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Worked Examples · Example 7.4

Q.Arrange the following compounds in increasing order of their acid strength:
Propan-1-ol, 2,4,6-trinitrophenol, 3-nitrophenol, 3,5-dinitrophenol, phenol, 4-methylphenol.

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Acid strength depends on the stability of the conjugate base after losing H⁺. For phenols, electron-withdrawing groups (like –NO₂) stabilize the phenoxide ion and increase acidity; electron-donating groups (like –CH₃) destabilize it and decrease acidity. Alcohols are far weaker acids than phenols. The increasing order is: Propan-1‑ol < 4‑methylphenol < phenol < 3‑nitrophenol < 3,5‑dinitrophenol < 2,4,6‑trinitrophenol.


Why this approach works

Acid strength is all about the stability of the conjugate base. When a compound loses a proton (H⁺), the remaining anion must be able to spread out (delocalise) the negative charge. The better it does this, the weaker the O–H bond becomes and the stronger the acid.

For phenols, the phenoxide ion can delocalise the negative charge into the aromatic ring via resonance. This makes phenols far more acidic than alcohols (where the alkoxide ion has no such resonance). Now, substituents on the ring either pull electron density away (electron-withdrawing groups, EWGs) or push electron density in (electron-donating groups, EDGs). EWGs stabilise the negative charge further, making the phenol more acidic. EDGs do the opposite — they concentrate the negative charge, making the conjugate base less stable and the phenol less acidic.

The –NO₂ group is a strong EWG (both by inductive and resonance effects). The –CH₃ group is a weak EDG (hyperconjugation/inductive). The more –NO₂ groups, and the closer they are to the –OH, the stronger the acid. 2,4,6‑Trinitrophenol (picric acid) is famously a strong acid — almost as strong as mineral acids — because three –NO₂ groups at the ortho and para positions massively stabilise the phenoxide.

Propan‑1‑ol is a simple alcohol. Its conjugate base (propan‑1‑oxide) has no resonance stabilisation at all, so it is the weakest acid here by a huge margin.


Step-by-step reasoning

  1. Identify the weakest acid

    Propan‑1‑ol is an aliphatic alcohol. The alkoxide ion’s negative charge is localised on oxygen — no resonance, no delocalisation. Phenols, even unsubstituted ones, are about 10610^6 times more acidic than alcohols. So propan‑1‑ol is the weakest.

  2. Order the phenols by substituent effects

    We have five phenols:

    • 4‑methylphenol (one –CH₃ at para)
    • phenol (no substituent)
    • 3‑nitrophenol (one –NO₂ at meta)
    • 3,5‑dinitrophenol (two –NO₂ at meta positions)
    • 2,4,6‑trinitrophenol (three –NO₂ at ortho and para)

    The –CH₃ group is electron-donating. It pushes electron density into the ring, which makes the phenoxide ion less stable (more negative charge concentrated on oxygen). So 4‑methylphenol is a weaker acid than phenol itself.

    Phenol is the reference. Its pKa is about 10.

    The –NO₂ group is strongly electron-withdrawing. It pulls electron density away from the oxygen, stabilising the phenoxide. A single –NO₂ at the meta position (3‑nitrophenol) increases acidity relative to phenol. Two –NO₂ groups (3,5‑dinitrophenol) increase it further. Three –NO₂ groups at the 2, 4, and 6 positions (2,4,6‑trinitrophenol) give the strongest effect — the ortho and para positions allow direct resonance delocalisation of the negative charge into the nitro groups.

    Tip

    The ortho and para positions are directly conjugated with the -OH group via resonance. A -NO2 at ortho or para can accept the negative charge onto its own oxygen atoms. A -NO2 at meta cannot do this -- it only works by inductive effect. That is why 2,4,6-trinitrophenol (three nitro groups, all ortho/para to the -OH) is so much stronger an acid than 3,5-dinitrophenol (only two nitro groups, both meta): ortho/para placement is far more powerful than meta, so both the extra nitro group and its favourable position push the acidity up.

  3. Arrange in increasing order

    From weakest to strongest acid:

    • Propan‑1‑ol (pKa ~16)
    • 4‑methylphenol (pKa ~10.2)
    • Phenol (pKa ~10.0)
    • 3‑nitrophenol (pKa ~8.4)
    • 3,5‑dinitrophenol (pKa ~6.7)
    • 2,4,6‑trinitrophenol (pKa ~0.4)
    Watch out

    A common mistake is to think that more nitro groups always means proportionally stronger acid. While true in trend, the position matters enormously. 2,4,6‑trinitrophenol is over a million times more acidic than 3,5‑dinitrophenol because of resonance stabilisation from the ortho and para nitro groups. Don’t just count groups — check where they are.


✓Final answer

The increasing order of acid strength is: Propan‑1‑ol < 4‑methylphenol < phenol < 3‑nitrophenol < 3,5‑dinitrophenol < 2,4,6‑trinitrophenol.

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