Group Cations (basic radicals)

Group 0 NH4+ (no group reagent )

Group 1 Pb2+ (dil HCl) ppt chlorides

Group 2 Cu2+ (dil HCl + hydrogen sulphide) sulphides

Group 3 Fe3+, Al3+ (amm. Hydroxide + amm.chloride) hydroxides

Group 4 Co2+, Mn2+, Ni2+, Zn2+ (amm. Hydroxide + amm.chloride + hydrogen sulphide gas) sulphide

Group 5 Ba2+, Ca2+, Sr2+ (amm. Hydroxide + amm.chloride + amm. Carbonate) carbonate

Group 6 Mg2+ ammonium hydrogen phosphate hydrogen phosphate

List of Common Anions (Acidic Radicals) for Salt Analysis

Group Anions

Group 1 CO32-, NO2–, SO32-, S2- dil.Sulphuric acid

Group 2 Cl–, Br–, I–, CH3COO–, NO3–, C2O42- Conc.sulhuric acid

Group 3
, SO42-
3-
indeoendent group no group reagent

Preliminary Test for Anions

In salt analysis, preliminary tests for anions are conducted group-wise to find the anion of the salt.
After getting a positive preliminary test for an anion, a confirmatory test must be conducted to
confirm the presence of that anion in the salt.

Preliminary Test for Group 1 Anions

Experiment: Add a few drops of dilute H2SO4 (sulfuric acid) to a small quantity of the salt in a test
tube (If nothing happens, move on to preliminary test for group 2 anions).

Anion Positive Result

Carbonate (CO32-) Colourless and odourless gas that turns limewater milky

Sulphite (SO32-) Colourless, pungent-smelling gas (burning sulphur smell)

Sulphide (S2-) Colourless gas which smells like rotten eggs

Nitrite (NO2–) Light brown gas having a pungent smell

Preliminary Test for Group 2 Anions
Experiment: Take a small chunk of the salt in a test tube and add a few drops of concentrated
H2SO4 (sulfuric acid) to it (If nothing happens, move on to preliminary test for group 2 anions).

Anion Positive Result

White, pungent-smelling fumes that intensify when a glass rod dipped in ammonium
Chloride (Cl–)
hydroxide is brought to the mouth of the test tube

Bromide (Br–) Reddish-brown fumes

Iodide (I–) Violet fumes

Acetate
Pungent fumes that smell like vinegar
(CH3COO–)

Nitrate (NO3–) Brown fumes with a pungent smell

Oxalate (C2O4–) Bubbly effervescence of a combination of carbon monoxide and carbon dioxide gas

Preliminary Test for Group 3 Anions

The sulphate and phosphate ions (group 3 anions) do not have any preliminary tests. If no positive
preliminary tests are obtained for group 1 and group 2 anions, you can directly jump to confirmatory
test for the sulphate and phosphate anions.

Confirmatory Test for Anions

*Note: Water extract of the salt can be prepared by dissolving a pinch of the inorganic salt in a few
drops of water.

Anion Confirmatory Test Positive Observation

Add magnesium sulphate (MgSO4) to the

Carbonate (CO32-) Formation of a white precipitate.
water extract of the salt

Formation of a white precipitate which

Add aqueous barium chloride (BaCl2) to
Sulphite (SO3 ) 2-
disappears when diluting hydrochloric
the water extract
acid (HCl) is added.

(i) Add sodium nitroprusside to the

water extract (i) The solution turns purple or violet
Sulphide (S2-)
(ii) Add aqueous lead acetate to the (ii) Formation of a black precipitate
water extract
 Boil a mixture of the water extract and
–
The solution develops a deep blue
Nitrite (NO2 ) dilute H2SO4. Now add solid potassium
colour
iodide and starch solution to it

Formation of a white precipitate which

–
Add silver nitrate (AgNO3) to the water
Chloride (Cl ) is soluble in ammonium hydroxide
extract
(NH4OH)

Formation of a yellow precipitate which

Bromide (Br–) Add silver nitrate to the water extract is partially soluble in ammonium
hydroxide

Formation of a yellow precipitate which

Iodide (I–) Add silver nitrate to the water extract
is insoluble in NH4OH

Mix the water extract with iron (II)

sulphate solution (FeSO4) and add one Formation of a brown ring at the
Nitrate (NO3–)
drop of concentrated sulphuric acid junction of the acid and the solution.
along the side of the test tube.

