Chemistry101 Chapter9

THECOVALENTBOND

Acovalentbondisachemicalbondformedbythesharingofapairofelectronsbetween
atoms.Itholdsatomstogetherinamolecule

ConsidertheformationoftheH2 moleculefromtwoHatoms:
AstwoHatomsapproacheachother,thesingle1selectrononeach atombeginsto
feeltheattractionofbothnuclei.
Theelectrondensityshiftstotheregionbetweenthenuclei:

H2

1s2 or -
1s

74pm BondLength=74pm

Thetwoelectronsaresharedbybothatomsandserveasasortofgluecementingtheatoms
together

Atadistanceof75pmbetweenthenuclei:

Theattraction Therepulsion
ofthetwoelectrons balancesout between
forbothnuclei thenuclei

Result:
ThePotentialEnergyisataminimum
Themoleculeisstable

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Chemistry101 Chapter9

EnergyDiagramfortheformationofH2 fromtwoHatoms

Potentialenergyof
2 isolatedHatoms

PotentialEnergyis
ataminimum
(attractionsandrepulsions
arebalanced)

PotentialEnergyrisessteeply
(nucleigetcloserandstarttorepel)

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Chemistry101 Chapter9

COVALENTBONDTERMINOLOGY

BONDDISSOCIATIONENERGY(orsimplyBondEnergy)
TheEnergythatmustbesuppliedtoseparateatomsfrommolecules

Example:ForH2 theBondEnergyis435kJ/mol)

BONDLENGTH(orsimplyBondDistance)
Thedistancebetweenthenucleioftheatomsinvolvedinacovalentbondwhentheenergyis
ataminimum.

Example:ForH2,theBondLengthis74pm

TheFormationoftheH2 moleculecanberepresentedinabbreviatedform:

1.Bywritingouttheelectronconfigurationsoftheatoms:

H + H H2
1s1 1s1 1s2 (stabledoublet)
[He]
2.ByLewiselectrondotformulas:

onepairofsharedelectrons
thatbelongstobothatoms
(stabledoublet)

Onepairofsharedelectronsiscommonlyrepresentedbyadash. ThedashstandsforOne
CovalentBond

ElectronDotFormula StructuralFormula MolecularFormula

Onepairof OneCovalent
sharedelectrons Bond

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Chemistry101 Chapter9

COVALENTBONDSBETWEENIDENTICALATOMS(Nonmetals)

ElectronDot Structural Molecular

Formula Formula Formula

8electronsaround 8electronsaround
ClatomClatom
(stable octet)(stable octet)

=onepairofbondingelectrons(sharedelectrons)

=onepairofnonbondingelectrons(lonepair)
NOTE:Thereare3nonbondingelectronpairs(lonepairs) aroundeachClatom.

Similarformulascanbewrittenforthefollowingmolecules:
F2, Br2, I2 (samegroup,samenumberofvalenceelectrons)

ElectronDot Structural Molecular

Formula Formula Formula

8electronsaround8electronsaround
NatomNatom
(stable octet)(stable octet)

triplecovalentbond
threepairsofbondingelectrons(sharedelectrons)

=onepairofnonbondingelectrons(lonepair)
NOTE:Thereisonenonbondingelectronpair(lonepair)oneachNatom.

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Chemistry101 Chapter9

COVALENTBONDSBETWEENUNLIKEATOMS(Nonmetalsonly)

ElectronDot Structural Molecular

Formula Formula Formula

stabledoublet stableoctet
aroundHatom aroundClatom

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Chemistry101 Chapter9
ElectronDot Structural Molecular
Formula Formula Formula

NOTE:
1.Insharingelectrons,atomsobtainaNobleGasConfiguration(ns2 np6 or1s2)
ThisisreferredtoastheOCTETRULE

TheOCTETRULEisthetendencyofatomsinmoleculestohave8electronsintheirvalenceshell
Hisanexceptionsinceithasonlyoneshell HobeysTHEDOUBLETRULE

2. Thenumber
ofcovalentbonds = 8 GroupNumber
anatomforms

NOTE:Halwaysformsonlyonebond(2 GroupNumber): H
ThisisausefulRuleofThumbthatworksformany(notall)elements

IVA VA VIA VIIA

(4bonds) (3bonds) (2bonds) (1bond)

C N O F

Si PSCl

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Chemistry101 Chapter9

DRAWINGLEWISSTRUCTURES

NotallLewisStructurescanbeeasilydetermined.
ForExample:DrawaLewisStructureforthemoleculeofCO2
Asystematicapproachisneeded:

Step1: Countallthevalenceelectronsofallatoms

CO2
4e- 2x6e-
4e- + 12e- =16valenceelectrons(16dotsmaybeused)

Step2: Drawaskeletonstructure,keepinginmindthat:
Themostsymmetricalarrangementisthemostlikely,
Hcannotbeacentralatom(formsonlyonebond)

O C O

Step3: Connectallatomswithonebond (placeonepairofelectronsineachbond)

O C O or O:C:O

Note:4electronsoftheavailable16havebeenused(12remainavailable)

Step4: Attempttocompletetheoctetsofallatomsbyusingtheavailableelectrons
(Recallthat12electronsarestillavailable)
.... ....
: : or : : : :
.... ....

