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Limit Tests

A limit test in chemistry is a qualitative or semi-quantitative analysis used to check whether the amount of a
specific impurity in a substance is within the maximum allowable limit. It is mainly applied in pharmaceuticals,
environmental monitoring, and chemical quality control to ensure that products are safe and free from harmful
impurities.
Key Features of Limit Test:

Examples of Limit Tests:

1. Limit Test for Chloride
2. Limit Test for Sulphate
3. Limit Test for Iron
4. Limit test for Lead
5. Limit test for Arsenic
6. Limit test for Heavy Metals
LIMIT TEST OF CHLORIDE
Principle:
The limit test for chloride is based on the reaction of soluble chlorides with silver nitrate in the presence of
dilute nitric acid, forming silver chloride (AgCl) as a white opalescent (turbid) precipitate. The intensity of this
opalescence is compared with a standard to determine whether the chloride content is within the prescribed limit.
Cl – + AgNO3 ⎯⎯⎯⎯
dil. HNO3
→ AgCl  + NO3−
(Soluble) (Insoluble)

Reagents Required for Limit Test of Chloride:

● Dilute HNO₃: Maintains acidic medium, prevents interference from other anions.
● AgNO₃(0.1% w/v): Reacts with chloride ions to form AgCl precipitate.
● Standard NaCl Solution: Provides a known chloride concentration for comparison.
● Test Solution: Sample under examination for chloride impurity.

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PROCEDURE:

Test Sample Standard Compound (25 ppm Cl⁻)

Dissolve the specified quantity of the compound in Take 1 ml of the standard chloride solution in a Nessler
water (or prepare the solution as directed in the cylinder.
pharmacopoeia) and transfer it to a Nessler cylinder.
Add 10 ml of dilute nitric acid. Add 10 ml of dilute nitric acid.
Dilute the solution to 50 ml with water in the Nessler Dilute the solution to 50 ml with water in the Nessler
cylinder. cylinder.
Add 1 ml of silver nitrate (AgNO₃) solution. Add 1 ml of silver nitrate (AgNO₃) solution.
Allow the solutions to stand for 5 minutes. Allow the solutions to stand for 5 minutes.
Observe the degree of opalescence or turbidity Observe the degree of opalescence or turbidity
produced. produced.
Standard chloride solution: 5 ml of 0.0824 % W/V solution of sodium chloride in 100 ml of water.
Observation: The opalescence produced in the sample solution should not be greater than the standard
solution. If the opalescence produced in the sample solution is less than the standard solution, the sample will
pass the limit test of chloride and vice versa.
Reasons: Nitric acid is added in the limit test of chloride to make the solution acidic and help silver chloride
precipitate to make the solution turbid at the end of the process
LIMIT TEST OF SULFATE
The limit test of sulfate is based on the reaction of soluble sulfate with barium chloride in the presence of dilute
hydrochloric acid to form barium sulfate, which appears as solid particles (turbidity) in the solution.
The reaction involved is:
SO24− + BaCl2 → BaSO4 (white precipitate) + 2Cl−
PROCEDURE:
Test Sample Standard Compound
Dissolve the specified quantity of the compound in Take 1 ml of 0.1089% w/v solution of potassium sulfate
water (or prepare the solution as directed in the in a Nessler cylinder.
pharmacopoeia) and transfer it to a Nessler cylinder.
Add 2 ml of dilute hydrochloric acid. Add 2 ml of dilute hydrochloric acid.
Dilute the solution to 45 ml with water in the Nessler Dilute the solution to 45 ml with water in the Nessler
cylinder. cylinder.
Add 5 ml of barium sulfate reagent. Add 5 ml of barium sulfate reagent.
Allow the solutions to stand for 5 minutes. Allow the solutions to stand for 5 minutes.
Observe the turbidity produced. Observe the turbidity
Barium sulfate reagent contains barium chloride, sulfate-free alcohol, and a small amount of potassium sulfate.
Preparation of ethanolic sulfate standard solution (10 ppm SO₄²⁻): Dilute 1 volume of a 0.181% w/v solution of
potassium sulfate in ethanol (30%) to 100 volumes with ethanol (30%).
Preparation of sulfate standard solution (10 ppm SO₄²⁻) : Dilute 1 volume of a 0.181% w/v solution of potassium
sulfate in distilled water to 100 volumes with distilled water.