Add concentrated H2SO4 and some Development of a fruity smell (due to

Acetate
ethanol to the salt. the formation of an ester)
(CH3COO–)
Salt+ water + ferric chloride Blood red colour

Formation of a white precipitate that

Add acetic acid and calcium chloride to
Oxalate (C2O4–) dissolves upon the addition of dilute
the water extract and boil the solution.
HNO3

Formation of a white precipitate which

Add aqueous barium chloride (BaCl2) to
Sulphate (SO4 ) 2-
is insoluble in concentrated
the water extract
hydrochloric acid (HCl)

Add dilute nitric acid (HNO3) and

ammonium molybdate ((NH4)2MoO4) to Formation of a yellow, crystalline
Phosphate (PO43-)
the water extract and boil the resulting precipitate
solution.
Shortcut: Ammonium bromide (NH4Br) is the most common salt containing the bromide ion in
school laboratories. If you confirm the presence of bromide ions in the salt, you can immediately
try a confirmatory test for the ammonium cation (NH4+)

Preliminary Test for Cations

In salt analysis. preliminary tests for cations must be conducted in order to check for the presence
of different cations in the inorganic salt. This is done in a manner that is similar to the preliminary
tests for anions. Note that some cation groups (such as group 0 and group 6 cations) do not have
any preliminary tests. For these cations, confirmatory tests may be conducted directly.
Note: The original solution (OS) of the salt can be prepared by mixing a small amount of the
inorganic salt with water and acid.
Salt +water +NaOH = Ammonical smell Nesseler reagent reddish brown ppt or brick
red colour

Preliminary Test for Group 1 Cations

Experiment: Add a few drops of dilute hydrochloric acid (HCl) to the original solution.

Cation Positive Result

Lead (Pb2+) Formation of a white precipitate

Preliminary Test for Group 2 Cations

Experiment: Add a few drops of dilute HCl and hydrogen sulphide (H2S) to the original solution.

Cation Positive Result

Copper (Cu2+) A black precipitate is formed

Preliminary Test for Group 3 Cations ( Salt + water amm. Chloride +

Amm hydroxide ( brown ppt (ferric ion ) Gelatinous ppt (aluminium)
• Ferrous salts (featuring Fe2+ ions) are green in colour and ferric salts (featuring Fe3+ ions)
are brown in colour.
• For aluminium (Al3+ ion), a gelatinous white precipitate is obtained when the solid
ammonium chloride (NH4Cl) and excess ammonium hydroxide are added to the original
solution.

Preliminary Test for Group 4 Cations

Experiment: Add solid NH4Cl and excess NH4OH to the original solution. Now pass H2S gas
through it.

Cation Positive Result

Cobalt (Co2+) and Nickel (Ni2+), conduct both confirmatory tests Formation of a black precipitate

Manganese (Mn2+) A skin-coloured precipitate is formed

Zinc (Zn2+) A greyish-white precipitate is formed

Preliminary Test for Group 5 Cations

Experiment: Add ammonium carbonate ((NH4)2CO3), ammonium chloride (NH4Cl), and ammonium
hydroxide to the original solution. If you obtain a white precipitate, the cation might be a group 5
cation. Add dilute acetic acid (CH3COOH) to dissolve the white precipitate. Now do the following
tests in the same order followed in the tabular column provided below.
 Cation Positive Result

Barium (Ba2+) A yellow precipitate is formed when K2CrO4 is added to the solution.

Strontium
A white precipitate is formed when aqueous (NH4)2SO4 is added to the solution.
(Sr2+)

Calcium A white precipitate is formed when aqueous (NH4)2C2O4 (ammonium oxalate) and NH4OH
(Ca2+) are added to the solution.

Confirmatory Tests for Cations

Cation Confirmatory Test Positive Observation

Formation of reddish
Add sodium hydroxide to the original solution and treat
Ammonium (NH4+) brown precipitate
it with Nessler’s reagent (K2HgI4)
(brick colour)

(i) Add potassium iodide (KI) to the original solution Formation of a yellow
Lead (Pb2+) (ii) Add potassium chromate (K2CrO4) to the original precipitate (for both the
solution tests)

A blue coloured
Copper (Cu2+) Salt+water+ ammonium hydroxide
solution is formed

Add HCl and potassium ferrocyanide (K4[Fe(CN)6]) to A blue precipitate is

Iron (Fe3+)
salt solution formed

A gelatinous white precipitate is obtained when NH4Cl

A floating, blue layer is
Aluminium (Al3+) and excess NH4OH are added to the original solution.
formed on the surface
(lake test) Isolate the precipitate and dissolve it in HCl. now add
of the clear solution
blue litmus and NH4OH to it drop-by-drop

Cobalt (Co2+) Blue coloured ppt is

Salt + water + ammonium thiocyanate
Cobalt nitrate obtained

Nickel (Ni2+) Salt + water + dimethylglyoxime Pink colour is obtained

Formation of a white
Manganese (Mn2+) In a salt solution add NaOH.
precipitate

Add NaOH (in excess) to the greyish-white precipitate The white precipitate is
Zinc (Zn2+)
obtained in the preliminary test. dissolved

Barium (Ba2+),
Flame test: Make a paste of the salt by mixing it with a Ba2+: Green-coloured
Strontium (Sr2+),
few drops of concentrated hydrochloric acid. Now skim flame
and Calcium (Ca2+)
 off some of the paste with a glass rod and expose it to a Sr2+: Crimson red
Bunsen Burner’s flame. flame
Salt + water + potassium chromate (yellow ppt)
Ca2+: Brick red flame
Salt + water + ammonium sulphate (white ppt)
Salt+ water + ammonium oxalate (white ppt)

Add NH4Cl, (NH4)3PO4 (ammonium phosphate) and A white precipitate is

Magnesium (Mg2+)
excess NH4OH to the original solution. obtained.