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Chemistry101 Chapter9

Step5:Checkifalloctets(doubletforH)aresatisfied.
(A) Ifoctets(respectivelydoublet)aresatisfied,theLewisstructureiscorrect.

.. ..
: :
.. ..

8electrons 8electrons
aroundO aroundO

4electrons NOTE:TheoctetofCisnotsatisfied!
aroundC(?)

(B)Iftheoctetsarenotsatisfied:
Placeanyadditionalelectronsonthecentralatominpairs,
Inthiscasetherearenoadditionalelectrons(all16havebeenused)

OR

Formmultiplebondsbyrearrangingelectrons,sothateachatomhasanoctet

:: : :
.. .. .. ..

8electrons 8electrons
aroundO aroundO

8electrons NOTE:TheoctetofCissatisfied!
aroundC

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Chemistry101 Chapter9
ExamplesofLewisStructures

1.DrawtheLewisStructureforC2H6 (ethane)
Step1: Countallthevalenceelectronsofallatoms

C2H6

2x4e- 6x1e-
8electrons+ 6electrons = 14valenceelectrons

Step2: Drawaskeletonstructure,keepinginmindthat:
Themostsymmetricalarrangementisthemostlikely,
Hcannotbeacentralatom(formsonlyonebond)

H H

H C C H

H H
Step3: Connectallatomswithonebond (placeonepairof electronsineachbond)

NOTE:All14electronshavebeenused
(7bondsx2electrons/bond=14electrons)

Step4: Attempttocompletetheoctetsofallatomsbyusingtheavailableelectrons
Thisstepwillbeskippedsincetherearenoavailableelectrons

Step5:Checkifalloctets(doubletforH)aresatisfied.

NOTE:TheoctetsofbothCsaresatisfied
Thedoubletsofall6Hsaresatisfied

Hence:TheLewisstructureiscorrect

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Chemistry101 Chapter9
2.DrawtheLewisStructureforC2H4 (ethene)

Step1:Countallthevalenceelectronsofallatoms

C2H4

2x4e- 4x1e-
8electrons + 4electrons = 12valenceelectrons

Step2: Drawaskeletonstructure,keepinginmindthat:
Themostsymmetricalarrangementisthemostlikely,
Hcannotbeacentralatom(formsonlyonebond)

H H

H C C H

Step3: Connectallatomswithonebond (placeonepairofelectronsineachbond)

NOTE:10electrons(5bonds)havebeenused
(2electronsremainavailable)

Step4: Attempttocompletetheoctetsofallatomsbyusingtheavailableelectrons
(Recallthat2electrons( ..)arestillavailable)

Step5:Checkifalloctets(doubletsforHs)aresatisfied.

NOTE:
TheoctetsforbothCsaresatisfied(4bonds=8electronssurroundbothCs)
Thedoubletsforall4Hsaresatisfied(eachHattachedby1bond=2electrons)

TheLewisStructureiscorrectaswritten

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Chemistry101 Chapter9

3.DrawtheLewisStructureforC2H2 (acetylene)
Step1:Countallthevalenceelectronsofallatoms

C2H2

2x4e- 2x1e-
8electrons + 2electrons = 10valenceelectrons

Step2: Drawaskeletonstructure,keepinginmindthat:
Themostsymmetricalarrangementisthemostlikely,
Hcannotbeacentralatom(formsonlyonebond)

H C C H

Step3: Connectallatomswithonebond (placeonepairofelectronsineachbond)

NOTE:6electrons(3bonds)havebeenused(4electronsremainavailable)

Step4: Attempttocompletetheoctetsofallatomsbyusingtheavailableelectrons
(Recallthat4electrons(:: )arestillavailable)

.
Step5:Checkifalloctets(doubletsforHs)aresatisfied:

NOTE:
TheoctetsforbothCsaresatisfied(4bonds=8electronssurroundbothCs)
Thedoubletsforall4Hsaresatisfied(eachHattachedby1bond=2electrons)

TheLewisStructureiscorrectaswritten

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Chemistry101 Chapter9

LEWISSTRUCTUREOFPOLYATOMICIONS

PolyatomicIonsareionsconsistingoftwoormoreatomsbondedtogetherbycovalentbondsand
carryinganelectriccharge.

