HomeChemistryQ
ChemistryQualitative Analysis
In a test tube containing a salt, a few drops of dilute H₂SO₄ was added, which gave colourless vapours having the smell of vinegar. The vapours turned the blue litmus paper red. Identify the correct anion from the following :
Options
1
Acetate, CH₃COO⁻
2
Carbonate, CO₃²⁻
3
Sulphate, SO₄²⁻
4
Sulphide, S²⁻
Correct Answer
Option 1 : Acetate, CH₃COO⁻
Step-by-Step Solution
1

Reaction of acetate salt with dil. H₂SO₄:

2CH₃COO⁻ + H₂SO₄ → 2CH₃COOH + SO₄²⁻

Acetic acid (CH₃COOH) is liberated — volatile liquid (bp 118°C)

2

Why the clues match:

✅ Colourless vapour — CH₃COOH vapour is colourless

✅ Smell of vinegar — vinegar IS dilute acetic acid! The characteristic pungent sour smell

✅ Turns blue litmus red — CH₃COOH is acidic (weak acid, but still acid)

3

Why other options are wrong:

CO₃²⁻: gives CO₂ (odourless gas, turns lime water milky — not vinegar smell)

SO₄²⁻: gives H₂SO₄ (no distinctive smell + not volatile from dilute H₂SO₄)

S²⁻: gives H₂S (rotten egg smell — NOT vinegar smell)

CH₃COO⁻ + H⁺ → CH₃COOH (acetic acid)

Acetic acid = vinegar smell + colourless + acidic (turns litmus red)

Answer: Acetate anion (CH₃COO⁻)

Theory: Qualitative Analysis of Anions
1. Identification of Anions Using Dilute H₂SO₄

Adding dilute H₂SO₄ to a salt liberates the corresponding acid, which can be identified by its properties. This is used in the preliminary tests for anion identification. The reactions are essentially double displacement/acid-base reactions where a stronger acid (H₂SO₄) displaces weaker acids from their salts. The gas or vapour evolved has characteristic properties that help identify the anion.

2. Gas Evolved with Dilute H₂SO₄ — Key Tests

📌 Acetate (CH₃COO⁻): Vinegar smell (acetic acid vapours), colourless, acidic. Brown ring test also positive.

📌 Carbonate (CO₃²⁻): Brisk effervescence of CO₂, odourless, turns lime water milky (Ca(OH)₂ + CO₂ → CaCO₃↓), turns moist red litmus blue then white (acidic then bleaches)... wait — CO₂ turns moist blue litmus red (acidic). Lime water test is the specific test.

📌 Sulphide (S²⁻): H₂S gas — rotten egg smell, turns lead acetate paper black (PbS). Colourless but distinctly foul-smelling.

📌 Nitrite (NO₂⁻): Brown fumes of NO₂, or colourless NO which turns brown in air.

📌 Sulphite (SO₃²⁻): SO₂ gas — pungent smell (burning matchstick), turns potassium dichromate paper green.

3. Gas Evolved with Concentrated H₂SO₄

📌 Chloride (Cl⁻): HCl gas — pungent, fumes with NH₃, white fumes with NH₃ aq. (NH₄Cl)

📌 Bromide (Br⁻): HBr + Br₂ (brown fumes) — H₂SO₄ oxidises HBr to Br₂

📌 Iodide (I⁻): HI + I₂ (violet vapour) + H₂S + SO₂ (further reduction of H₂SO₄)

📌 Nitrate (NO₃⁻): Brown fumes of NO₂ with conc. H₂SO₄ + copper. Ring test with FeSO₄ (brown ring = iron-NO complex).

📌 Phosphate (PO₄³⁻): Ammonium molybdate test — yellow precipitate (ammonium phosphomolybdate)

4. Acetic Acid — Properties and Uses

Acetic acid (ethanoic acid, CH₃COOH) is a weak organic acid (Ka = 1·8×10⁻⁵). Pure acetic acid is called glacial acetic acid (freezes at 16·6°C). Vinegar is 5–8% aqueous acetic acid. Produced industrially by: (1) Oxidation of ethanol. (2) Carbonylation of methanol (Monsanto/Cativa process). Properties: colourless liquid, pungent characteristic smell, boiling point 118°C, miscible with water. Uses: food preservative, vinegar, synthesis of esters (ethyl acetate — solvent, nail polish remover), synthesis of aspirin (acetylsalicylic acid), manufacture of plastics, pharmaceuticals.

