ARSENIC - HIGH CONCENTRATION

The principal minerals are arsenopyrite (FeAsS), realgar (As2S2) and orpiment (As2S3) and many
arsenides and sulpharsenides of lead, copper, gold and tin.

Determination of arsenic (Volumetry)

Principle of the method

Arsenic is distilled out at 110oC in the presence of cuprous chloride and hydrochloric acid as arsenious
trichloride (AsCl3). The distillate is trapped in water and determined volumetrically by titrating with
standard iodine solution at a specified pH.

Procedure (for sulphide minerals)

Weigh 0.5 to 5 g (according to the anticipated amount) of the finely powdered sample; add 15 ml of
fuming nitric acid and digest over hot plate at low temperature.Add 10 ml 1:1 sulphuric acid and
evaporate to dense fumes.Allow the mass to cool. Add water and transfer the entire mass into a
distillation flask. Wash the beaker thoroughly and pour the washings into the distillation flask. Add 1 gm
of hydrazine sulphate, 0.5 g of cuprous chloride to ensure reduction of arsenic to the trivalent
condition.Add 70-ml. conc. arsenic free hydrochloric acid, and set up the distillationapparatus. The end of
the condenser should be submerged in 50 ml. of water in the collecting beaker. Slowly raise the
temperature and distilled out nearly 100 ml.between 100 and 110oC (at a very slow rate). The collecting
beaker can be graduated to indicate the various volumes of the distillate. Disconnect, wash out the
condenser into the collecting beaker. Transfer the distillate to a 500 ml. beaker for titration.

Cool, add a piece of litmus paper and make it slightly alkaline with 20% NaOH, then re-acidify slightly
with HCl. Cool again. To the cold, slightly acidic solution, add 3-4 g. of NaHCO3 (in excess), and then a
little starch solution. Titrate with standard iodine solution to permanent blue tinge.

Calculate the percentage of the arsenic in the sample using the following

factor:

1 ml. 1N iodine = 0.03746 gm. of As = 0.04946 gm. of As2O3

Reaction involved:

H3AsO3 + I2 + H2O = H3AsO4 + 2HI

Determination of minute amount of Arsenic

(Spectrophotometry heteropoly molybdenum blue method)

Principle
Following the separation of arsenic from matrix elements by distilledlation as the trichloride, the arsenic
(III) is oxidized to the pentavalent state with nitric acid and ammonium molybdate is added to form a
heteropolymolybdioarsenate which is then reduced by a suitable reducing agent to strongly coloured
molybdenum blue and measured at 840 nm.
Reagents
1. Standard arsenic solution Dissolve 0.1320 gm. of Ar arsenic trioxide As2O3 in the minimum volume
of 1 M sodium hydroxide solution, make slightly acidic with hydrochloric acid, make up to 100 ml in a
volumetric flask.
1 ml. = 1 mg. As
A solution containing 0.001 mg. of As per ml. is prepared by dilution.

2. Ammonium molybdate solution 0.1% W/V, - Dissolve 5 gm. of ammonium molybdate (NH4)6 Mo7
O24.4H2O in approximately 200 ml. of 2.5 M sulphuric acid and dilute to 500 ml. with the same solution,
store in a polythene bottle.
3. Ascorbic acid solution, 0.1% W/V prepare fresh solution daily in water.
4. Sulphuric acid 2.5 M Add 130 ml. of conc. sulphuric acid slowly while stirring to approximately 800
ml. of water. Allow the solution to cool to room temperature, transfer to a 1 litre volumetric flask, and
dilute to volume with water.

Procedure
Distill arsenic by the method given under arsenic ore and make up in a volumetric flask, to 250 ml. Take
an aliquot of the distillate, add 10 ml. conc. nitric acid and evaporate to dryness, bake the residue at
130oC for 15 minutes to ensure complete removal of nitric acid. Cool and add 2 ml. ammonium
molybdate, 2 ml. ascorbic acid solution, keep on a steam bath for 30 minutes. Transfer the solution in a
100 ml. volumetric flask and make it up to the volume with water and mix well. Determine the
absorbance of the solution at 840 nm
or with a red filter with maximum transmission above 700 nm. Prepare a standard curve from known
amounts of arsenic treated in the same way as the unknown, carry out reagent blank,and measure the
optical density against this. Compute the percent or arsenic from the standard graph.
Note
1. The acid concentration of the solution must be controlled. If the acidity is too low even molybdate
alone
will give a blue colour and if it is too high the colour due to arsenic is decreased in intensity.
2. Oxalic, tartaric, citric acids, fluorides and oxidizing agents interfere in this method.