SALT ANALYSIS

By:
Aashrith Vennelakanti
EE15B002
Contents
1 Introduction to Salt Analysis 4
2 Preliminary Tests 4
2.1 Colour Test 4
2.2 Solubility Test 5
2.3 Heating of Dry Salt 5
2.4 Flame Test 5
2.5 Borax Bead Test 6
2.6 Charcoal Cavity Test 7
2.7 Cobalt Nitrate Test 7
3 Systematic Analysis of Anions 8
3.1 Group I 8
3.1.1 Carbonate 8
3.1.2 Bicarbonate 9
3.1.3 Sulphite 9
3.1.4 Nitrite 10
3.1.5 Sulphide 11
3.1.6 Acetate 11
3.2 Group II 12
3.2.1 Chloride 12
3.2.2 Bromide 13
3.2.3 Iodide 13
3.2.4 Nitrate 14
3.2.5 Oxalate 15
3.3 Group III 15
3.3.1 Sulphate 15
3.3.2 Phosphate 15
3.3.3 Borate 16
4 Classification of Cations into Groups 16
5 Systematic Analysis of Cations 17
5.1 Group 0 (ammonium ion) 17
5.2 Group I 17
5.2.1 Lead (II) 17
5.2.2 Mercury (I) 18
5.2.3 Silver (I) 18
5.3 Group IIA 19
5.3.1 Lead (II) 19
5.3.2 Cadmium (II) 19
5.3.3 Copper (II) 19
5.3.4 Mercury (II) 20
5.3.5 Bismuth (III) 20
5.4 Group IIB 20
5.4.1 Arsenic (III) 20
5.4.2 Tin (II) 21
5.4.3 Tin (IV) 21
5.4.4 Antimony (III) 21
5.5 Group III 21
5.5.1 Iron (III) 22
5.5.2 Chromium (III) 22
5.5.3 Aluminium (III) 22
5.6 Group IV 23
 5.6.1 Manganese (II) 23
5.6.2 Nickel (II) 23
5.6.3 Cobalt (II) 23
5.6.4 Zinc (II) 24
5.7 Group V 24
5.7.1 Barium (II) 24
5.7.2 Strontium (II) 24
5.7.3 Calcium (II) 25
5.8 Group VI 25
5.8.1 Magnesium (II) 25
5.8.2 Sodium (I) 25
5.8.3 Potassium (I) 25
6 References 25
1 Introduction to Salt Analysis
Salt analysis is the systematic procedure of determining the components of a salt (cation +
anion) using several physical and chemical tests. Based on observations like visual changes
like colour change or formation of precipitate, or the evolution of a gas, one can deduce a
cation or anion in a salt. Further tests are conducted to confirm the ion.
The three steps in systematic salt analysis are:
Preliminary tests, performed on the solid salt (dry tests) and its solution (wet tests), then
the determination of the anion by carrying out reactions in the solution phase (wet tests),
and the confirmatory tests, and finally
the determination of the cation by carrying out reactions in the solution phase (wet tests),
and the confirmatory tests.
Preliminary tests usually aren't conclusive but are helpful in simplifying further analysis of
the salt by providing important information like colour, smell, and solubility of the salt.
Heating of dry salt, flame test, solubility test, borax bead test, and cobalt nitrate test are
examples of preliminary tests which will be discussed in the next section.

2 Preliminary Tests
Preliminary tests are conducted before further analysis of the salt. Commonly conducted
preliminary tests are:
Colour test
Solubility test
Heating of dry salt
Flame test
Borax Bead test
Charcoal Cavity test
Cobalt Nitrate test
Let us discuss the preliminary tests in detail.

2.1 Colour Test

Observe the colour of the salt. The colour of the salt may give useful information about the
cation. Below is a table giving the characteristic colours of salts of some cations.
Colour Cation
Blue Cu2+ (Hydrated)
Yellow/Brown Fe3+
Green Fe2+ (Light Green, Hydrated), Ni2+, Cr3+ (Hydrated)
Reddish Pink/Blue Co2+
Light Pink Mn2+ (Hydrated)
2.2 Solubility Test
Add a small amount of the salt in water and stir well. If the salt dissolves, then it is water-
soluble. Heating might be required to dissolve the salt in water. Some salts require acids like
HCl or HNO3 or basic solutions like sodium carbonate extract to be dissolved in a solution.
The solution containing the salt is called original solution (O.S.) and portions of it will be
used for the entire analysis. If a salt cannot be dissolved using HCl or HNO 3, aqua regia (3:1
HCl to HNO3) is used to dissolve the salt. If the salt cannot be dissolved by even aqua regia,
then the salt is said to be insoluble. We will be focusing only on soluble salts though.

