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Analysis of Ammonium Oxalate ((NH₄)₂C₂O₄)

Class 12 Chemistry Practical

Aim

To analyse the given inorganic salt for one acidic and one basic radical.

Preliminary Test

ExperimentObservationInference
Physical examinationWhite solid; ammoniacal smellAmmonium salt
SolubilitySoluble in waterAmmonium oxalate is soluble
Dry heatingNH₃ evolved; residue may char slightly; CO / CO₂ on stronger heating with acid laterAmmonium + oxalate
Dilute H₂SO₄No brisk CO₂ like carbonateNot carbonate
Conc. H₂SO₄CO + CO₂; CO burns with a blue flameOxalate indicated
Flame testNo characteristic colourNot Ba / Ca / Sr

Test of Anion (C₂O₄²⁻)

ExperimentObservationInference
Heat the salt with conc. H₂SO₄Colourless gases (CO + CO₂); CO burns with a blue flame at the mouthC₂O₄²⁻ may be present
Confirmatory Tests
Calcium chloride
Acidify the extract with acetic acid and add CaCl₂
White ppt of calcium oxalate, insoluble in acetic acid, soluble in HClC₂O₄²⁻ is confirmed
KMnO₄
To the oxalate ppt add dilute H₂SO₄ and warm with dilute KMnO₄
Pink colour of KMnO₄ is dischargedC₂O₄²⁻ is confirmed

Ionic equations

  • C₂O₄²⁻ + 2H⁺ + conc. H₂SO₄ → CO ↑ + CO₂ ↑ + H₂O
  • Ca²⁺ + C₂O₄²⁻ → CaC₂O₄ ↓
  • 2MnO₄⁻ + 5C₂O₄²⁻ + 16H⁺ → 2Mn²⁺ + 10CO₂ + 8H₂O

Test of Cation (NH₄⁺)

ExperimentObservationInference
Heat the salt with NaOH solutionAmmoniacal smell; gas turns red litmus blueNH₄⁺ may be present (Group 0)
Bring a glass rod dipped in conc. HCl near the mouth of the tubeDense white fumes of NH₄ClNH₄⁺ may be present
Confirmatory Test
Nessler’s reagent
Pass the gas into Nessler’s reagent (K₂[HgI₄] in KOH)
Brown colouration or brown ppt of basic mercury(II) amidoiodideNH₄⁺ is confirmed. Stop cation analysis here for ammonium salts.

Ionic equations

  • NH₄⁺ + OH⁻ → NH₃ ↑ + H₂O
  • NH₃ + HCl → NH₄Cl (white fumes)
  • 2K₂[HgI₄] + 3KOH + NH₃ → H₂N–Hg–O–Hg–I ↓ + 7KI + 2H₂O

Result

The given salt contains NH₄⁺ as the cation (basic radical) and C₂O₄²⁻ as the anion (acidic radical). The salt is Ammonium Oxalate ((NH₄)₂C₂O₄).

Precautions

  1. Use small quantities of salt and reagents; do not use excess.
  2. Keep the mouth of the test tube away from the face while heating.
  3. Use freshly prepared FeSO₄ for the brown ring test.
  4. Nessler’s reagent is toxic (mercury); handle with care and do not pipette by mouth.

Viva voce

  1. Why blue flame at the mouth with conc. H₂SO₄?

    CO burns with a blue flame; CO₂ does not burn.

  2. Why CaCl₂ in acetic acid?

    Calcium oxalate is insoluble in acetic acid; calcium phosphate / carbonate would not survive acetic acid the same way.

  3. Why warm KMnO₄?

    The redox reaction is slow in the cold; it is autocatalysed by Mn²⁺ on warming.

  4. Why Nessler?

    Ammonium cation.

  5. Why not lime water as the main anion test?

    CO₂ from oxalate + conc. H₂SO₄ is mixed with CO; dilute acid does not give brisk carbonate-like CO₂.

  6. Why Group 0 first?

    Always, for any ammonium salt.

  7. Difference from ammonium carbonate?

    Carbonate: dilute acid, lime water. Oxalate: conc. H₂SO₄, CaCl₂, KMnO₄.

  8. Why is the salt used as a Group V reagent?

    (NH₄)₂C₂O₄ ppts Ca²⁺ as oxalate. Here it is the unknown itself.