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Observations
Observation: The turbidity produced in the sample solution should not be greater than the standard solution. If the
turbidity produced in the sample solution is less than the standard solution, the sample will pass the limit test of sulfate
and vice versa.
Reasons: Hydrochloric acid helps to make the solution acidic. Potassium sulfate is used to increase the sensitivity of
the test by giving an ionic concentration in the reagent. Alcohol helps to prevent supersaturation
LIMIT TEST OF IRON
The limit test of Iron is based on the reaction of iron in an ammonical solution with thioglycollic acid in the
presence of citric acid to form iron thioglycolate, which is pale pink to deep reddish-purple in colour.

PROCEDURE:
Test Sample Standard Compound (20 ppm Fe)
Dissolve the specified amount of the sample in water Take 2 ml of the standard iron solution and dilute with
and make up the volume to 40 ml in a Nessler cylinder. water up to 40 ml in a Nessler cylinder.
Add 2 ml of 20% w/v citric acid solution (iron-free). Add 2 ml of 20% w/v citric acid solution (iron-free).
Add 2 drops of thioglycolic acid. Add 2 drops of thioglycolic acid.
Add ammonia solution to make the solution alkaline, Add ammonia solution to make the solution alkaline,
then adjust the total volume to 50 ml with water. then adjust the total volume to 50 ml with water.
Allow the solutions to stand for 5 minutes. Allow the solutions to stand for 5 minutes.
Observe the color developed vertically and compare it Observe the color developed vertically and compare it
with the standard solution. with the test solution.
Iron Standard Solution (20 ppm Fe): Dilute 1 volume of a 0.1726 percent w/v solution of ferric ammonium sulfate
in 0.05 M sulfuric acid to 10 volumes with water. Contains iron in the ferric state. Earlier, ammonium thiocyanate
reagent was used for the limit test of iron. Since thioglycolic acid is a more sensitive reagent, it has replaced
ammonium thiocyanate in the test.
Observation: The purple colour produced in the sample solution should not be greater than the standard solution. If
the purple colour produced in the sample solution is less than the standard solution, the sample will pass the limit test
of iron and vice versa.
Reasons: Citric acid helps in preventing the precipitation of iron by ammonia by forming a complex with it.
Thioglycolic acid helps to oxidise iron (II) to iron (III). Ammonia to make the solution alkaline
LIMIT TEST OF LEAD
Principle: The Limit test of lead is based on the reaction of lead and diphenyl thiocarbazone (dithizone) in alkaline
solution to form a lead dithizone complex, which is red in colour. Dithizone is green in colour in chloroform, and
the lead-dithizone complex is violet in colour, so the resulting colour at the end of the process is red.

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PROCEDURE:
Test Sample Standard Compound
Transfer a known quantity of the sample solution into a Prepare a standard lead solution equivalent to the
separating funnel. amount of lead permitted in the sample and transfer it
into a separating funnel.
Add 6 ml of ammonium citrate solution. Add 6 ml of ammonium citrate solution.
Add 2 ml of potassium cyanide and 2 ml of Add 2 ml of potassium cyanide and 2 ml of
hydroxylamine hydrochloride. hydroxylamine hydrochloride.
Add 2 drops of phenol red indicator. Add 2 drops of phenol red indicator.
Make the solution alkaline by adding ammonia solution. Make the solution alkaline by adding ammonia solution.
Extract with 5 ml of dithizone solution until the Extract with 5 ml of dithizone solution until the
dithizone layer turns green. dithizone layer turns green.
Combine the dithizone extracts and shake with 30 ml of Combine the dithizone extracts and shake with 30 ml of
nitric acid for 30 minutes; discard the chloroform layer. nitric acid for 30 minutes; discard the chloroform layer.
To the acid solution, add 5 ml of standard dithizone To the acid solution, add 5 ml of standard dithizone
solution. solution.
Add 4 ml of ammonium cyanide solution. Add 4 ml of ammonium cyanide solution.
Shake the mixture for 30 minutes. Shake the mixture for 30 minutes.
Observe the color developed in the solution. Observe the color developed in the solution.

