Q.Reduction of nitrobenzene by which of the following reagent gives aniline?
(Two or more options may be correct.)
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🔒 Start your 14-day free trial to unlock the full solution →Concept understanding — Electrophilic Aromatic Substitution
Electrophilic Aromatic Substitution – The First Meeting
Imagine you have a benzene ring — that perfect, flat hexagon of six carbons with alternating double bonds. It's stable, almost stubbornly so. You want to attach something new to it, say a bromine atom or a nitro group. But benzene doesn't react like an alkene. It doesn't just add across a double bond. Instead, it does something more elegant: it kicks out a hydrogen and keeps its aromatic ring intact.
That's the heart of Electrophilic Aromatic Substitution (EAS).
The Intuition: Why "Substitution" and Not "Addition"?
Benzene's stability comes from its delocalised π electrons — a cloud above and below the ring. This cloud is electron-rich, so it attracts electrophiles (electron-loving species). But if an electrophile simply added to a double bond, the ring would break its aromaticity, losing that huge stabilisation. That would be energetically costly.
So benzene does something smarter: it lets the electrophile attack, temporarily breaks aromaticity to form a high-energy intermediate (the arenium ion), and then loses a proton to restore the aromatic ring. The net result? A hydrogen is replaced by the electrophile. The ring is back to its stable, aromatic self.
The key trade-off: temporary loss of aromaticity is acceptable because the final product regains it. Addition reactions would permanently destroy aromaticity — benzene avoids that.
The Precise Statement
Electrophilic Aromatic Substitution is a reaction in which an electrophile (E+) replaces a hydrogen atom on an aromatic ring, proceeding through a sigma complex (arenium ion) intermediate, and restoring aromaticity after deprotonation.
The general equation:
Ar−H+EX+Ar−E+HX+
where Ar represents an aromatic ring.
The Mechanism in Three Steps
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Generation of the electrophile – Many EAS reactions need a catalyst to create a strong enough E+. For example, bromination uses FeBrX3 to polarise BrX2 into BrX+.
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Attack by the aromatic ring – The π electrons of benzene attack the electrophile, forming a sigma complex (also called the arenium ion or Wheland intermediate). This intermediate is non-aromatic — it has four π electrons delocalised over five carbons, and one sp3 carbon bearing the electrophile and a hydrogen.
Benzene+E+⟶Sigma complex (non-aromatic)
- Deprotonation – A base (often the counterion of the catalyst, like FeBrX4X−) removes the proton from the sp3 carbon. The pair of electrons from the C–H bond flows back into the ring, restoring the aromatic sextet.
Sigma complex+Base⟶Product+HX+
The sigma complex is not aromatic. It's a high-energy intermediate. Students often mistakenly think it's still aromatic — it isn't. That's why the step is fast and the complex is short-lived.
Why This Matters for Exams
EAS is the gateway to understanding how to put groups onto benzene rings. The rate-determining step is usually the formation of the sigma complex (step 2). The regiochemistry (where the electrophile goes) depends on whether the ring already has a substituent — that's the topic of activating/deactivating groups and ortho/para vs. meta directors.
But for now, remember this: …
Why this formula?
Electrophilic Aromatic Substitution: Why the Mechanism Holds
The Core Puzzle: Why Benzene Doesn't Just Add
Benzene (C6H6) has three double bonds — so why doesn't it undergo addition reactions like alkenes?
The answer lies in aromatic stabilisation: benzene's delocalised π-electron cloud (the "aromatic sextet") is about 150 kJ/mol more stable than a hypothetical cyclohexatriene with localised double bonds.
If benzene simply added an electrophile (like Br2), it would lose this stabilisation — a huge energy penalty.
So, nature chooses a different path: substitution instead of addition, preserving the aromatic ring.
The Key Formula: The Reaction Profile
The rate-determining step in electrophilic aromatic substitution (EAS) is the formation of the arenium ion (σ-complex):
Ar-H+E+slowAr-E+H(σ-complex)
Then, fast deprotonation restores aromaticity:
Ar-E+H+B−fastAr-E+BH
Why This Holds: The Energy Barrier Logic
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First step (slow): The electrophile E+ attacks the electron-rich ring. The σ-complex is non-aromatic — it has only 4 π-electrons delocalised over 5 carbons (the sixth carbon is sp3 hybridised). This intermediate is higher in energy than the starting benzene.
