvalidLewisstructuresformolecularsubstances
PredictingmoleculargeometryfromLewisstructures(VSEPR
theory)
Understandingelectronegativityandhowthisconceptallowsthe
distinctionbetweenpolarbondsandnonpolarbonds
UsingLewisstructurestodeterminewhetheramoleculehasa
dipolemomentornot
Usingtheoctetruletocomputeformalchargesonatomsand
multiplebondingbetweenatoms

Sections3.3&3.4 CovalentBondingandLewis
Structures
(1) Lewisdot(electron)structuresofvalenceelectronsfor
atoms
(2) UseofPeriodicTabletodeterminethenumberofdots
(3) UseofLewisstructurestodescribetheelectronic
structuresofatomsandmolecules
(4) Worksbestforcovalentbondsandforelementsinthe
firstfullrowofthePeriodicTable:H,He,Li,Be,B,C,
N,O,F,Ne
(5) Workswithrestrictionsforsecondfullrowofthe
PeriodicTableandbeyond:Na,Mg,Al,Si,P,S,Cl,Ar

SomeissuesaboutLewisStructurestobediscussed:
(1) DrawingvalidLewisstructureswhichfollowtheoctetrule
(holdsalmostwithoutexceptionforfirstfullrow)
(2) Drawingstructureswithsingle,doubleandtriplebonds
(3) Dealingwithisomers(samecomposition,differentconstitution)
(4) Dealingwithresonancestructures(sameconstitution,different
bondingbetweenatoms)
(5) DealingwithformalchargesonatomsinLewisstructures
(6) Dealingwithviolationsoftheoctetrule:
Moleculeswhichpossessanoddnumberofelectrons
Moleculeswhichareelectrondeficient
Moleculeswhicharecapableofmakingmorethanfourcovalent

bonds

Lewisdotlinerepresentationsofatomsandmolecules
(1) Electronsofanatomareoftwotypes:coreelectronsand
valenceelectrons.Onlythevalenceelectronsareshown
inLewisdotlinestructures.
(2) Thenumberofvalenceelectronsisequaltothegroup
numberoftheelementfortherepresentativeelements.
(3) Foratomsthefirstfourdotsaredisplayedaroundthefour
sidesofthesymbolfortheatom.
(4) Iftherearemorethanfourelectrons,thedotsarepaired
withthosealreadypresentuntilanoctetisachieved.
(5) Ioniccompoundsareproducedbycompletetransferofan
electronfromoneatomtoanother.
(6) Covalentcompoundsareproducedbysharingofoneor
morepairsofelectronsbytwoatoms.

Thevalencecapacityofanatomistheatomsabilityto
formbondswithotheratoms.Themorebondsthehigher
thevalence.
Thevalenceofanatomisnotfixed,butsomeatomshave
typicalvalenceswhicharemostcommon:
Carbon:valenceof4
Nitrogen:valenceof3(neutralmolecules)or4(cations)
Oxygen:valenceof2(neutralmolecules)or3(cations)
Fluorine:valenceof1(neutralmolecules)or2(cations)

CovalentbondingandLewisstructures
(1) Covalentbondsareformedfromsharingofelectronsby
twoatoms.
(2) Moleculespossessonlycovalentbonds.
(3) ThebedrockruleforwritingLewisstructuresforthe
firstfullrowoftheperiodictableistheoctetruleforC,
N,OandF:C,N,OandFatomsarealways
surroundedbyeightvalenceelectrons.
(4) Forhydrogenatoms,thedoubletruleisapplied:H
atomsaresurroundedbytwovalenceelectrons.

3.4
CovalentBonds
andLewis
Structures

TheLewisModelofChemical
TheLewisModelofChemical
Bonding
Bonding
In1916G.N.Lewisproposedthatatoms
combineinordertoachieveamorestable
electronconfiguration.
Maximumstabilityresultswhenanatom
isisoelectronicwithanoblegas.
Anelectronpairthatissharedbetween
twoatomsconstitutesacovalentbond.