5. Brown Ring Test for Nitrate

Specific test for NO₃⁻: Add freshly prepared FeSO₄ solution to the salt solution. Slowly add conc. H₂SO₄ along the side of the test tube. A brown ring appears at the interface of two layers = presence of NO₃⁻. Reaction: NO₃⁻ + 3Fe²⁺ + 4H⁺ → NO + 3Fe³⁺ + 2H₂O; then NO + FeSO₄ → [Fe(H₂O)₅NO]²⁺ (brown ring complex = pentaaquanitrosyliron(II) complex). Important: NO₂⁻ (nitrite) also gives positive brown ring but the ring disappears on shaking — this distinguishes nitrite from nitrate.

6. Lime Water Test for CO₂

Lime water = Ca(OH)₂ solution. On passing CO₂: Ca(OH)₂ + CO₂ → CaCO₃↓ (white precipitate) + H₂O — turns lime water milky. Excess CO₂: CaCO₃ + CO₂ + H₂O → Ca(HCO₃)₂ (soluble) — milky solution clears again. This dual behaviour (milky then clear) is a unique and confirmatory test for CO₂. Used to distinguish CO₂ from SO₂ — SO₂ also turns lime water milky (CaSO₃↓) but CaSO₃ dissolves in excess SO₂ forming Ca(HSO₃)₂, similar to CO₂.

7. Lassaigne's Sodium Fusion Test

Organic compound is fused with sodium metal to convert covalent elements into ionic salts: N → NaCN, S → Na₂S, halogens → NaX (X=Cl, Br, I). The fused mass is dissolved in water (sodium fusion extract = SFE). Tests on SFE: N: add FeSO₄ + FeCl₃ + dil. HCl → Prussian blue (Fe₄[Fe(CN)₆]₃) confirms N. S: add sodium nitroprusside → purple colour (sodium nitroprusside test) OR lead acetate → black PbS. Cl: add AgNO₃ → white AgCl ppt (soluble in NH₃). Br: add AgNO₃ → pale yellow AgBr ppt (slightly soluble in NH₃). I: add AgNO₃ → yellow AgI ppt (insoluble in NH₃).

8. Confirmatory Test for Acetate Ion

The vinegar smell with dilute H₂SO₄ is a strong indicator. Confirmatory test: Add neutral FeCl₃ solution to acetate salt solution → blood red/reddish brown coloration (ferric acetate complex [Fe(CH₃COO)₃]). On boiling: red colour deepens and brown precipitate forms (basic ferric acetate). This is the standard confirmatory test for acetate in qualitative analysis. Acetate is also confirmed by the ester test: add alcohol + conc. H₂SO₄ and warm → fruity smell (ester formation).

