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UPSC Combined Geo-Scientist

Chemist

  • 3 descriptive papers
  • 200 marks each
  • 3 h per paper

Mains Paper III covers analytical and organic chemistry.

UPSC Combined Geo-Scientist, Mains · 2022 · Mains Paper III

Q1(d). Cold-vapour atomisation for mercury

Question

Describe the atomization method for determining mercury at parts per billion level concentrations by AAS.

Answer in brief

Cold-vapour technique: Hg²⁺ is reduced to Hg⁰ by SnCl₂, swept by a gas stream into a quartz-windowed cell at room temperature, and its absorbance at 253.7 nm is measured.

Key points

  • Mercury is the only metal with an appreciable pressure of monatomic vapour at room temperature, so no flame or furnace is needed.
  • Sample is digested with HNO₃–H₂SO₄ and KMnO₄ to oxidise organo-mercury to Hg²⁺; excess oxidant is destroyed with hydroxylamine hydrochloride.
  • Reduction with SnCl₂ in acid: Hg²⁺ + Sn²⁺ → Hg⁰ + Sn⁴⁺; NaBH₄ reduces organically bound Hg as well.
  • Ar, N₂ or air sweeps Hg vapour through a drying tube into a long-path quartz-windowed cell; absorbance of the 253.7 nm line is measured.
  • Detection limit about 1 ng; matrix isolation, as the analyte leaves the matrix as vapour.

The full model answer

As written for the answer booklet: the diagram carries the working, the lines stay short. Read here only; it is not offered as a download.

Model answer to Q1(d), 2022 Mains Paper III: solution pages 5 and 6
Solution pages 5 and 6 of 38

Coverscold vapour AASmercury determinationSnCl₂ reduction253.7 nmatomic absorption