CovalentBonding
CovalentBonding
inH
inH22

Two hydrogen atoms, each with 1 electron,

H.

.H

can share those electrons in a covalent bond.

H: H
Sharingtheelectronpairgiveseachhydrogenan
electronconfigurationanalogoustohelium.

CovalentBonding
CovalentBonding
inF
inF22

Two fluorine atoms, each with 7 valence electrons,

..
..
. F:
: ..F .
..
can share those electrons in a covalent bond.
.. ..
: ..
F : ..
F:

Sharingtheelectronpairgiveseachfluorine
anelectronconfigurationanalogoustoneon.

TheOctetRule
TheOctetRule
In forming compounds, atoms gain, lose, or
share electrons to give a stable electron
configuration characterized by 8 valence
electrons.
.. ..
: ..
F : ..
F:

Theoctetruleisthemostusefulincases
involvingcovalentbondstoC,N,O,andF.

Example
Example
Combine carbon (4 valence electrons) and
four fluorines (7 valence electrons each)
.
. C.
.

..
: ..
F.

to write a Lewis structure for CF4.

..
.. : ..F: ..
:
:
F
: ..F: C
..
..
: ..F:

The octet rule is satisfied for carbon and

each fluorine.

Example
Example
It is common practice to represent a covalent
bond by a line. We can rewrite
..
.. : ..F: ..
:
:
F
: ..F: C
..
..
: ..F:

as

..
: ..
F

..
: F:
C
: ..F:

..
..F:

3.4
DoubleBondsand
TripleBonds

Inorganic
Inorganicexamples
examples
..
..
..
:O : : C : : O :
:O
C
Carbon dioxide

H : C : :: N:

Hydrogen cyanide

..
O:

N:

Organic
Organicexamples
examples
H
.. H
..
H : C : : C :H

H
Ethylene

H
C

H : C : :: C :H

Acetylene

3.4
FormalCharges
Formalchargeisthechargecalculatedforan
atominaLewisstructureonthebasisofan
equalsharingofbondedelectronpairs.

Nitricacid
Nitricacid
Formal charge of H

..
O
..

..
O:
N
:O
.. :

Wewillcalculatetheformalchargeforeach
atominthisLewisstructure.

Nitricacid
Nitricacid
Formal charge of H

..
O
..

..
O:
N
:O
.. :

Hydrogenshares2electronswithoxygen.
Assign1electrontoHand1toO.
Aneutralhydrogenatomhas1electron.
Therefore,theformalchargeofHinnitricacidis
0.

Nitricacid
Nitricacid
Formal charge of O

..
O
..

..
O:
N
:O
.. :

Oxygenhas4electronsincovalentbonds.
Assign2ofthese4electronstoO.
Oxygenhas2unsharedpairs.Assignall4ofthese
electronstoO.
Therefore,thetotalnumberofelectronsassignedtoO
is2+4=6.

Nitricacid
Nitricacid
Formal charge of O

..
O
..

..
O:
N
:O
.. :

ElectroncountofOis6.
Aneutraloxygenhas6electrons.
Therefore,theformalchargeofOis0.

Nitricacid
Nitricacid
Formal charge of O

..
O
..

..
O:
N
:O
.. :

ElectroncountofOis6(4electronsfrom
unsharedpairs+halfof4bondedelectrons).
Aneutraloxygenhas6electrons.
Therefore,theformalchargeofOis0.

Nitricacid
Nitricacid
Formal charge of O

..
O
..

..
O:
N
:O
.. :

ElectroncountofOis7(6electronsfrom
unsharedpairs+halfof2bondedelectrons).
Aneutraloxygenhas6electrons.
Therefore,theformalchargeofOis1.

Nitricacid
Nitricacid
Formal charge of N

..
O
..

..
O:
N

:
:O
..

ElectroncountofNis4(halfof8electrons
incovalentbonds).
Aneutralnitrogenhas5electrons.
Therefore,theformalchargeofNis+1.

Nitricacid
Nitricacid
Formal charges

..
O
..

