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15.2 Structure and Stability of Benzene

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  • Page ID
    67316
  • Objectives

    After completing this section, you should be able to

    1. compare the reactivity of a typical alkene with that of benzene.
    2. Use the heat of hydrogenation data to show that benzene is more stable than might be expected for “cyclohexatriene.”
    3. state the length of the carbon-carbon bonds in benzene, and compare this length with those of bonds found in other hydrocarbons.
    4. describe the geometry of the benzene molecule.
    5. describe the structure of benzene in terms of resonance.
    6. describe the structure of benzene in terms of molecular orbital theory.
    7. draw a molecular orbital diagram for benzene.

    Key Terms

    Make certain that you can define, and use in context, the key term below.

    • degenerate

    Study Notes

    You may wish to review Sections 1.5 and 14.1 before you begin to study this section.

    Note that the figure showing the molecular orbitals of benzene has two bonding (π2 and π3) and two anti-bonding (π* and π5*) orbital pairs at the same energy levels. Orbitals with the same energy are described as degenerate orbitals.

    Among the many distinctive features of benzene, its aromaticity is the major contributor to why it is so unreactive. This section will try to clarify the theory of aromaticity and why aromaticity gives unique qualities that make these conjugated alkenes inert to compounds such as Br2 and even hydrochloric acid. It will also go into detail about the unusually large resonance energy due to the six conjugated carbons of benzene.

    dd.bmp

    The delocalization of the p-orbital carbons on the sphybridized carbons is what gives the aromatic qualities of benzene.

    This diagram shows one of the molecular orbitals containing two of the delocalized electrons, which may be found anywhere within the two "doughnuts". The other molecular orbitals are almost never drawn.

    • Benzene (\(C_6H_6\)) is a planar molecule containing a ring of six carbon atoms, each with a hydrogen atom attached.
    • The six carbon atoms form a perfectly regular hexagon. All of the carbon-carbon bonds have exactly the same lengths - somewhere between single and double bonds.
    • There are delocalized electrons above and below the plane of the ring, which makes benzene particularly stable.
    • Benzene resists addition reactions because those reactions would involve breaking the delocalization and losing that stability.

    Because of the aromaticity of benzene, the resulting molecule is planar in shape with each C-C bond being 1.39 Å in length and each bond angle being 120°. You might ask yourselves how it's possible to have all of the bonds to be the same length if the ring is conjugated with both single (1.47 Å) and double (1.34 Å), but it is important to note that there are no distinct single or double bonds within the benzene. Rather, the delocalization of the ring makes each count as one and a half bonds between the carbons which makes sense because experimentally we find that the actual bond length is somewhere in between a single and double bond. Finally, there are a total of six p-orbital electrons that form the stabilizing electron clouds above and below the aromatic ring.

    Benzene Structure (1).bmp

    If benzene is forced to react by increasing the temperature and/or by addition of a catalyst, It undergoes substitution reactions rather than the addition reactions that are typical of alkenes. This further confirms the previous indication that the six-carbon benzene core is unusually stable to chemical modification. The conceptual contradiction presented by a high degree of unsaturation (low H:C ratio) and high chemical stability for benzene and related compounds remained an unsolved puzzle for many years. Eventually, the presently accepted structure of a regular-hexagonal, planar ring of carbons was adopted, and the exceptional thermodynamic and chemical stability of this system was attributed to resonance stabilization of a conjugated cyclic triene.

    The High Stability of Benzene

    Here, two structurally and energetically equivalent electronic structures for a stable compound are written, but no single structure provides an accurate or even an adequate representation of the true molecule. The six-membered ring in benzene is a perfect hexagon (all carbon-carbon bonds have an identical length of 1.40 Å). The cyclohexatriene contributors would be expected to show alternating bond lengths, the double bonds being shorter (1.34 Å) than the single bonds (1.54 Å). An alternative representation for benzene (circle within a hexagon) emphasizes the pi-electron 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 composed of such molecules often show exceptional stability and related properties.

    Evidence for the enhanced thermodynamic stability of benzene was obtained from measurements of the heat released when double bonds in a six-carbon ring are hydrogenated (hydrogen is added catalytically) to give cyclohexane as a common product. In the following diagram cyclohexane represents a low-energy reference point. Addition of hydrogen to cyclohexene produces cyclohexane and releases heat amounting to 28.6 kcal per mole. If we take this value to represent the energy cost of introducing one double bond into a six-carbon ring, we would expect a cyclohexadiene to release 57.2 kcal per mole on complete hydrogenation, and 1,3,5-cyclohexatriene to release 85.8 kcal per mole. These heats of hydrogenation would reflect the relative thermodynamic stability of the compounds. In practice, 1,3-cyclohexadiene is slightly more stable than expected, by about 2 kcal, presumably due to conjugation of the double bonds. Benzene, however, is an extraordinary 36 kcal/mole more stable than expected. This sort of stability enhancement is now accepted as a characteristic of all aromatic compounds.

     

    A molecular orbital description of benzene provides a more satisfying and more general treatment of "aromaticity". We know that benzene has a planar hexagonal structure in which all the carbon atoms are sp2 hybridized, and all the carbon-carbon bonds are equal in length. As shown below, the remaining cyclic array of six p-orbitals ( one on each carbon) overlap to generate six molecular orbitals, three bonding and three antibonding. The plus and minus signs shown in the diagram do not represent electrostatic charge, but refer to phase signs in the equations that describe these orbitals (in the diagram the phases are also color coded). When the phases correspond, the orbitals overlap to generate a common region of like phase, with those orbitals having the greatest overlap (e.g. π1) being lowest in energy. The remaining carbon valence electrons then occupy these molecular orbitals in pairs, resulting in a fully occupied (6 electrons) set of bonding molecular orbitals. It is this completely filled set of bonding orbitals, or closed shell, that gives the benzene ring its thermodynamic and chemical stability, just as a filled valence shell octet confers stability on the inert gases.

    The Molecular Orbitals of Benzene

     

    Exercises

    Questions

    Q15.2.1

    The molecule shown, p-methylpyridine, has similar properties to benzene (flat, 120° bond angles). Draw the pi-orbitals for this compound.

    Solutions

    S15.2.1

    The nitrogen has a lone pair of electrons perpendicular to the ring.

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