2.3 Heating of Dry Salt

A small amount of dry salt is taken in a test tube and the test tube is heated for one minute.
The table below gives a list of common observations and their inferences.
Observation Inference
A reddish brown gas is evolved. The salt may contain NO3- , NO2- , or Br-
(excluding ammonium salts).
The salt sublimates. The salt may be an ammonium halide.
Small bubbles are seen and a crackling noise is The salt may be hydrated.
heard.
A white residue is left just after heating. The salt The salt may contain Cu2+.
heated was originally blue in colour. Adding
water to the residue makes it blue again.
The residue left after heating is yellow when hot The salt may contain Zn2+.
and white when cold.
A colourless gas is evolved which turns lime The salt may contain CO32- , HCO3- , or SO32-.
water milky.

2.4 Flame Test

A small amount of salt is mixed with concentrated HCl to make a paste. A small amount of
the paste is then picked up using a platinum wire loop and introduced to the non-luminous
(oxidizing) part of a bunsen burner flame. Depending on the radical (cation or anion)
present in the salt, the flame exhibits characteristic colours. Below is a table indicating the
radicals corresponding to the flame colour.
Flame Colouration Radical
Golden-Yellow Na+
Lilac K+
Brick-Red Ca2+
Crimson Sr2+
Apple-Green Ba2+
Green BO33-, Cu2+
Blue/Silver Pb2+, As3+, Sb3+, Bi3+, Cu+
Flames coloured by certain cations when viewed through a cobalt glass appear to have a
different colour. A list of such cations is given below along with flame colouration when
 viewed normally and through cobalt glass.
Flame colouration when Flame colouration when Cation
viewed normally viewed through cobalt glass
Golden-Yellow Nil Na+
Lilac Crimson K+
Brick-Red Light-Green Ca2+
Crimson Purple Sr2+
Apple-Green Bluish-Green Ba2+
Green (with blue centre) Same Colouration Cu2+
Below is a picture showing the luminous and non-luminous parts of a flame.

The inner part of the flame is

luminous and reducing and the
outer part is non-luminous and
oxidizing.

2.5 Borax Bead Test

A small quantity of borax (Na2B4O7.10H2O) is taken using a hot platinum wire loop and
introduced to a Bunsen flame to form a bead. Coat the bead with a small amount of salt
and reintroduce the bead to either the luminous (inner, reducing) or non-luminous (outer,
oxidizing) part of the Bunsen burner flame. Depending on whether the bead was exposed
to the luminous or non-luminous part of the flame, the flame exhibits a different
colouration.
When borax is heated, it loses it water of crystallization and decomposes to sodium
metaborate and boric anhydride.
Na2B4O7.10H2O (borax) Na2B4O7 2NaBO2 (sodium metaborate) + B2O3 (boric anhydride)
The boric anhydride bead reacts with the metal salt coated on it when introduced to flame
to form metaborates which give different colours in oxidizing and reducing flame. For
copper sulphate,
CuSO4 + B2O3 [in oxidizing flame] Cu(BO2)2 (blue-green) + SO3
Cu(BO2)2 (cupric metaborate) can undergo two reactions in reducing flame:
2Cu(BO2)2 + 2NaBO2 + C 2CuBO2 (colourless) + Na2B4O7 + CO
2Cu(BO2)2 + 4NaBO2 + 2C 2Cu (reddish-brown) + 2Na2B4O7 + 2CO
The salt bead can show different colours when it is hot or cold. A list of a few metals with
their bead colourations is given below.
 Oxidizing Flame Reducing Flame Metal
In cold In hot In cold In hot
Blue Green Reddish-brown Colourless Copper
(opaque)
Reddish-brown Violet Grey Grey Nickel
Light Violet Light Violet Colourless Colourless Manganese
Yellow Yellowish-Brown Green Green Iron
Blue Blue Blue Blue Cobalt

2.6 Charcoal Cavity Test

A small cavity is made in a charcoal block and is filled with small amount of salt and sodium
carbonate. The salt mixture is moistened with a small amount of water. A blowpipe is used
to heat the salt in a luminous flame. The colour of the residue formed in the cavity is to be
observed both when it is hot and it is cold. Below is a picture showing how to produce
oxidizing and reducing flames using a blowpipe.