Examples:NH4+(ammonium),SO42- (sulfate), NO3-(nitrate), OH- (hydroxide)

Recall: Positiveionsareshortofelectrons
Negativeionshaveexcesselectrons.

WriteLewisstructureforthefollowingPolyatomicIons:
I. TheNH4+ (ammonium)ion
Step1:Countallthevalenceelectronsofallatoms.
Subtract1electronsincetheionhasachargeof+1:

N = 5e
4H = 4e
(+1)Charge = 1e -

Total: = 8e 8dotsareavailable

Step2:Drawaskeletonstructure,keepinginmindthat:
Themostsymmetrical arrangementisthemostlikely
Hcannotbeacentralatom(formsonlyonebond)

H N H

Step3:Connectallatomswithonebond(placeonepairofelectronsineachbond)
+

Step4: Checkifalloctets(doubletforH)aresatisfied.

Theoctetof Nissatisfied(4bondsx2electrons/bond=8electrons)
Thedoubletsofall4Hsaresatisfied(1bond=2electrons)

Hence:TheLewisstructureiscorrect

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Chemistry101 Chapter9
II. TheSO42- (sulfate)ion
Step1:Countallthevalenceelectronsofallatoms.
Add2electronssincetheionhasachargeof -2:

S = 1x6e - = 6e -
4O = 4x6e - = 24e -
(2 )Charge = +2e - = 2e

Total: = 32e - 32dotsareavailable

Step2:Drawaskeletonstructure,keepinginmindthat:
Themostsymmetricalarrangementisthemostlikely.

O S O

Step3:Connectallatomswithonebond(placeonepairofelectronsineachbond)
2-

Note:8electronshavebeenused(4bonds)
Availableelectrons:32 8= 24

Step4:Attempttocompletetheoctetsofallatomsbyusingtheavailableelectrons
(Recallthat24electronsarestillavailable)
2

Step5: Checkifalloctetsare satisfied.

Theoctetof Sissatisfied(4bondsx2electrons/bond= 8electrons)

Theoctetsofall4Osaresatisfied: 1bond = 2electrons
3lonepairs = 6electrons
TotalelectronssurroundingO = 8electrons

Hence:TheLewisStructureiscorrect

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Chemistry101 Chapter9

EXCEPTIONSTOTHEOCTETRULE

I.Moleculeswithatomsthataresurroundedbylessthananoctet
BeandBcompoundsaretypicalexamples

BeH2 1Be = 1x2electrons =2electrons

2H = 2x1electron =2electrons

Totalnumberofelectrons =4electrons

H Be H

Bedoesnothaveanoctet(only 4electronssurroundBe)
Beiselectrondeficient

BCl3 1B = 1x3electrons =3electrons

3Cl = 3x7electrons =21electrons

Total =24electrons

Bdoesnothaveanoctet(only 6electronssurroundB)
Biselectrondeficient
Bcannotformdoubleortriplebonds
(Reasonwillbegivenlater)

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Chemistry101 Chapter9

EXCEPTIONSTOTHEOCTETRULE

II.Moleculeswithatomsthataresurroundedbymorethananoctet
Thisoccursifthemoleculecontainsatomswith availabledorbitals
Thisimplies:
theseatomsmusthaveatleast3energylevels
theseatomsmustbein Periods3,4,5,6,or7
theseatomscannotbe: inPeriod1(H)or
inPeriod2(B,C,N,O,Cl)
Examples:
1. PCl5

1P = 1x5electrons =5electrons
5Cl = 5x7electrons =35electrons

Totalnumberofelectrons: =40electrons

Mostsymmetricalarrangement:

Note:10electronshavebeenused(5bonds)
Availableelectrons:40 10= 30

Connectallatomswithonebond

Attempttocompletetheoctetsofallatomsbyusingtheavailableelectrons
(Recallthat30electronsarestillavailable)

Adding6electronstoeachofthe
5Clatoms(6x5=30electrons)
willcompletetheoctetsoftheClatoms.

