why sulphuric acid not used during the reaction of alcohols with ki

Why Sulphuric Acid Is Not Used with KI in Alcohol Reactions: Explained

When it comes to organic chemistry reactions, choosing the right acid can make or break the reaction. A common query among students and enthusiasts is:

“Why don’t we use sulphuric acid (H₂SO₄) when converting alcohols to alkyl iodides using potassium iodide (KI)?”

Let’s break it down step by step.


🔹 The Reaction Context

The reaction we’re talking about is the conversion of alcohols (R–OH) into alkyl iodides (R–I) using KI. The general reaction is:

R–OH+KI+acid→R–I+H2OR–OH + KI + acid → R–I + H_2O

Here, an acid is needed to activate the alcohol, making it more reactive.


🔹 Why Sulphuric Acid Doesn’t Work

Although sulphuric acid is a strong acid, it has a major drawback: it is a strong oxidizing agent.

When you add H₂SO₄ to KI, the iodide ions (I⁻) get oxidized into iodine (I₂) instead of reacting with the alcohol:

2I−+H2SO4→I2+SO2+2H2O2 I^- + H_2SO_4 → I_2 + SO_2 + 2 H_2O

Result:

  • The solution turns brown due to free iodine.

  • KI is destroyed, reducing the amount of iodide available.

  • The alcohol fails to convert into the desired alkyl iodide.

So using sulphuric acid ruins the reaction.


🔹 The Ideal Acid Choice

Instead of sulphuric acid, chemists use phosphoric acid (H₃PO₄) or sometimes hydroiodic acid (HI).

Why phosphoric acid?

  • It is a non-oxidizing acid, so it doesn’t attack iodide ions.

  • It effectively protonates the alcohol, forming a better leaving group (R–OH₂⁺).

  • This ensures a smooth reaction to form the alkyl iodide.

Reaction with phosphoric acid:

R–OH+KI+H3PO4→R–I+H2OR–OH + KI + H_3PO_4 → R–I + H_2O


🔹 Quick Comparison Table

Acid Used Effect on KI Result
H₂SO₄ Oxidizes I⁻ → I₂ Alkyl iodide not formed
H₃PO₄ Non-oxidizing Smooth formation of R–I
HCl Weak acid Less effective
HI Provides I⁻ directly Ideal, high yield

🔹 Conclusion

Sulphuric acid is avoided in the conversion of alcohols to alkyl iodides using KI because it oxidizes iodide ions, stopping the reaction. Phosphoric acid or HI are preferred, ensuring a high-yield formation of the desired product.

Key takeaway: Always consider both acidity and oxidizing properties when choosing an acid for substitution reactions.

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