To produce a reducing flame, blow air just

outside the flame. To produce an
oxidizing flame, blow air about one-third
within the flame.
For example, if the test is performed on CuSO4,
CuSO4 + Na2CO3 [heating] CuCO3 + Na2SO4
CuCO3 [heating] CuO + CO2
CuO + C [heating] Cu (reddish-brown) +CO
Below is a list of a few common ions and the observations when the charcoal cavity test is
performed on their salts.
Observations Cation
Yellow residue when hot and grey metal when Pb2+
cold
Residue that is yellow when hot and white Zn2+
when cold
Brown Residue Cd2+
White residue with a garlic smell As3+

2.7 Cobalt Nitrate Test

If the residue from the charcoal cavity test was white without any other characteristic
observations (like the odious residue resulting from As 3+), then the cobalt nitrate test is
performed. The residue is treated with a small amount of cobalt nitrate solution and heated
strongly using a non-luminous flame produced with the help of a blowpipe. Cobalt nitrate
decomposes to cobalt (II) oxide on heating and the cobalt oxide gives a characteristic colour
with the metal oxide present in the cavity. For a cation M2+,
2Co(NO3)2 [heating] 2CoO + 4NO2 + O2
 CoO + MO CoO.MO (some colour)
For M3+,
CoO + M2O3 CoO.M2O3 (some colour)
Below is a table listing a few cations with the cobalt-metal double oxides and their colours.
Cation Cobalt-metal double oxide, colour
Al3+ CoO.Al2O3, Blue
Mg2+ CoO.MgO, Pink
Zn2+ CoO.ZnO (Rinman's Green) , Green

3 Systematic Analysis of Anions

After the preliminary tests are performed, the anion in the salt is classified into a group
based on whether a gas or acid vapours is evolved when the salt reacts with dilute or
concentrated sulphuric acid. Generally, anions are classified into three groups:
Group I, if gases or acid vapours are evolved when they react with dilute sulphuric acid,
Group II, if gases or acid vapours are evolved when they react with concentrated sulphuric
acid (group I anions are included), or
Group III, if no gas is evolved even with the application of concentrated sulphuric acid.

Group I anions can evolve gas even when they react with dilute hydrochloric acid.

Here are some examples of anions classified by groups (and the ones which we are going to
study).
Group I Group II Group III
Carbonate (CO32-) Chloride (Cl-) Sulphate (SO42-)
Bicarbonate (HCO3-) Bromide (Br-) Phosphate (PO43-)
Sulphite (SO32-) Iodide (I-) Borate (BO33-)
Nitrite (NO2-) Nitrate (NO3-)
Sulphide (S2-) Oxalate (C2O42-)
Acetate (CH3COO-)
Let us study each anion's identification and confirmatory tests, groupwise.

3.1 Group I
The group anions liberate gases or vapours with dilute hydrochloric acid or sulphuric acid.

3.1.1 Carbonate
Identification Test: To a small amount of salt, dilute HCl or H 2SO4 is added. A colourless and
odourless gas (CO2) is evolved that turns lime water milky and the milkiness disappears if
excess of the gas is passed through.

CO32- + 2H+ CO2(colourless) + H2O

 CO2 + Ca(OH)2 (lime water) CaCO3(the milkiness) + H2O

CO2 + H2O + CaCO3 Ca(HCO3)2 (soluble in water, colourless)

Carbon dioxide can turn baryta water (Ba(OH)2) milky (BaCO3) as well.

Confirmatory Test:
(a) A solution of barium chloride is added to the salt. A white precipitate (BaCO 3) appears
which dissolves in mineral acids or carbonic acid.

CO32- + Ba2+ BaCO3(ppt.)

BaCO3 + 2H+ Ba2+ + CO2 + H2O [mineral acid added to ppt]

BaCO3+ CO2 + H2O Ba2+ + 2HCO3- [carbonic acid added to ppt]

3.1.2 Bicarbonate
Identification Test: Similar to that for carbonates. The reactions are given below.

HCO3- + H+ CO2 + H2O

CO2 + Ca(OH)2 CaCO3 + H2O

CO2 + H2O + CaCO3 Ca(HCO3)2

Confirmatory Tests:
(a) Boiling the salt solution leads to the decomposition of the bicarbonate:
2HCO3- CO2 + CO32- + H2O
CO2 thus formed can be identified using lime water or baryta water.

(b)No precipitation occurs on addition of magnesium sulphate to bicarbonates, whereas

adding magnesium sulphate to carbonates gives magnesium carbonate precipitate.
However, on heating the mixture, magnesium carbonate is formed.

Mg2+ + 2HCO3- MgCO3 + H2O + CO2

(c)No precipitation occurs on addition of mercuric chloride. But on adding mercuric

chloride to carbonates, a reddish-brown precipitate of basic mercury(II) carbonate
(3HgO.HgCO3 Hg4O3CO3) is formed.