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Second step (fast): A base removes the proton, restoring the aromatic sextet. This step is strongly exothermic — the system regains ~150 kJ/mol of stabilisation.
The overall reaction is exothermic, but the activation energy is dominated by the destabilisation of the σ-complex.
The Rate Law: Why It's First Order in Both
From the mechanism:
Rate=k[Arene][E+]
Reasoning:
- The slow step involves one molecule of arene and one molecule of electrophile.
- No other species appear before the rate-determining step.
- Therefore, the rate law is bimolecular — first order in each reactant.
This is not derived from the overall stoichiometry — it comes directly from the molecularity of the slow step.
The Hammett Equation: Quantifying Substituent Effects
For substituted benzenes, the rate constant k relative to benzene (k0) follows:
logk0k=σρ
Why This Holds
- σ (sigma constant): Measures the electronic effect of a substituent (electron-donating or withdrawing) relative to hydrogen. It is derived from the ionisation constants of benzoic acids — a purely empirical scale.
- ρ (rho constant): Measures the sensitivity of the reaction to substituent effects. A positive ρ means the reaction is favoured by electron-withdrawing groups (rare in EAS); a negative ρ means electron-donating groups accelerate the reaction.
Why it works:
The σ-complex has a positive charge delocalised over the ring. Substituents that stabilise this positive charge (electron-donating groups like −OH, −NH2) lower the activation energy — hence σ is negative for such groups. Electron-withdrawing groups (−NO2, −CN) destabilise the σ-complex — σ is positive.
The linear free-energy relationship holds because the transition state resembles the σ-complex in charge distribution.
The Directing Effect: Why Ortho/Para vs Meta
The position of substitution is governed by the stability of the σ-complex for each possible attack site. …
The key idea is Electrophilic Aromatic Substitution — specifically, the reduction of the nitro group (−NO2) to an amino group (−NH2) on the benzene ring.
Reasoning steps:
- Nitrobenzene is reduced to aniline by catalytic hydrogenation (H2-Pd) or by chemical reduction using a metal and acid (Sn/HCl or Fe/HCl). …
Nitrobenzene is reduced to aniline by Sn/HCl, Fe/HCl, and H₂-Pd — all three are standard reducing systems. Sn/NH₄OH does not work because the medium is not acidic enough to complete the reduction.
The question is about the reduction of the nitro group (−NO2) to the amino group (−NH2) in an aromatic ring. This is a classic transformation in organic chemistry, and the key point is that the reduction requires a source of active hydrogen atoms, usually generated in situ by a metal-acid combination or by catalytic hydrogenation.
Let’s go through each option.
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Sn/HCl — Tin and hydrochloric acid. This is a classic chemical reduction. Tin reacts with HCl to produce nascent hydrogen ([H]), which reduces the nitro group stepwise: nitrobenzene → nitrosobenzene → phenylhydroxylamine → aniline. The reaction is carried out in acidic medium, and aniline is obtained as the salt (anilinium chloride), which is then neutralized. This works perfectly.
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Fe/HCl — Iron and hydrochloric acid. This is the Béchamp reduction, historically the most common industrial method. Iron also generates nascent hydrogen with HCl. The mechanism is similar, and it cleanly gives aniline. This works.
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H2-Pd — Catalytic hydrogenation using palladium on carbon. Molecular hydrogen in the presence of a metal catalyst (Pd, Pt, Ni) reduces the nitro group directly to the amino group. This is a heterogeneous catalytic reduction and works efficiently for nitrobenzene to aniline. No acidic medium is required here — the hydrogen adds across the N–O bonds. This works. …
Concept: Reduction of Nitrobenzene to Aniline
Nitrobenzene (C6H5NO2) can be reduced to aniline (C6H5NH2) using different reducing agents. The key is to identify which reagents provide active hydrogen in acidic or neutral medium to reduce the nitro group (−NO2) to an amino group (−NH2).
