STEP-1

In acidic medium, arsenic impurity present in the test sample is converted to arsenious acid
or arsenic acid depending upon valence state of arsenic
As3+ ------------> As(OH)3 or H3AsO3 (Arsenious acid)
Trivalent
As5+ ------------> O=As(OH)3 or H3AsO4 (Arsenic acid)
Pentavalent
STEP -2
Potassium iodide is converted to hydriodic acid in presence hydrochloric acid which
reduce unreacted pentavalent arsenic to trivalent arsenic. This ensure reproducible
results. If it is not used then some pentavalent arsenic remains unreacted.

HI
As5+ ------------> As3+
STEP-3
This solution is then reacted with reducing agent like stannous chloride to converts
pentavalent arsenic acid into the trivalent arsenious acid.

SnCl2
O=As(OH)3 ----------------> As(OH)3
STEP-4
The presences of small quantity of stannous chloride in the hydrochloric acid ensure
the rapid reaction between the acid and the zinc and steady evolution of hydrogen gas.
Zn+2 + 2 SnHCI3 ZnCl2 + 2 SnCl2 + 2 [H]
STEP-5
The arsenious acid is then converted into gaseous arsenious hydride (Arsine gas) with
the help of nascent hydrogen (which is produced by zinc and hydrochloric acid).
H3AsO3 + 6H AsH3 + 3H2O
Arsenious acid Nascent hydrogen Arsine gas

STEP-6
Arsine gas is carried through the tube by the steam of hydrogen and out through the
mercuric chloride paper. A reaction occurs between arsine and mercuric chloride,
which produces yellow color stain,
AsH2
2AsH3 + HgCl2 Hg + 2HCl
Arsine gas Mercuric AsH2
Chloride Paper Mercuric Hydrogen Arsenide
(Yellow /Brown in Colour)

‘ The yellow stain produced by test sample compared with that of standard arsenic
solution.
STEP-7
Zinc contains sulphide as impurities. These sulphide gives black stain to mercuric
chloride paper and thus can interfere in the test. Hence, gases evolved are passed
through cotton wool plug moistened with lead acetate.
Sulphide impurities gets converted to hydrogen sulphide gas which are then trapped
by this lead acetate as lead sulphide.
H2S + Pb(CH3COO)2 -----------------> PbS