VKC ScienceChemistry for written exams Telegram

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 · 2023 · Mains Paper III

Q1(g). Interference of calcium in the ICP–MS determination of iron

Question

How does high concentration of calcium interfere with ICP-MS analysis of iron?

Answer in brief

Calcium forms polyatomic ions in the plasma with the same nominal mass as the iron isotopes: ⁴⁰Ca¹⁶O⁺ falls on ⁵⁶Fe⁺ (m/z 56), so the iron result is too high; the heavy Ca matrix also suppresses the signal and clogs the cones.

Key points

  • Spectroscopic (polyatomic) interference: Ca combines with O, H and N; the molecular ions have the same nominal m/z as iron isotopes, unresolved by a quadrupole.
  • Overlaps: ⁴⁰Ca¹⁶O⁺ on ⁵⁶Fe⁺, ⁴⁰Ca¹⁶O¹H⁺ on ⁵⁷Fe⁺, ⁴⁰Ca¹⁴N⁺ on ⁵⁴Fe⁺, ⁴²Ca¹⁶O⁺ on ⁵⁸Fe⁺: positive error.
  • Matrix effects: signal suppression by space charge and the easily ionised matrix; CaO deposits on the cones cause downward drift.
  • Remedies: collision/reaction cell (He with KED; H₂ or NH₃), high-resolution instrument (m/Δm about 2500), dilution, matrix-matched standards, internal standard.

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(g), 2023 Mains Paper III: solution pages 7 and 8
Solution pages 7 and 8 of 40

CoversICP-MSpolyatomic interferenceCaO+ on Fe-56collision cellmatrix effect