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.

Coverscold vapour AASmercury determinationSnCl₂ reduction253.7 nmatomic absorption
All parts of Question 1
- 1(a) Accuracy and precision5 marks
- 1(b) Phases in GLC and choice of carrier gas5 marks
- 1(c) Matching techniques with sources and detectors5 marks
- 1(d) Cold-vapour atomisation for mercury5 marks
- 1(e) Components of a thermogravimetric analyser5 marks
- 1(f) X-rays from radioactive isotopes5 marks
- 1(g) Generation of the argon plasma in ICP–MS5 marks
- 1(h) Manganese in pyrolusite by redox back-titration5 marks