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ChemWiki:TheDynamicChemistryHypertext>Core>OrganicChemistry>Hydrocarbons>Arenes>PropertiesofArenes>
PropertiesofBenzene

Properties of Benzene

Becauseofthelowhydrogentocarbonratioinaromaticcompounds(notethattheH:Cratioinanalkaneis>2),chemistsexpected
theirstructuralformulaswouldcontainalargenumberofdoubleortriplebonds.Sincedoublebondsareeasilycleavedbyoxidative
reagents such as potassium permanganate or ozone, and rapidly add bromine and chlorine, these reactions were applied to these
aromaticcompounds.Surprisingly,productsthatappearedtoretainmanyofthedoublebondswereobtained,andthesecompounds
exhibitedahighdegreeofchemicalstabilitycomparedwithknownalkenesandcycloalkenes(aliphaticcompounds).Ontreatmentwith
hotpermanganatesolution,cinnamaldehydegaveastable,crystallineC7H6O2compound,nowcalledbenzoicacid.TheH:Cratioin
benzoic acid is <1, again suggesting the presence of several double bonds. Benzoic acid was eventually converted to the stable
hydrocarbonbenzene,C6H6,whichalsoprovedunreactivetocommondoublebondtransformations,asshownbelow.Forcomparison,
reactions of cyclohexene, a typical alkene, with these reagents are also shown (green box). As experimental evidence for a wide
assortmentofcompoundswasacquired,thoseincorporatingthisexceptionallystablesixcarboncorecametobecalled"aromatic".

Ifbenzeneisforcedtoreactbyincreasingthetemperatureand/orbyadditionofacatalyst,Itundergoessubstitutionreactionsrather
thantheadditionreactionsthataretypicalofalkenes.Thisfurtherconfirmsthepreviousindicationthatthesixcarbonbenzenecoreis
unusuallystabletochemicalmodification.Theconceptualcontradictionpresentedbyahighdegreeofunsaturation(lowH:Cratio)and
high chemical stability for benzene and related compounds remained an unsolved puzzle for many years. Eventually, the presently
accepted structure of a regularhexagonal, planar ring of carbons was adopted, and the exceptional thermodynamic and chemical
stabilityofthissystemwasattributedtoresonancestabilizationofaconjugatedcyclictriene.
Benzene:
Here, two structurally and energetically equivalent electronic structures for a stable compound are written, but no single structure
providesanaccurateorevenanadequaterepresentationofthetruemolecule.Thesixmemberedringinbenzeneisaperfecthexagon
(allcarboncarbonbondshaveanidenticallengthof1.40).Thecyclohexatrienecontributorswouldbeexpectedtoshowalternating
bondlengths,thedoublebondsbeingshorter(1.34)thanthesinglebonds(1.54).Analternativerepresentationforbenzene(circle
within a hexagon) emphasizes the pielectron delocalization in this molecule, and has the advantage of being a single diagram. In
cases such as these, the electron delocalization described by resonance enhances the stability of the molecules, and compounds
composedofsuchmoleculesoftenshowexceptionalstabilityandrelatedproperties.
Evidencefortheenhancedthermodynamicstabilityofbenzenewasobtainedfrommeasurementsoftheheatreleasedwhendouble
bonds in a sixcarbon ring are hydrogenated (hydrogen is added catalytically) to give cyclohexane as a common product. In the
following diagram cyclohexane represents a lowenergy reference point.Addition of hydrogen to cyclohexene produces cyclohexane
andreleasesheatamountingto28.6kcalpermole.Ifwetakethisvaluetorepresenttheenergycostofintroducingonedoublebond
into a sixcarbon ring, we would expect a cyclohexadiene to release 57.2 kcal per mole on complete hydrogenation, and 1,3,5
cyclohexatrienetorelease85.8kcalpermole.Theseheatsofhydrogenationwouldreflecttherelativethermodynamicstabilityofthe
compounds.Inpractice,1,3cyclohexadieneisslightlymorestablethanexpected,byabout2kcal,presumablyduetoconjugationof
the double bonds. Benzene, however, is an extraordinary 36 kcal/mole more stable than expected. This sort of stability
enhancementisnowacceptedasacharacteristicofallaromaticcompounds.

A molecular orbital description of benzene provides a more satisfying and more general treatment of "aromaticity". We know that
benzenehasaplanarhexagonalstructureinwhichallthecarbonatomsaresp2hybridized,andallthecarboncarbonbondsareequal
inlength.Asshownbelow,theremainingcyclicarrayofsixporbitals(oneoneachcarbon)overlaptogeneratesixmolecularorbitals,
threebondingandthreeantibonding.Theplusandminussignsshowninthediagramdonotrepresentelectrostaticcharge,butreferto
phase signs in the equations that describe these orbitals (in the diagram the phases are also color coded). When the phases
correspond,theorbitalsoverlaptogenerateacommonregionoflikephase,withthoseorbitalshavingthegreatestoverlap(e.g.1)
being lowest in energy. The remaining carbon valence electrons then occupy these molecular orbitals in pairs, resulting in a fully
occupied(6electrons)setofbondingmolecularorbitals.Itisthiscompletelyfilledsetofbondingorbitals,orclosedshell,thatgivesthe
benzeneringitsthermodynamicandchemicalstability,justasafilledvalenceshelloctetconfersstabilityontheinertgases.

TheMolecularOrbitalsofBenzene

Contributors
WilliamReusch,ProfessorEmeritus(MichiganStateU.),VirtualTextbookofOrganicChemistry
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