Frequently Asked Questions
1. Why does acetate give vinegar smell but sulphide gives rotten egg smell?
Different acids formed: Acetate + H₂SO₄ → acetic acid (CH₃COOH) — vinegar is dilute acetic acid. The characteristic sour, pungent smell is well-known. Sulphide + H₂SO₄ → hydrogen sulphide (H₂S) — a gas with the distinctive rotten egg smell (extremely foul, even at low concentrations). H₂S is also toxic (similar to HCN in toxicity at high concentrations). Both are colourless — but the smell is completely different and diagnostic.
2. Why does CO₂ not smell like vinegar?
CO₂ is an odourless gas — it has no smell at all. Carbonate + H₂SO₄ → CO₂ + H₂O + SO₄²⁻. CO₂ gives brisk effervescence (bubbles) and turns lime water milky — these are its specific tests. It has no vinegar smell because acetic acid is not formed. CO₂ does turn blue litmus red (it's acidic — dissolves in water to form carbonic acid), so that clue alone is not specific. The vinegar smell is the unique clue pointing to acetate.
3. What is the brown ring test?
Test for nitrate (NO₃⁻): (1) Add freshly prepared FeSO₄ to the salt solution and mix. (2) Slowly pour conc. H₂SO₄ along the walls of the inclined test tube. (3) A brown ring (iron-nitrosyl complex) forms at the interface of two layers. Reaction: 8FeSO₄ + 6H₂SO₄ + 2HNO₃ → 4Fe₂(SO₄)₃ + 2NO + 8H₂O; NO + FeSO₄ → [Fe(NO)]SO₄ (brown ring). The ring disappears on shaking if nitrite is present (confirming it's nitrate).
4. Why is H₂SO₄ used in anion identification tests?
H₂SO₄ is used because: (1) It's a strong acid that can displace weak acids from their salts (stronger acid displaces weaker). (2) Dilute H₂SO₄ gives non-oxidising conditions — only acid-base displacement occurs. Conc. H₂SO₄ can also oxidise some anions (Br⁻, I⁻), giving additional information. (3) H₂SO₄ itself doesn't interfere with most anion tests. (4) Both dilute and concentrated versions are useful for different anion groups.
5. How is the acetate ion confirmed by ferric chloride test?
Add neutral FeCl₃ (ferric chloride) solution to acetate salt solution: 3CH₃COO⁻ + Fe³⁺ → Fe(CH₃COO)₃ (iron(III) acetate — blood red/reddish-brown complex). On boiling: the complex decomposes → brown precipitate of basic ferric acetate forms + further reddening. This blood red colour with FeCl₃ is the confirmatory test for acetate. Other anions that give colour with FeCl₃: phenol (violet), salicylate (purple-violet), formate (yellow), oxalate (yellow-white precipitate).
6. What is the ester test for acetate?
Add ethyl alcohol (C₂H₅OH) + conc. H₂SO₄ to the salt → warm gently. A fruity smell indicates formation of ethyl acetate (ester): CH₃COO⁻ + C₂H₅OH + H⁺ →(H₂SO₄) CH₃COOC₂H₅ + H₂O. Ethyl acetate has a characteristic fruity/pear-like smell. This confirms the acetate ion. Other esters formed from different alcohols also have fruity smells — amyl acetate (banana), isoamyl acetate (banana oil), ethyl formate (rum-like).
7. How is H₂S identified in qualitative analysis?
H₂S has rotten egg smell — unmistakable. Confirmatory tests: (1) Lead acetate paper test: H₂S turns lead acetate paper black (PbS — lead sulphide precipitate). Pb(CH₃COO)₂ + H₂S → PbS↓ (black) + 2CH₃COOH. (2) Sodium nitroprusside test: add Na₂[Fe(CN)₅NO] to sulphide solution → purple/violet colour. (3) Group II precipitation: H₂S passed through acidic solution → sulphides of Cu²⁺, Pb²⁺, Bi³⁺ etc. precipitate as coloured sulphides.
8. What is the difference between acetic acid and glacial acetic acid?
Acetic acid = CH₃COOH. Glacial acetic acid = pure (100%) anhydrous acetic acid. It's called "glacial" because it freezes to ice-like crystals at 16·6°C (room temperature in cold weather). Vinegar = 5–8% acetic acid in water. Glacial acetic acid: density 1·05 g/mL, boiling point 118°C, strongly corrosive to skin. Industrial acetic acid is ~80–90% (for synthesis). Laboratory use: glacial acetic acid + acetic anhydride are used for acetylation reactions, aspirin synthesis (salicylic acid + acetic anhydride → aspirin).
Previous Questions
Q.
Bulb 150W, 8% to light, photon energy 4·42×10⁻¹⁹J — photons per second
Atomic Structure · Answer: 2·71 × 10¹⁹
Q.
Benzene + CH₃Cl (AlCl₃) → toluene; nitration → X + Y; separation
Organic Chemistry · Answer: Fractional distillation
Q.
Ti²⁺ (3d²) — calculated spin-only magnetic moment
d-Block · Answer: 2·84 BM
Q.
Pt|H₂(2atm)|HCl(0·02M) — emf using Nernst equation
Electrochemistry · Answer: 0·109 V
Q.
ClF₃ — geometry and lone pairs on Cl atom
p-Block · Answer: T-shaped, 2 lone pairs