..
O:
N+

:
:O
..

ALewisstructureisnotcompleteunless
formalcharges(ifany)areshown.

Formal
FormalCharge
Charge
An arithmetic formula for calculating formal charge.
Formal charge =
group number
number of
number of

in periodic table
bonds
unshared electrons

"Electron counts" and formal

charges in NH4+ and BF4-

H
H

..
: ..
F

..
: F:

B
: ..F:

7
..
..F:
4

3.5
DrawingLewisStructures

Constitution
Theorderinwhichtheatomsofa
moleculeareconnectediscalledits
constitutionorconnectivity.
Theconstitutionofamoleculemust
bedeterminedinordertowritea
Lewisstructure.

Table1.4HowtoWriteLewis
Structures

Step1:
Themolecularformulaandthe
connectivityaredeterminedby
experiment.

Table1.4HowtoWriteLewis
Structures
Step1:
Themolecularformulaandthe
connectivityaredeterminedby
experiment.

Example:
Methylnitritehasthemolecular
formulaCH3NO2.Allhydrogensare
bondedtocarbon,andtheorderof
atomicconnectionsisCONO.

Table1.4HowtoWriteLewis
Structures

Step2:
Countthenumberofvalenceelectrons.
Foraneutralmoleculethisisequalto
thenumberofvalenceelectronsofthe
constituentatoms.

Table1.4HowtoWriteLewis
Structures
Step2:
Countthenumberofvalenceelectrons.For
aneutralmoleculethisisequaltothenumber
ofvalenceelectronsoftheconstituentatoms.
Example(CH3NO2):
Eachhydrogencontributes1valence
electron.Eachcarboncontributes4,nitrogen
5,andeachoxygen6foratotalof24.

Table1.4HowtoWriteLewis
Structures

Step3:
Connecttheatomsbyacovalentbond
representedbyadash.

Table1.4HowtoWriteLewis
Structures

Step3:
Connecttheatomsbyacovalentbond
representedbyadash.
Example:
Methylnitritehasthepartialstructure:
H
H

Table1.4HowtoWriteLewis
Structures

Step4:
Subtractthenumberofelectronsin
bondsfromthetotalnumberofvalence
electrons.

H
H

Table1.4HowtoWriteLewis
Structures

Step4:
Subtractthenumberofelectronsin
bondsfromthetotalnumberofvalence
electrons.
Example:
24valenceelectrons12electronsin
bonds.Therefore,12moreelectronsto
assign.

Table1.4HowtoWriteLewis
Structures

Step5:
Addelectronsinpairssothatasmany
atomsaspossiblehave8electrons.
Startwiththemostelectronegative
atom.

Table1.4HowtoWriteLewis
Structures

Step5:
Addelectronsinpairssothatasmanyatomsas
possiblehave8electrons.Startwiththemost
electronegativeatom.

Example:
Theremaining12electronsinmethylnitriteare
addedas6pairs.

C
H

..
O
..

N
..

..
:
O
..

Table1.4HowtoWriteLewis
Structures

Step6:
Ifanatomlacksanoctet,useelectronpairsonan
adjacentatomtoformadoubleortriplebond.

Example:
Nitrogenhasonly6electronsinthestructureshown.

H
H

C
H

..
O
..

N
..

..
:
O
..

Table1.4HowtoWriteLewis
Structures

Step6:
Ifanatomlacksanoctet,useelectronpairsonan
adjacentatomtoformadoubleortriplebond.

Example:
AlltheatomshaveoctetsinthisLewisstructure.

H
H

C
H

..
O
..

N
..

..
O:

Table1.4HowtoWriteLewis
Structures

Step7:
Calculateformalcharges.

Example:
Noneoftheatomspossessaformalchargeinthis
Lewisstructure.

C
H

..
O
..

N
..

..
O:

Table1.4HowtoWriteLewis
Structures

Step7:
Calculateformalcharges.

Example:
Thisstructurehasformalcharges;islessstable
Lewisstructure.

C
H

+
O
..

N
..

