Notes

Virtual Lab Link:

1.Qualitative Analysis of Cations-https://amrita.olabs.edu.in/?sub=73&brch=7&sim=180&cnt=1

2.Qualitative Analysis of Anions-https://amrita.olabs.edu.in/?sub=73&brch=7&sim=31&cnt=1

3.Basic Lab Techniques-https://amrita.olabs.edu.in/?sub=73&brch=7&sim=32&cnt=1

What is Salt Analysis?

Salt analysis (also known as systematic qualitative analysis or qualitative inorganic analysis) involves
the identification of the cation and anion of an inorganic salt. This is done by conducting a series of
tests in a systematic manner and using the observations to confirm the absence or presence of specific
cations and anions.

Step-by-Step Process for Salt Analysis

 Step 1: Obtain the inorganic salt whose cation and anion you must identify.
 Step 2: Conduct preliminary tests for the anion group-wise until you obtain a positive result.
Anions and cations are classified into groups that share the same group reagent and therefore,
have similar preliminary tests.
 Step 3: Once you get a positive result for a preliminary test for an anion, conduct a
confirmatory test for that anion. (If you get a positive result, move on to step 4. If you don’t, go
back to conducting preliminary tests for anions.)
 Step 4: Conduct preliminary tests for cations group-wise until you obtain a positive result.
 Step 5: Once a positive result is obtained, conduct a confirmatory test for that cation.
 Step 6: Now that the cation and the anion are identified, obtain the chemical formula of the
salt by balancing the charges of the cation and anion. For example, if your cation is Fe3+ and
your anion is Cl–, the chemical formula of the salt will be FeCl3.
Note: You can also identify the cation first and then move on to identifying the anion.

Tricks and Shortcuts for Salt Analysis

Always check the colour of the salt first. Certain cations have coloured salts. If the salt is coloured,
you can directly conduct a preliminary test for the cation that forms salts of that colour. The cations
that form coloured salts are tabulated below:

Colour of the Inorganic Salt Cation

Blue Cu2+

Deep blue Co2+ (anhydrous salt)

 Greenish-blue Cu2+ (hydrated salt)

Green Ni2+ (hydrated salt)

Light green Fe2+

Yellow, brown, or yellowish-brown Fe3+

Pale pink Mn2+

Rose-red Co2+ or mercuric iodide (HgI2)

Purple or dark green Cr3+

If the salt is colourless, perform a flame test first (since the presence of 3 different cations can be
confirmed by it). An easier way to perform the flame test is to pick up a chunk of the salt with test tube
holders, pour a few drops of concentrated HCl on it, and expose it to the flame of a Bunsen burner.
If you do not gain any insight into the cation from the flame test (or from visual inspection), proceed
with group-wise preliminary tests for cations. Note that some cations do not form salts with certain
anions, as listed below.

 Ba2+, Sr2+, Pb2+, and Ca2+ do not form salts with the sulphate anion (SO42-).
 Only group 0, group 1, and group 2 cations form salts with the phosphate anion (PO43-).
If you identify one of these cations in the salt analysis, you need not conduct tests for the corresponding
anions.
Finally, certain salts are very common in salt analysis examinations. For example, the most common
salt containing the bromide ion (Br–) is NH4Br and the most common salt containing the calcium cation
(Ca2+) is CaCl2. Also, some salts can be identified by observing their texture and appearance (for
example, calcium carbonate has the texture of powdered chalk). Therefore, visiting your chemistry
laboratory and physically examining the salts may help you quickly analyze the salt in the practical
examination.

List of Common Cations (Basic Radicals) for Salt Analysis

*Note: Multiple Ions belonging to the same group have the same preliminary test but different
confirmatory tests.

Group Cations
 Group 0 NH4+

Group 1 Pb2+

Group 2 Cu2+

Group 3 Fe3+, Fe2+, Al3+

Group 4 Co2+, Mn2+, Ni2+, Zn2+

Group 5 Ba2+, Ca2+, Sr2+

Group 6 Mg2+

List of Common Anions (Acidic Radicals) for Salt Analysis

Group Anions

Group 1 CO32-, NO2–, SO32-, S2-

Group 2 Cl–, Br–, I–, CH3COO–, NO3–, C2O42-

Group 3 PO43-, SO42-

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

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
tests 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

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

Formation of a white precipitate which

Add aqueous barium chloride (BaCl2) to
Sulphite (SO ) 3
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 (NO ) 2
– 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 nitric acid (HNO3) 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 (CH3COO–)
ethanol to the salt. the formation of an ester)
 Formation of a white precipitate that
Add acetic acid and calcium chloride to
Oxalate (C2O )4
– 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 (SO42-) 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.

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

 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+)

A white precipitate is formed when aqueous (NH4)2C2O4 (ammonium oxalate) and NH4OH
Calcium (Ca2+)
are added to the solution.
Confirmatory Tests for Cations
Cation Confirmatory Test Positive Observation

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

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

In the preliminary test, a black precipitate is obtained

from the addition of dilute HCl and H2S to the original A blue coloured solution
Copper (Cu2+)
solution. Isolate the black precipitate and add excess is formed
ammonium hydroxide to it

Add concentrated nitric acid to the original solution

A blue precipitate is
Iron (Fe )
3+ and heat it. A brown precipitate will form. Add HCl and
formed
potassium ferrocyanide (K4[Fe(CN)6]) to it

A gelatinous white precipitate is obtained when NH4Cl

A floating, blue layer is
and excess NH4OH are added to the original solution.
Aluminium (Al ) 3+ formed on the surface of
Isolate the precipitate and dissolve it in HCl. now add
the clear solution
blue litmus and NH4OH to it drop-by-drop

Add solid NH4Cl and excess NH4OH to the original

solution and pass H2S gas through it. Dissolve the A yellow precipitate is
Cobalt (Co2+)
resulting blue residue in water and add dilute CH3COOH obtained.
and KNO2 to it. Now warm the mixture.

Add solid NH4Cl and excess NH4OH to the original

solution and pass H2S gas through it. Dissolve the
A black precipitate is
Nickel (Ni2+) resulting yellow residue in water (you will now obtain a
formed
green-coloured solution). Add NaOH and bromine
water to this mixture and boil it.

To the skin-coloured precipitate obtained in the

Manganese Formation of a white
preliminary test, add dilute HCl and boil off the H2S.
(Mn2+) precipitate that turns
Now add NaOH.
 brown or black when
bromine water is added

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 off some of the paste with a glass rod and expose it to a Sr2+: Crimson red flame
(Ca2+) Bunsen Burner’s flame.
Ca2+: Brick red flame

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

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