Electrophilic Aromatic Substitution
During the nitration of benzene using a mixture of concentrated nitric and sulphuric acids, the actual attacking electrophile generated in the reaction mixture must be identified.
Select the correct option:
Solution
Nitronium ion NO2+
Nitration of benzene is a classic electrophilic aromatic substitution in which a strong electrophile attacks the delocalized pi system of the ring. Concentrated sulphuric acid protonates nitric acid, which then loses water to generate the nitronium ion: HNO3+2H2SO4→NO2++H3O++2HSO4−. This linear nitronium ion is the effective electrophile that adds to benzene to form a resonance-stabilized arenium ion (sigma complex), which then loses a proton to restore aromaticity and yield nitrobenzene. The nitrosonium ion NO+ forms in nitrosation reactions with nitrous acid, not in nitration, so it is wrong. The nitrate ion NO3− is negatively charged and cannot act as an electrophile toward an electron-rich ring, so it is incorrect. The NO2∙ radical belongs to radical chemistry, not to this ionic substitution, so it does not apply. The overall reaction preserves aromaticity because, unlike addition, substitution allows the ring to regain its fully delocalised sextet of pi electrons after the proton is lost from the sigma complex. This explains why benzene undergoes substitution rather than addition despite being formally unsaturated. This is precisely the NCERT mechanism for aromatic nitration. A plausibility check: only a positively charged species can be attracted to the electron-rich benzene ring, confirming the nitronium ion.
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About This Question
- Subject
- chemistry
- Chapter
- hydrocarbons
- Topic
- electrophilic aromatic substitution
- Difficulty
- Medium
- Year
- 2025
Solution
Correct Answer:
Nitronium ion NO2+
Nitration of benzene is a classic electrophilic aromatic substitution in which a strong electrophile attacks the delocalized pi system of the ring. Concentrated sulphuric acid protonates nitric acid, which then loses water to generate the nitronium ion: HNO3+2H2SO4→NO2++H3O++2HSO4−. This linear nitronium ion is the effective electrophile that adds to benzene to form a resonance-stabilized arenium ion (sigma complex), which then loses a proton to restore aromaticity and yield nitrobenzene. The nitrosonium ion NO+ forms in nitrosation reactions with nitrous acid, not in nitration, so it is wrong. The nitrate ion NO3− is negatively charged and cannot act as an electrophile toward an electron-rich ring, so it is incorrect. The NO2∙ radical belongs to radical chemistry, not to this ionic substitution, so it does not apply. The overall reaction preserves aromaticity because, unlike addition, substitution allows the ring to regain its fully delocalised sextet of pi electrons after the proton is lost from the sigma complex. This explains why benzene undergoes substitution rather than addition despite being formally unsaturated. This is precisely the NCERT mechanism for aromatic nitration. A plausibility check: only a positively charged species can be attracted to the electron-rich benzene ring, confirming the nitronium ion.
This medium difficulty chemistry question is from the chapter hydrocarbons, covering the topic of electrophilic aromatic substitution. It appeared in the 2025 exam.
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