CO32- + 4Hg2+ + 3H2O Hg4O3CO3 + 6H+

The above reaction can be used confirm the carbonate ion.

3.1.3 Sulphite
Identification Test: To a small amount of salt, dilute HCl or H 2SO4 is added. A colourless gas
with a pungent smell (SO2) is evolved that turns lime water milky and turns acidified
potassium dichromate solution green.
SO32- + 2H+ SO2 + H2O
 SO2 + Ca(OH)2 (lime water) CaSO3(the milkiness) + H2O

3SO2 + Cr2O72- + 2H+ 2Cr3+ (green in colour) + 3SO42- + H2O

Confirmatory Tests:
(a) Some barium chloride solution is added to the salt solution. A white precipitate is
formed which dissolves in mineral acids. The precipitate on standing gets atmospherically
oxidized and is no longer soluble in dilute mineral acids.

SO32- + Ba2+ BaSO3(ppt.)

BaSO3 + 2H+ Ba2+ + SO2 + H2O [mineral acid added to ppt]

2BaSO3 + O2 2BaSO4 (insoluble in dilute mineral acids)

The SO2 evolved in the second reaction can be tested.

(b) Sulphite decolourizes acidified potassium permanganate solution due to the reduction
of permanganate to manganese (II) ions.

5SO32- + 2MnO4- + 6H+ 2Mn2+ + 5SO42- + 3H2O

3.1.4 Nitrite
Identification Test: To a small amount of salt, dilute HCl or H 2SO4 is added. A reddish-brown
gas (NO2) is evolved which turns acidified potassium iodide solution containing starch
solution blue.

NO2- + H+ HNO2 (unstable)

3HNO2 HNO3 + 2NO(colourless) + H2O

2NO + O2 2NO2 (reddish-brown)

4NO2 + 2KI 2KNO3 + I2 + 2NO

I2 + starch solution blue complex

Confirmatory Tests:
(a) Nitrite reacts with potassium iodide solution acidified with acetic acid to liberate iodine
which turns starch solution blue.

NO2- + CH3COOH CH3COO- + HNO2

2HNO2 + 2KI + 2CH3COOH 2CH3COOK + I2 + 2H2O + 2NO

I2 + starch solution blue complex

(b) A solution of acidified nitrite diazotizes sulphanilic acid which in turn couples with 1-
 naphthylamine to form a red azo-dye.

The confirmatory test for

the nitrite ion.

3.1.5 Sulphide
Identification Test: To a small amount of salt, dilute HCl or H 2SO4 is added. A gas which
smells of rotten eggs (H2S) is evolved with turns lead acetate paper black.

S2- + 2H+ H2S

H2S + Pb(CH3COO)2 PbS(black) + 2CH3COOH

Confirmatory Tests:
(a) A few drops of sodium nitroprusside (Na 2[Fe(CN)5NO]) are added to the salt solution. A
purple colouration appears, due to the formation of the complex anion [Fe(CN) 5NOS]4-.

S2- + [Fe(CN)5NO]2- [Fe(CN)5NOS]4- (purple)

H2S normally cannot give the above test as it can't furnish enough sulphide due to it being a
weak acid.

(b) A few drops each of ferric chloride and N,N-Dimethyl-p-phenylenediamine solution are
added to a strongly acidified sulphide salt solution. A blue colouration of methylene blue
appears within some time.

The test to the left is called Methylene

Blue test and the final product is the
eponymous blue pigment. Here hydrogen
sulphide is used. Sulphide salts can be
used in place of H2S.

3.1.6 Acetate
Identification Test: To a small amount of salt, dilute HCl or H 2SO4 is added. Colourless
vapours with a vinegary smell (CH3COOH) are evolved which turn blue litmus red.

CH3COO- + H+ CH3COOH

CH3COOH is acidic, so it turns blue litmus red.

Confirmatory Tests:
 (a) Esterification Test: To a small amount of salt, a few drops of ethanol and concentrated
sulphuric acid are added and the mixture is heated. A fruity odour of ester is detected.

CH3COO- + H2SO4 CH3COOH + HSO4-

CH3COOH + C2H5OH CH3COOC2H5 (has a fruity odour) + H2O

(b) To a small amount of salt, neutral ferric chloride solution is added. A deep-red
colouration is formed due to the formation of the complex [Fe 3(OH)2(CH3COO)6]+. On boiling
the solution, the red colouration disappears, and a reddish-brown precipitate of basic
iron(III) acetate is formed.

