MCQEasyJEE 2024Qualitative Analysis (N, S, Halogens)

JEE Chemistry 2024 Question with Solution

The Lassaigne’s extract is boiled with dilute HNO3\text{HNO}_3 before testing for halogens because:

  • A

    AgCN is soluble in HNO3\text{HNO}_3

  • B

    Silver halides are soluble in HNO3\text{HNO}_3

  • C

    Ag2S\text{Ag}_2\text{S} is soluble in HNO3\text{HNO}_3

  • D

    Na2S\text{Na}_2\text{S} and NaCN\text{NaCN} are decomposed by HNO3\text{HNO}_3

Answer

Correct answer:D

Step-by-step solution

Standard Method

Given: The Lassaigne's extract is boiled with dilute HNO3\text{HNO}_3 before testing for halogens.

Find: The reason for this boiling step.

The Lassaigne's extract may contain sodium halides along with interfering species such as Na2S\text{Na}_2\text{S} and NaCN\text{NaCN} formed during sodium fusion.

These ions interfere with the halogen test because they can react with AgNO3\text{AgNO}_3 and give precipitates that may be confused with silver halides.

Boiling with dilute nitric acid decomposes these interfering compounds:

Na2S+2HNO32NaNO3+H2O+S\text{Na}_2\text{S}+2\text{HNO}_3\rightarrow2\text{NaNO}_3+\text{H}_2\text{O}+\text{S} NaCN+HNO3NaNO3+HCN\text{NaCN}+\text{HNO}_3\rightarrow\text{NaNO}_3+\text{HCN}

After removal of S2\text{S}^{2-} and CN\text{CN}^- ions, the extract can be safely treated with AgNO3\text{AgNO}_3 to test for halides.

Therefore, the correct option is D, because Na2S\text{Na}_2\text{S} and NaCN\text{NaCN} are decomposed by dilute HNO3\text{HNO}_3.

Why Dilute Nitric Acid Is Used

Given: Lassaigne's test is used to detect halogens, nitrogen, and sulfur in an organic compound.

Find: Why the extract is boiled with dilute HNO3\text{HNO}_3 before adding AgNO3\text{AgNO}_3.

During sodium fusion, the extract can contain sodium halides, sodium sulfide, and sodium cyanide.

If Na2S\text{Na}_2\text{S} and NaCN\text{NaCN} are not removed, they interfere in the silver nitrate test by producing species such as silver sulfide or silver cyanide, which may lead to false identification.

Dilute HNO3\text{HNO}_3 removes these interfering ions by decomposition before the actual halogen test is performed.

Thus, the boiling step is not to dissolve silver halides, but to destroy interfering Na2S\text{Na}_2\text{S} and NaCN\text{NaCN}.

Hence, the correct option is D.

Common mistakes

  • Thinking dilute HNO3\text{HNO}_3 is added to dissolve silver halides. This is wrong because silver halides are identified as precipitates in the test. Instead, the acid is used first to remove interfering S2\text{S}^{2-} and CN\text{CN}^- species.

  • Assuming AgCN\text{AgCN} or sulfide formation is the main purpose of the acid step itself. This is incomplete because those silver salts form only after adding AgNO3\text{AgNO}_3. The correct idea is that dilute HNO3\text{HNO}_3 decomposes NaCN\text{NaCN} and Na2S\text{Na}_2\text{S} beforehand.

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