Method: Reagent-Specific Reduction Analysis
Steps:
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Identify the functional group change
Nitrobenzene → Aniline: −NO2 is reduced to −NH2 (6-electron reduction).
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Check each reagent’s reducing capability
- Sn/HCl → Strong acidic reducing agent. Sn + HCl produces nascent hydrogen ([H]) which reduces −NO2 to −NH2. ✓ Works
- Fe/HCl → Same mechanism as Sn/HCl. Fe + HCl gives [H] for reduction. ✓ Works
- H2-Pd → Catalytic hydrogenation. H2 gas with Pd catalyst reduces −NO2 to −NH2. …
Common Mistakes Students Make on This Question
This question tests your understanding of reduction of nitrobenzene to aniline — a classic reaction in organic chemistry. The key is knowing which reducing agents work and which give different products.
✗ Mistake 1: Assuming all reducing agents give aniline
Many students think any reducing agent will convert nitrobenzene (C6H5NO2) to aniline (C6H5NH2). This is not true.
- Correct fact:
- Sn/HCl and Fe/HCl reduce nitrobenzene to aniline.
- H2-Pd also reduces it to aniline (catalytic hydrogenation).
- Sn/NH4OH does not give aniline — it gives azoxybenzene or other intermediates (like phenylhydroxylamine) because the medium is alkaline.
How to avoid:
Memorise the medium dependence:
- Acidic medium (HCl with Sn or Fe) → aniline
- Neutral/alkaline medium (Sn/NH4OH) → different products (azoxy, azo, hydrazo compounds)
✗ Mistake 2: Forgetting that catalytic hydrogenation works
Some students think only metal-acid reductions work, and ignore H2-Pd.
- Correct fact: H2 with Pd/C (or Pt, Ni) reduces nitrobenzene to aniline cleanly.
How to avoid:
Remember: Catalytic hydrogenation is a standard method for reducing nitro groups to amines. Include it in your list of valid reagents.
✗ Mistake 3: Confusing Sn/NH4OH with Sn/HCl
Students often misread or misremember the reagent — Sn/NH4OH looks similar to Sn/HCl but behaves very differently.
- Correct fact: Sn/NH4OH is alkaline → gives azoxybenzene (not aniline). Sn/HCl is acidic → gives aniline.
How to avoid: …
- GSEB Higher Secondary Certificate (HSC) Examination 2026Set ANNUAL1 markMCQQ.[benzene ring]-NH2 --HNO3/H2SO4, 288K--> ____ is a major product.(a) para-Nitroaniline (NH2, NO2 para)(b) ortho-Nitroaniline (NH2, NO2 ortho)(c) meta-Nitroaniline (NH2, NO2 meta)(d) 1,3-Dinitrobenzene (two NO2 groups meta, no NH2 shown)
›Reveal solutionSolution
Nitrating aniline with HNO3/H2SO4 partly protonates the -NH2 to -NH3+ (a meta director), so the reaction gives a mixture of ortho, meta, and para nitroanilines; the major SINGLE product is still para-nitroaniline.
Aniline's –NH2 group is normally a strong ortho/para director. But in the strongly acidic HNO3/H2SO4 medium, a large fraction of aniline is protonated to the anilinium ion (–NH3+), which is a deactivating, META-directing group. So nitration of aniline actually gives a MIXTURE of all three isomers (ortho, meta, and para nitroaniline) — unusual for an activating substituent, and a well-known exception highlighted in NCERT.
…
- GSEB Higher Secondary Certificate (HSC) Examination 2023Set ANNUAL1 markMCQQ.Which reagent is used to distinguish aniline and benzylamine?(a) Br2/H2O(b) C6H5SO2Cl(c) CHCl3 + KOH(d) CH3COCl/pyridine
›Reveal solutionSolution
Bromine water gives a white ppt (2,4,6-tribromoaniline) with aniline but not with benzylamine.