6CH3COO- + 3Fe3+ + 2H2O [Fe3(OH)2(CH3COO)6]+ (red) + 2H+

[Fe3(OH)2(CH3COO)6]+ + 4H2O [heating] 3Fe(OH)2CH3COO(reddish-brown) + 3CH3COOH

+ H+

3.2 Group II
The group anions liberate gases or vapours with concentrated sulphuric acid.

3.2.1 Chloride
Identification Test: To a small amount of salt, concentrated H2SO4 is added. A colourless gas
with a pungent smell (HCl) is evolved which forms dense white fumes when it makes
contact with a rod dipped in ammonium hydroxide.

Cl- + H+ HCl

HCl + NH4OH NH4Cl(dense white fumes) + H2O

Confirmatory Tests:
(a) Chloride reacts with manganese dioxide and concentrated sulphuric acid to liberate
chlorine.

2Cl- + MnO2 + 2H2SO4 Cl2 + SO42- + MnSO4 + 2H2O

(b) Acidified chloride reacts with silver nitrate to produce curdy white precipitate of silver
chloride which dissolves in ammonium hydroxide solution.

Cl- + Ag+ AgCl(curdy white ppt)

AgCl + 2NH4OH [Ag(NH3)2]Cl (soluble) + 2H2O

(c)Chromyl Chloride Test: Chloride reacts with potassium dichromate and concentrated
sulphuric acid to evolve a deep-red gas (chromyl chloride, CrO 2Cl2) which when passed to
sodium hydroxide solution to obtain a yellow-coloured solution of sodium chromate. One
part of sodium chromate is made to react with lead acetate to obtain yellow precipitate of
lead chromate and the other, an acidified solution of sodium chromate with hydrogen
peroxide to give chromium pentoxide (blue in amyl alcohol).
 4Cl- + K2Cr2O7 + 6H2SO4 2KHSO4 + CrO2Cl2 + 4HSO4- + 3H2O

CrO2Cl2 + 4NaOH Na2CrO4 + 2NaCl + 2H2O

(CH3COO)2Pb + Na2CrO4 PbCrO4 + 2(CH3COO)Na

2H2O2 + 2H+ + CrO42- CrO5 + 3H2O

3.2.2 Bromide
Identification Test: To a small amount of salt, concentrated H2SO4 is added. A reddish-
brown gas with a pungent smell (Br 2) is evolved whose intensity rises on heating with MnO 2
addition to the reaction mixture.

2Br- + 2H2SO4 Br2 + SO2 + SO42- + 2H2O

2Br- + 2H2SO4 + MnO2 Br2 + MnSO4 + SO42- + 2H2O

Confirmatory Tests:
(a) Organic Layer Test: A few drops of CCl4/CHCl3 and excess chlorine water are added to the
test tube containing the salt solution. The test tube is shaken vigorously. The organic layer
(CCl4/CHCl3) turns brown due to the dissolution of bromine in it.

Cl2 + 2Br- Br2 (dissolved in organic layer) + 2Cl-

(b) Acidified bromide reacts with silver nitrate to produce pale yellow precipitate of silver
bromide which is sparingly soluble in ammonium hydroxide solution.

Br- + Ag+ AgBr(pale yellow ppt)

3.2.3 Iodide
Identification Test: To a small amount of salt, concentrated H 2SO4 is added. Violet vapours
(I2) are evolved whose intensity rises on heating with MnO2 addition to the reaction mixture
and turns starch solution blue.

2I- + 2H2SO4 I2 + SO2 + SO42- + 2H2O

2I- + 2H2SO4 + MnO2 I2 + MnSO4 + SO42- + 2H2O

I2 + starch solution blue complex

Due to the reaction of iodide with H2SO4, some HI, H2S, SO2 and sulphur are formed.

I- + H2SO4 HI + HSO4-

2HI + H2SO4 I2 + SO2 + 2H2O

6I- + 4H2SO4 3I2 + 4H2O + S + 3SO42-

8I- + 5H2SO4 4I2 + 4H2O + H2S + 4SO42-

 Confirmatory Tests:
(a) Organic Layer Test: A few drops of CCl4/CHCl3 and excess chlorine water are added to the
test tube containing the salt solution. The test tube is shaken vigorously. The organic layer
turns violet due to the dissolution of iodine in it.

Cl2 + 2I- I2 (dissolved in organic layer) + 2Cl-

(b) Acidified iodide reacts with silver nitrate to produce yellow precipitate of silver iodide
which is insoluble in ammonium hydroxide solution.

I- + Ag+ AgI(yellow ppt)

3.2.4 Nitrate
Identification Test: To a small amount of salt, concentrated H 2SO4 is added. A reddish-
brown gas with a pungent smell (NO 2) is evolved whose intensity rises on heating with the
addition of copper turnings to the reaction mixture and the solution turns blue.