..
:
O
..

Condensedstructural
formulas
Lewisstructuresinwhichmany(or
all)covalentbondsandelectronpairs
areomitted.
H

H : O: H
H

can be condensed to:

CH3CHCH3 or (CH3)2CHOH
OH

Bondlineformulas

CH3CH2CH2CH3 is shown as
CH3CH2CH2CH2OH is shown as

Omitatomsymbols.Represent
structurebyshowingbondsbetween
carbonsandatomsotherthan
hydrogen.
Atomsotherthancarbonand

hydrogenarecalledheteroatoms.

OH

Bondlineformulas
H
H2C

Cl
C

H2C

Cl

CH2
CH2

is shown as

C
H

Omitatomsymbols.Represent
structurebyshowingbondsbetween
carbonsandatomsotherthan
hydrogen.
Atomsotherthancarbonand

hydrogenarecalledheteroatoms.

3.5
ConstitutionalIsomers

Constitutionalisomers

Isomersaredifferentcompoundsthat
havethesamemolecularformula.

Constitutionalisomersareisomers
thatdifferintheorderinwhichtheatoms
areconnected.

Anoldertermforconstitutional
isomersisstructuralisomers.

AHistorical
Note

NH4OCN
Ammonium cyanate

H2NCNH2
Urea

In1823FriedrichWhlerdiscoveredthat
whenammoniumcyanatewasdissolvedinhot
water,itwasconvertedtourea.

Ammoniumcyanateandureaare
constitutionalisomersofCH4N2O.

Ammoniumcyanateisinorganic.Ureais
organic.Whleriscreditedwithanimportant
earlycontributionthathelpedoverturnthetheory
ofvitalism.

Examplesofconstitutional
isomers
H
H

C
H

..
O:

N+

:O
.. :

..
O
..

N
..

..
O:

Nitromethane

Methyl nitrite

BothhavethemolecularformulaCH3NO2butthe
atomsareconnectedinadifferentorder.

3.5
Resonance

Resonance
twoormoreacceptableoctetLewisstructures
maybe
writtenforcertaincompounds(orions)

Table1.4HowtoWriteLewis
Structures

Step6:
Ifanatomlacksanoctet,useelectronpairsonan
adjacentatomtoformadoubleortriplebond.

Example:
Nitrogenhasonly6electronsinthestructureshown.

H
H

C
H

..
O
..

N
..

..
:
O
..

Table1.4HowtoWriteLewis
Structures

Step6:
Ifanatomlacksanoctet,useelectronpairsonan
adjacentatomtoformadoubleortriplebond.

Example:
AlltheatomshaveoctetsinthisLewisstructure.

H
H

C
H

..
O
..

N
..

..
O:

Table1.4HowtoWriteLewis
Structures

Step7:
Calculateformalcharges.

Example:
Noneoftheatomspossessaformalchargeinthis
Lewisstructure.

C
H

..
O
..

N
..

..
O:

Table1.4HowtoWriteLewis
Structures

Step7:
Calculateformalcharges.

Example:
Thisstructurehasformalcharges;islessstable
Lewisstructure.

C
H

+
O
..

N
..

..
:
O
..

ResonanceStructuresofMethyl
Nitrite
sameatomicpositions
differinelectronpositions
H
H

..
O
..

N
..

..
O:

N
..

more stable
Lewis
structure

+
O
..

less stable
Lewis
structure

..
O
.. :

ResonanceStructuresofMethyl
Nitrite
sameatomicpositions
H
H

..
O
..

differinelectronpositions
N
..

..
O:

N
..

more stable
Lewis
structure

+
O
..

less stable
Lewis
structure

..
O
.. :

WhyWriteResonance
Structures?

Electronsinmoleculesareoftendelocalized
betweentwoormoreatoms.

ElectronsinasingleLewisstructureare
assignedtospecificatomsasingleLewisstructure
isinsufficienttoshowelectrondelocalization.

Compositeofresonanceformsmoreaccurately
depictselectrondistribution.