★ Preparation of standard lead solution (1 ppm Pb): Dissolve 0.400 g of lead nitrate in water containing 2 ml
of dilute nitric acid and add sufficient water to produce 250.0 ml. This gives a standard lead solution (1% Pb).
★ Standard lead solution (1 ppm Pb) is prepared by diluting 1 volume of standard lead solution (1% Pb) to
1000 volumes with water.
★ Preparation of dithizone extraction solution: Dissolve 30 mg of dithizone in 1000 mL of chloroform and
add 5 ml of ethanol (95%). The solution is stored in the refrigerator. Before use, the solution is shaken with
about half of its volume of 1% v/v nitric acid solution and the acid is discarded.
★ Preparation of Dithizone standard solution: Dissolve 10 mg of dithizone in 1000 mL of chloroform.
★ Observation: The intensity of the colour of the complex depends on the amount of lead in the solution. The
colour produced in the sample solution should not be greater than the standard solution. If the colour produced
in the sample solution is less than the standard solution, the sample will pass the limit test of lead and vice versa
LIMIT TEST OF ARSENIC
Principle:
★ The Limit Test for Arsenic (also known as the Gutzeit Test) is based on the formation of a yellow stain on
mercuric chloride paper when arsine gas (AsH₃) reacts with it.
★ In this test, arsenic present as arsenic acid in the sample is reduced to arsenious acid using potassium iodide,
stannous chloride, zinc, and hydrochloric acid.
★ The arsenious acid is then further reduced by nascent hydrogen to form arsine gas.
★ The arsine gas reacts with mercuric chloride paper, producing a yellow stain, and the intensity of the colour is
directly proportional to the amount of arsenic present in the sample.

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As3 + ⎯⎯
→ H 3 AsO 4
( Arsenic acid )

H 3 AsO 4 ⎯⎯
→ H 3 AsO3
( Arsenic acid ) ( Arsenious acid )

H3AsO3 + 3H 2 ⎯⎯
→ AsH3 (g)+ 3H 2 O
( Arsenious acid ) ( Arsin e )

2AsH3 + HgCl2 ⎯⎯
→ Hg(AsH 2 ) 2 + 2HCl
( Arsin e ) ( Mercurous chloride ) ( Yellow strain )

APPARATUS AS PER IP 1996:

The Gutzeit apparatus used for the Limit Test of Arsenic consists of the
following key parts:
A generator bottle of about 60 ml capacity marked at 40 ml for the reaction
mixture.
A glass tube with a a 6.5 mm inner diameter for gas passage.
A ground joint glass tube (6.5 mm inner diameter, 18 mm outer diameter
at the joint) forming concentric inner and outer joints for tight fitting.
A rubber stopper to seal the generator bottle and prevent gas leakage.
A narrow glass tube section (part B) is packed with glass wool to trap impurities.
A lead acetate cotton plug or wool to absorb moisture and prevent
interference from hydrogen sulfide or other gases.
PROCEDURE
Test solution:
1. The test solution is prepared by dissolving a specific amount in water and stannated HCl (arsenic-free) and
kept in a wide-mouthed bottle.
2. To this solution, 1 gm of KI, 5 ml of stannous chloride acid solution and 10 gm of zinc are added (all these
reagents must be arsenic-free).
3. Keep the solution aside for 40 min, and the stain obtained on mercuric chloride paper is compared with the
standard solution.
Standard solution: A known quantity of dilute arsenic solution is kept in wide wide-mouthed bottle,
and rest procedure is followed as described in the test solution
LIMIT TEST OF HEAVY METALS
Principle: The Limit test of heavy metals is based on the reaction of metallic impurities with hydrogen sulfide
in an acidic medium to form a brownish-colored solution. Metals that respond to this test are lead, mercury,
bismuth, arsenic, antimony, tin, cadmium, silver, copper, and molybdenum. The metallic impurities in
substances are expressed as parts of lead per million parts of the substance. The usual limit as per the Indian
Pharmacopoeia is 20 ppm.
Procedure: Method A: Use for the substance that gives a clear, colourless solution under the specific condition.

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Test Sample Standard Compound

Prepare the solution as directed in the monograph and Take 2 ml of standard lead solution and dilute to 25 ml
transfer 25 ml to a Nessler cylinder. with water in a Nessler cylinder.
Adjust the pH between 3 and 4 by adding either dilute Adjust the pH between 3 and 4 by adding either dilute
acetic acid or dilute ammonia solution. acetic acid or dilute ammonia solution.
Dilute the solution with water to 35 ml. Dilute the solution with water to 35 ml.
Add 10 ml of freshly prepared hydrogen sulfide Add 10 ml of freshly prepared hydrogen sulfide
solution. solution.
Dilute the solution with water to 50 ml. Dilute the solution with water to 50 ml.
Allow the solution to stand for 5 minutes. Allow the solution to stand for 5 minutes.
View the colour developed by looking downwards over View the colour developed by looking downwards over
a white surface. a white surface.

OBSERVATION:
♦ The colour produced in the sample solution should not be greater than the standard solution.
♦ If the colour produced in the sample solution is less than the standard solution, the sample will pass the limit
test of heavy metals and vice versa.

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