NO3- + H+ HNO3

4HNO3 4NO2+ O2 + 2H2O

2NO3- + 4H2SO4 + 3Cu 3CuSO4 (blue) + SO42- + 4H2O + 2NO

2NO + O2 2NO2

The NO2 evolved turns acidified potassium iodide solution containing starch solution blue.

Confirmatory Test (Brown Ring Test): A few drops of concentrated sulphuric acid are added
to the test tube containing the salt solution and the test tube is cooled under tap water.
Freshly prepared ferrous sulphate solution is added along the side of the solution test tube
dropwise so that it forms a layer above the existing solution. A dark brown ring is formed at
the interface/junction of the two layers due to the formation of nitroso ferrous(I) sulphate.
One can do this test by adding ferrous sulphate first and then concentrated sulphuric acid.

The brown ring, ([Fe(NO)]SO4).

NO3- + H+ HNO3

6FeSO4 + 3H2SO4 + 2HNO3 3Fe2(SO4)3 + 4H2O + 2NO

FeSO4 + NO [FeI(NO)]SO4 (nitroso ferrous sulphate, the brown ring)

3.2.5 Oxalate
Identification Test: To a small amount of salt, concentrated H 2SO4 is added. A colourless,
odourless mixture of gases (CO and CO2) is evolved which turns lime water milky (CO 2) and
the gas leaving the lime water burns with a blue flame (CO).

(COO)22- + H2SO4 SO42- + H2O + CO + CO2

Confirmatory Tests:
(a) Calcium chloride is added to an acidified oxalate solution. A white precipitate of calcium
oxalate is formed, which is insoluble in ammonium oxalate and oxalic acid.

(COO)22- + CaCl2 CaC2O4 (white ppt) + 2Cl-

(b) The precipitate from (a) is filtered and dilute H 2SO4 and then dilute KMnO4 solution are
added and the resulting mixture is heated. Pink colouration of KMnO 4 is discharged.

CaC2O4 + H2SO4 H2C2O4 + CaSO4

5H2C2O4 + 2 KMnO4 + 3H2SO4 2MnSO4 + K2SO4 + 8H2O + 10CO2

The CO2 can be tested.

3.3 Group III

The group anions don't liberate gases or vapours even with concentrated sulphuric acid.

3.3.1 Sulphate
Confirmatory Tests:
(a) A few drops of barium chloride are added to the salt solution. A white precipitate
(BaSO4) is formed which is insoluble in concentrated hydrochloric or nitric acids.

SO42- + Ba2+ BaSO4(white ppt)

(b) A few drops of lead acetate are added to an acidified salt solution. A white precipitate
(PbSO4) is formed.

SO42- + Pb2+ PbSO4(white ppt)

3.3.2 Phosphate
Confirmatory Tests:
(a) Concentrated HNO3 and ammonium molybdate ((NH 4)2MoO4) are added to the salt
solution and the mixture is boiled. A canary-yellow precipitate of ammonium-
phospomolybdate (NH4)3[P(Mo3O10)4] is formed.

HPO42- + 3NH4+ + 12MoO42- + 23H+ (NH4)3[P(Mo3O10)4](canary-yellow ppt) + 12H2O

(b) Siver nitrate is added to the salt solution. A yellow precipitate of silver phosphate
(Ag3PO4) is formed, and is soluble in dilute nitric acid and in ammonia solution.
 HPO42- + 3Ag+ Ag3PO4(yellow ppt) + H+

Ag3PO4 + 2H+ H2PO4- + 3Ag+

Ag3PO4 + 6NH3 [Ag(NH3)2]3(PO4) (soluble)

3.3.3 Borate
Confirmatory Test: Add some ethanol and concentrated sulphuric acid to the salt solution
and then ignite the gas evolved. A green flame confirms borate ion.

