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Hydrocarbons - Aromatic Hydrocarbons (Benzene)

Grade 11ICSEChemistry

Review the key concepts, formulae, and examples before starting your quiz.

🔑Concepts

Structure of Benzene: Benzene is a cyclic hydrocarbon with the formula C6H6C_6H_6. All six carbon atoms are sp2sp^2 hybridized, forming a planar hexagonal ring. Each carbon is bonded to one hydrogen atom and two other carbons via σ\sigma bonds, with a delocalized π\pi electron cloud above and below the plane.

Resonance and Stability: Benzene is a resonance hybrid of two Kekulé structures. The delocalization of π\pi electrons (resonance) provides extra stability called resonance energy, making it less reactive than typical alkenes.

Hückel's Rule of Aromaticity: For a compound to be aromatic, it must be cyclic, planar, completely conjugated, and possess (4n+2)π(4n + 2) \pi electrons, where nn is an integer (0,1,2,0, 1, 2, \dots).

Electrophilic Substitution Reactions (ESR): Benzene undergoes substitution rather than addition to maintain its aromatic stability. Key reactions include Nitration, Sulphonation, Halogenation, and Friedel-Crafts Alkylation/Acylation.

Directive Influence: Functional groups already present on the benzene ring determine the position of the incoming electrophile. Activating groups (e.g., OH,NH2,CH3-OH, -NH_2, -CH_3) are orthoortho and parapara directing, while deactivating groups (e.g., NO2,CHO,COOH-NO_2, -CHO, -COOH) are metameta directing (except halogens, which are deactivating but o,po, p directing).

Toxicity: Benzene and polynuclear hydrocarbons (like Benzo[a]pyrene) produced by incomplete combustion of organic matter are carcinogenic and toxic.

📐Formulae

CnH2n6 (General formula for Benzene series)C_nH_{2n-6} \text{ (General formula for Benzene series)}

Hu¨ckel’s Rule: (4n+2)π electrons\text{Hückel's Rule: } (4n + 2)\pi \text{ electrons}

Nitration: C6H6+HNO3conc.H2SO4,323333KC6H5NO2+H2O\text{Nitration: } C_6H_6 + HNO_3 \xrightarrow{conc. H_2SO_4, 323-333K} C_6H_5NO_2 + H_2O

Halogenation: C6H6+Cl2Anhyd.FeCl3C6H5Cl+HCl\text{Halogenation: } C_6H_6 + Cl_2 \xrightarrow{Anhyd. FeCl_3} C_6H_5Cl + HCl

Friedel-Crafts Alkylation: C6H6+CH3ClAnhyd.AlCl3C6H5CH3+HCl\text{Friedel-Crafts Alkylation: } C_6H_6 + CH_3Cl \xrightarrow{Anhyd. AlCl_3} C_6H_5CH_3 + HCl

Sulphonation: C6H6+H2SO4(fuming)ΔC6H5SO3H+H2O\text{Sulphonation: } C_6H_6 + H_2SO_4 (fuming) \xrightarrow{\Delta} C_6H_5SO_3H + H_2O

💡Examples

Problem 1:

Explain why the Cyclooctatetraene (C8H8C_8H_8) molecule is not aromatic even though it is cyclic and contains conjugated double bonds.

Solution:

Cyclooctatetraene has 8π8 \pi electrons. According to Hückel's Rule, (4n+2)π(4n+2)\pi electrons are required for aromaticity. For C8H8C_8H_8, 4n+2=84n+2 = 8 gives n=1.5n = 1.5, which is not an integer. Furthermore, the molecule adopts a non-planar 'tub' shape to minimize strain.

Explanation:

To be aromatic, a compound must strictly satisfy all four criteria: cyclic, planar, fully conjugated, and the (4n+2)(4n+2) electron count. C8H8C_8H_8 fails the electron count and planarity tests.

Problem 2:

Predict the major product when Toluene (C6H5CH3C_6H_5CH_3) undergoes nitration with a mixture of conc.HNO3conc. HNO_3 and conc.H2SO4conc. H_2SO_4.

Solution:

The major products are orthoortho-nitrotoluene and parapara-nitrotoluene.

Explanation:

The methyl group (CH3-CH_3) is an electron-releasing group due to inductive effect (+I+I) and hyperconjugation. This increases the electron density at the orthoortho and parapara positions, making them more reactive towards the electrophile NO2+NO_2^+. Thus, it is an o,po, p-directing activator.

Problem 3:

What is the catalyst used in Friedel-Crafts reaction and what is its role?

Solution:

The catalyst is Anhydrous Aluminium Chloride (AlCl3AlCl_3).

Explanation:

AlCl3AlCl_3 acts as a Lewis acid. It reacts with the alkyl or acyl halide to generate a powerful electrophile (carbocation, R+R^+) by accepting a lone pair from the halogen atom: RCl+AlCl3R++[AlCl4]R-Cl + AlCl_3 \rightarrow R^+ + [AlCl_4]^-. This electrophile then attacks the benzene ring.

Aromatic Hydrocarbons (Benzene) - Revision Notes & Key Formulas | ICSE Class 11 Chemistry