In aniline (C6H5NH2), the -NH2 is directly on the ring and strongly activates it, so aniline reacts instantly with bromine water to give a white precipitate of 2,4,6-tribromoaniline:
C6H5NH2 + 3 Br2 -> 2,4,6-Br3C6H2NH2 (white ppt) + 3 HBr. …
- GSEB Higher Secondary Certificate (HSC) Examination 2022Set ANNUAL1 markMCQQ.Aniline + HNO3/H2SO4 at 288 K -> In this reaction, which product is obtained in greater proportion?(a) o-nitroaniline(b) m-nitroaniline(c) p-nitroaniline(d) a dinitrobenzene (no -NH2 group)
›Reveal solutionSolution
Nitration of aniline under strongly acidic conditions is complicated because much of the aniline is protonated to the anilinium ion, but the overall product mixture is still dominated by ortho and, most of all, para substitution.
In concentrated H2SO4, most aniline exists as the anilinium ion (C6H5NH3+), which is weakly meta-directing/deactivating; however, a small fraction of free -NH2 (a powerful ortho/para director) still directs nitration, and because the -NH2 group is a much stronger activator than the deactivated anilinium ring, the observed product distribut …
- GUJCET 2021Set 151 markMCQQ.Which product is obtained by nitration of aniline? (A) o-nitroaniline (B) m-nitroaniline (C) p-nitroaniline (D) All above
›Reveal solutionSolution
Protonation of aniline in acid makes the ring less selective → o, m and p nitroanilines all form.
Concept: −NH2 is normally o/p-directing, but in strong acid aniline becomes anilinium (−NH3+), a deactivating m-director. The competition between the free amine and its cation gives a mixture: substantial para (~51%), signif …
- GSEB Higher Secondary Certificate (HSC) Examination 2020Set ANNUAL1 markMCQQ.Phenol --(X, 273K)--> parabromophenol In the above reaction reagent 'X' is ______(a) Bromine water(b) Br2/FeBr3(c) Br2/CH3COOH(d) Br2/CS2
›Reveal solutionSolution
Phenol is so strongly activated toward electrophilic substitution that even mild bromine (dissolved in a non-polar solvent, at low temperature) brominates it; using a non-polar solvent at low temperature favours controlled monosubstitution at the less hindered para position.
Phenol reacts readily with molecular bromine even without a Lewis acid catalyst (unlike benzene) because the ring is strongly activated by the -OH group. With aqueous bromine (bromine water), the reaction proceeds all the way to 2,4,6-tribromophenol (an instant white precipitate, used as a qualitative test for phenol). To obtain a controlled MONO-bromination product, phenol is instead treated with Br2 dissol …
- GSEB Higher Secondary Certificate (HSC) Examination 2018Set ANNUAL1 markMCQQ.Give the correct order of proportion of products obtained by nitration of aniline.(a) o-nitroaniline > p-nitroaniline > m-nitroaniline(b) m-nitroaniline > o-nitroaniline > p-nitroaniline(c) m-nitroaniline > p-nitroaniline > o-nitroaniline(d) p-nitroaniline > m-nitroaniline > o-nitroaniline
›Reveal solutionSolution
Nitration of aniline gives para (about 51%) > meta (about 47%) > ortho (about 2%).
The -NH2 group is strongly ortho/para directing. But nitration is done in a strongly acidic medium (HNO3/H2SO4), where aniline is largely protonated to the anilinium ion (C6H5NH3+). The -NH3+ group is deactivating and meta-directing.
…
- GUJCET 2015Set C1 markMCQQ.Which reagent is used for bromination of methyl phenyl ether? (A) Br2 / CH3COOH (B) Br2 / Red P (C) Br2 / FeBr3 (D) HBr / Δ
›Reveal solutionSolution
[!TLDR]
Anisole's ring is activated by –OCH3, so plain Br2 in acetic acid brominates it (no FeBr3 needed) — option (A).
Concept
The methoxy group is an electron-donating, ortho/para-directing activator. It raises the ring's electron density enough that electrophilic bromination occurs readily with molecular bromine; a Lewis-acid catalyst (needed for deactivated/benzene rings) is unnecessary and would only be used for less reactive arenes.
Solution
- (A) Br2/CH3COOH — acetic acid is a suitable polar solvent; the activated ring brominates directly to give mainly p-bromoanisole. Correct. …
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