BO33- + 3C2H5OH B(C2H5O)3(triethyl borate, burns with green flame) + 3OH-

4 Classification of Cations into Groups

Cations can be classified into seven groups 0, I, II, III, IV, V and VI based on the common
reagent(s) used to obtain the cation's precipitate. Group II has two further subdivisions:
Group IIA and Group IIB. Below is a groupwise classification of the cations, their group
reagents and the type and colour of the precipitate obtained by using the group reagent.
Group Group Reagent, Type of ppt Cation Colour of Precipitate
I Dil. HCl, Chlorides Pb2+ White
Hg22+ White
Ag+ White
IIA H2S added to the solution after Pb2+ Black
testing for Group I ions, Sulphides Cd2+ Yellow
that are insoluble in yellow
2+
ammonium sulphide (YAS, (NH4)2S) Cu Black
Hg2+ Black
Bi3+ Black/Brown
IIB H2S added to the solution after As3+ Yellow
testing for Group I ions, Sulphides Sn2+ Brown
that are soluble in yellow
ammonium sulphide Sn4+ Yellow
Sb3+ Orange
III HNO3 + heat then solid NH4Cl + Fe3+ Reddish-brown
NH4OH solution, Hydroxides Cr3+ Grey-Green
Al3+ Gelatinous White
IV H2S added to the solution after Mn2+ Pale Pink
testing for Group III ions, Sulphides Ni2+ Black
Co2+ Black
Zn2+ White
V NH4OH solution with solid (NH4)2CO3, Ba2+ White
Carbonates Sr2+ White
Ca2+ White
 Group 0 has NH4+ and Group VI has Mg2+, Na+ and K+. Groups 0 and VI don't have a group
reagent and hence don't have a precipitate. The groups are tested in the order they are
numbered. If no cation is found in a group, one is obligated to move on to the next group. If
a cation in a group is detected, confirmatory tests are performed.

5 Systematic Analysis of Cations

In this section, we will discuss only the confirmatory tests for the cations except for NH 4+, as
the identification tests for the cations from Groups I to V are already covered in the
previous section, which are nothing but the formation of the precipitate by treating the salt
solution with the group reagent. Group VI has no identification tests.

5.1 Group 0 (ammonium ion)

Identification Test: To a small amount of salt solution, a few drops of sodium hydroxide are
added and the mixture is heated. A colourless gas that smells of ammonia (ammonia of
course) is evolved which forms dense white fumes when it makes contact with a glass rod
dipped in hydrochloric acid.

NH4+ + NaOH NH3 + Na+

NH3 + HCl NH4Cl(dense white fumes)

Confirmatory Test: Pass the gas obtained in the identification test through Nessler's reagent
(K2HgI4 made alkaline with KOH). A brown precipitate of basic mercury(II) amido-iodine
(HgO.Hg(NH2)I) is formed.

2K2HgI4 + NH3 + 3KOH HgO.Hg(NH2)I(brown ppt) + 7KI + 2H2O

5.2 Group I
The group cations give chloride precipitate when treated with dilute HCl.

5.2.1 Lead (II)

PbCl2 dissolves in hot water as well as in excess HCl (due to the formation of [PbCl 4]2-). PbCl2
is the only group I chloride to dissolve in hot water, so it can be separated from the other
two ions this way. The precipitate is first dissolved in hot water and then the confirmatory
tests are performed. The confirmatory tests are as follows:
(a) To a hot solution of lead chloride, some KI solution is added. A yellow precipitate of lead
iodide is formed which is also soluble in hot water. If a hot solution of lead iodide is cooled
down, yellow spangles of lead iodide are formed.
PbCl2 + 2KI PbI2(yellow ppt) + 2KCl
(b) Adding potassium chromate to lead chloride solution gives a yellow precipitate of lead
chromate which dissolves in excess or hot NaOH solution, suggesting lead's amphoteric
nature. Lead chromate doesn't dissolve in ammonium acetate solution.
PbCl2 + K2CrO4 PbCrO4(yellow ppt) + 2KCl
PbCrO4 + 4NaOH Na2[Pb(OH)4] (soluble) + Na2CrO4
5.2.2 Mercury (I)
Mercurous chloride (Hg2Cl2) or calomel is insoluble in dilute acids. Calomel dissolves in aqua
regia giving soluble mercuric chloride (HgCl2).
3Hg2Cl2 + 2HNO3 + 6HCl 6HgCl2 + 2NO + 4H2O
Confirmatory Tests:
(a) Ammonia solution is added to calomel. A black mixture of mercury and mercuric
amidochloride (Hg(NH2)Cl) is precipitated out. The precipitate appears black due to
mercury.
Hg2Cl2 + 2NH3 Hg(NH2)Cl + Hg(black) + NH4+ + Cl-
(b) Adding KI solution slowly to mercurous salt solution gives a green precipitate of
mercurous iodide.
Hg22+ + 2I- Hg2l2 (green)
Adding excess KI gives soluble tetraiodomercurate(II) ions and black Hg precipitate.
Hg2I2 + 2I- [HgI4]2- + Hg
Boiling mercurous iodide in water gives red HgI2 precipitate and black Hg precipitate.
Hg2I2 Hg + Hgl2 (scarlet red)