Checkifallatomshaveatleastanoctet.
NOTE:Theoctetsofall5oftheCl atomsaresatisfied

TotalelectronssurroundingCl=8electrons
TheP atomissurroundedby 10electrons
RecallthatPhas3shells(3dsubshellavailable)
Therefore:Pcanhaveupto18electronssinceadditional electronscanbeaccommodated
onthe3dsubshell

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Chemistry101 Chapter9

2. SF6

1S = 1x6electrons =6electrons
6F = 6x7electrons = 42electrons

Totalnumberofelectrons: = 48electrons

Mostsymmetricalarrangement,connectingallatomswithonebond:

Note:12electronshavebeenused(6bonds)
Availableelectrons:4812=36

Attempttocompletetheoctetsofallatomsbyusingtheavailableelectrons
(Recallthat36electronsarestillavailable)

Adding6electronstoeachofthe
6Fatoms(6x6=36electrons)
willcompletetheoctetsoftheFatoms

Checkifallatomshaveatleastanoctet:
NOTE:Theoctetsofall6oftheF atomsaresatisfied

TheSatomissurroundedby 12electrons
RecallthatShas3shells(3dsubshellavailable)

Therefore: Scanhaveupto18electronssinceadditional electronscanbe

accommodatedonthe3dsubshell.

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Chemistry101 Chapter9

BONDPROPERTIES

BondLength
isthedistancebetweenthenucleioftheatomsformingacovalentbond.

isdeterminedexperimentallybyXraydiffraction,amethodthatlocates thenucleiof
theatomsinvolvedinacovalentbond.

isthesumofthecovalentradiioftheatomsjoinedinabond.

BondOrder
isthenumberofelectronpairsthatformacovalentbond

CCBondLength 154pm 137pm 120pm

CCBondOrder 1 2 3

NOTE:AstheBondOrderincreases,theBondLengthdecreases
Reason: AstheBondOrderincreases,electrondensityincreases.
Hence:thehigherelectrondensitypullstheatomsclosertogether.

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Chemistry101 Chapter9

BONDENERGIES

Bondenergyistheenergyrequiredtobreakacovalentbond
Itisameasureofthestrengthofthebond:

THEHIGHERTHEBONDENERGY,THESTRONGERTHEBOND

CCBondLength 154pm 137pm 120pm

CCBondOrder 1 2 3

BondEnergy: +346 +602 +835

(kJ/mol)

NOTE:
BondEnergiesarealwayspositive(ittakesenergytobreakabond)

Conversely:Formation ofabondisanexothermicprocess(BondEnergyisreleased)

ThehighertheBondEnergy,theshortertheBondLength,thestrongerthebond

HighBondEnergy ShortBondLength StrongBond

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Chemistry101 Chapter9

ThermochemicalDefinitionofBONDENERGY

BondenergiescanbedefinedastheAverageEnthalpychangeforthebreakingofacovalentbondina
moleculeingasphase

(g) C(g)+4H(g) DH=+1644kJ/mol

+1644kJ/mol
BondEnergyfortheCHbond = = +411kJ/mol
4

ItfollowsthatHeatsofReactions(EnthalpyChanges)canbecalculatedfromknownvaluesofBond
Energies.

Considerthefollowingreaction:

DH=?

BondsbrokenareshowninBlue BondsformedareshowninRed

BondEnergies(kJ/mol)forSingleBonds

411 240 327 428

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Chemistry101 Chapter9

Considerthesteps:

CH3 H
CH3 +H DH=+411kJ/mol(bondbreaking)

Cl Cl
Cl+Cl DH=+240kJ/mol(bondbreaking)

CH3 +Cl
CH3Cl DH= 327kJ/mol(bondformation)

H+Cl
HCl DH= 428kJ/mol(bondformation)

AccordingtoHesssLaw:

DH= (+411kJ) + (+240kJ) + (327kJ) + (428kJ)= 104kJ/mol Exothermic!

Energyused Energyreleased
forbondbreaking bybondformation

InGeneral:
SumofBondEnergies SumofBondEnergies
DHofReaction = required givenoff
forBondBreaking byBondFormation

WhatmakesaReaction Exothermic(DH <0) or Endothermic(DH >0) ?

Exothermic:
EnergygivenoffbyBondFormation > EnergyrequiredtoBreakBonds

Meaning:WeakBondsarereplacedStrongBonds

Endothermic:
EnergygivenoffbyBondFormation < EnergyrequiredtoBreak Bonds

Meaning:StrongBondsarereplacedbyWeakBonds

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Chemistry101 Chapter9

Examples:
1. CalculatetheEnthalpyofReactionforthefollowingReaction:

2H2(g) + O2(g) 2H2O(g) DH=?

IstheReactionExothermicorEndothermic?

BondEnergies(kJ/mol)

432 142 459

SumofBondEnergies SumofBondEnergies
DHofReaction = required givenoff
forBondBreaking byBondFormation

DHofReaction = [2(+432kJ)+(142kJ)] [4(459kJ)] = 830kJ

TheReactionisstronglyexothermic!

2. UsebondenergiesinTable9.5inyourtextbooktodetermine DHforthereactionshownbelow:

2NCl3 N2 +3Cl2

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