Example
Ozone(O3)
Lewisstructureof
ozoneshowsone
doublebondand
onesinglebond

Expect: one short bond and one

long bond
Reality: bonds are of equal length
(128 pm)

+
O

Example
Ozone(O3)
Lewisstructureof
ozoneshowsone
doublebondand
onesinglebond

+
O

Resonance:

+
O

+
O

3.7
TheShapesofSomeSimple
Molecules

Methane
tetrahedralgeometry
HCHangle=109.5

Methane
tetrahedralgeometry
eachHCHangle=109.5

ValenceShellElectronPair
Repulsions
Themoststablearrangementofgroups
attachedtoacentralatomistheonethathas
themaximumseparationofelectronpairs
(bondedornonbonded).

Water
bentgeometry
HOHangle=105

H
O

..
but notice the tetrahedral arrangement
of electron pairs

Ammonia
trigonalpyramidalgeometry
HNHangle=107

H
N

H
but notice the tetrahedral arrangement
of electron pairs

BoronTrifluoride
FBFangle=120
trigonalplanargeometry
allowsformaximumseparation
ofthreeelectronpairs

MultipleBonds
Fourelectrondoublebondsandsixelectron
triplebondsareconsideredtobesimilartoa
twoelectronsinglebondintermsoftheirspatial
requirements.

Formaldehyde:CH2=O
HCHandHCO
anglesarecloseto120
trigonalplanargeometry

H
C

Figure1.12:CarbonDioxide
OCOangle=180
lineargeometry

3.7:
PolarCovalentBonds
andElectronegativity

Electronegativity
Electronegativity

Electronegativityisameasureof
Electronegativityisameasureof
anelementtoattractelectrons
anelementtoattractelectrons
towarditselfwhenbondedto
towarditselfwhenbondedto
anotherelement.
anotherelement.

Anelectronegativeelementattractselectrons.
Anelectropositiveelementreleaseselectrons.

Pauling
PaulingElectronegativity
ElectronegativityScale
Scale
Li

Be

1.0

1.5

2.0

2.5

3.0

3.5

4.0

Na

Mg

Al

Si

Cl

0.9

1.2

1.5

1.8

2.1

2.5

3.0

Electronegativityincreasesfromlefttoright
intheperiodictable.

Electronegativitydecreasesgoingdownagroup.

Generalization
Generalization
Thegreaterthedifferenceinelectronegativity
betweentwobondedatoms;themorepolarthe
bond.
HH

..
F:
..

..
: ..
F

:N

N:

nonpolar bonds connect atoms of

the same electronegativity

Generalization
Generalization
Thegreaterthedifferenceinelectronegativity
betweentwobondedatoms;themorepolarthe
bond.

..
F:
..

..

O H
..

:
:O C O
..
..

polar bonds connect atoms of

different electronegativity

3.7
MolecularDipoleMoments

DipoleMoment
Asubstancepossessesadipolemoment
ifitscentersofpositiveandnegativecharge
donotcoincide.
=exd
(expressedinDebyeunits)
+

not polar

DipoleMoment
Asubstancepossessesadipolemoment
ifitscentersofpositiveandnegativecharge
donotcoincide.
=exd
(expressedinDebyeunits)

+
polar

MolecularDipoleMoments
-

moleculemusthavepolarbonds
necessary,butnotsufficient

needtoknowmolecularshape
becauseindividualbonddipolescancancel

MolecularDipoleMoments
O

Carbon dioxide has no dipole moment; = 0 D

ComparisonofDipoleMoments

Carbon tetrachloride

=0D

Dichloromethane

= 1.62 D

Carbontetrachloride
Resultant of these
two bond dipoles is

Resultant of these
two bond dipoles is

=0D
Carbon tetrachloride has no dipole
moment because all of the individual
bond dipoles cancel.

Dichloromethane
Resultant of these
two bond dipoles is

Resultant of these
two bond dipoles is

= 1.62 D
The individual bond dipoles do not
cancel in dichloromethane; it has
a dipole moment.