5.2.3 Silver (I)

Silver chloride is insoluble in dilute HCl but in concentrated HCl, it dissolves due to the
formation of [AgCl2]-. Silver chloride is also soluble in ammonia solution as described
before. Hypo (sodium thiosulphate) dissolves silver chloride by the formation of
[Ag(S2O3)2]3-.
AgCl + 2S2O32- [Ag(S2O3)2]3- + Cl-
The above reaction takes place when fixing photographic negatives or positive prints during
development.
Confirmatory Tests:
(a) When hydrogen sulphide is passed through silver salt solution, a black precipitate of
silver sulphide is formed.
2Ag+ + H2S Ag2S(black) + 2H+
Silver sulphide is decomposed by hot nitric acid, and a white precipitate of sulphur is left
behind.
3Ag2S + 8HNO3 3S + 2NO + 6Ag+ + 6NO3- + 4H2O
(b) When potassium chromate is added to silver salt solution, a red precipitate of silver
chromate is formed.
2Ag+ + CrO42- Ag2CrO4(red)
(c) Adding disodium hydrogen phosphate to silver salt solution gives a yellow precipitate of
silver phosphate, which dissolves in nitric acid and ammonia solution.
3Ag+ + HPO42- Ag3PO4 + H+
5.3 Group IIA
The group cations give sulphide precipitate when H2S gas is passed through them in the
presence of HCl. The sulphides are insoluble in yellow ammonium sulphide. H 2SO4 is not
used as Group V ions like Ba2+ precipitate out as sulphate.

5.3.1 Lead (II)

Lead pops up again in Group II due to lead chloride being relatively soluble.
Confirmatory Tests:
(a) Lead sulphide is soluble in dilute HNO 3, forming lead nitrate and a precipitate of sulphur.
Adding dil. H2SO4 and alcohol to the lead nitrate solution gives a white precipitate of lead
sulphate which is soluble in boiling ammonium acetate solution.
3PbS + 8HNO3 3Pb(NO3)2 + 2NO + 4H2O + 3S
Pb(NO3)2 + H2SO4 PbSO4 + 2HNO3
PbSO4 + 4CH3COONH4 (NH4)2[Pb(CH3COO)4] (ammonium tetraacetoplumbate(II),
soluble) + (NH4)2SO4
(b) Taking the solution of the above lead complex and acidifying it, adding potassium
chromate gives a yellow precipitate of lead chromate. Adding potassium iodide to the
solution gives a yellow precipitate of lead iodide.
Pb2+ + CrO42- PbCrO4
Pb2+ + 2I- PbI2

5.3.2 Cadmium (II)

The formation of cadmium sulphide is reversible if concentration of acid is more than 0.5M.
Confirmatory Tests:
(a) Adding ammonia solution to salt solution gives white precipitate of cadmium hydroxide.
Adding excess ammonia solution dissolves the precipitate.
Cd2+ + 2NH3 + 2H2O Cd(OH)2 + 2NH4+
Cd(OH)2 + 4NH3 [Cd(NH3)4]2+ (soluble) + 2OH-
(b) Adding potassium cyanide slowly to the salt solution gives white precipitate of cadmium
cyanide. Excess KCN dissolves the precipitate by forming a complex, [Cd(CN)4]2-.
Cd2+ + 2CN- Cd(CN)2
Cd(CN)2 + 2CN- [Cd(CN)4]2-
[Cd(CN)4]2- isn't very stable; when H2S is introduced, CdS is precipitated.
[Cd(CN)4]2- + H2S CdS + 2H+ + 4CN-

5.3.3 Copper (II)

Confirmatory Tests:
(a) Copper sulphide dissolves in nitric acid due to the formation of copper(II) nitrate.
3CuS + 8HNO3 3Cu(NO3)2 + 2NO + 4H2O + 3S
 Heating the reaction mixture leads to the sulphur precipitated out getting oxidized to
sulphate and CuSO4 is formed. Adding a little NH4OH precipitates basic copper sulphate
(blue) and adding excess NH4OH dissolves the aformentioned precipitate due to the
formation of [Cu(NH3)4]2+.
S + 2HNO3 H2SO4 + 2NO
2Cu2+ + 2SO42- + 2NH3 + 2H2O Cu(OH)2.CuSO4(blue) + (NH4)2SO4
Cu(OH)2.CuSO4 + 8NH3 2[Cu(NH3)4]2+ + 2OH- + SO42-
(b) The above solution is acidified with acetic acid and potassium ferrocyanide is added. A
chocolate brown precipitate of copper ferrocyanide (Cu2[Fe(CN)6]) is formed.
[Cu(NH3)4]SO4 + 4CH3COOH CuSO4 + 4CH3COONH4
2CuSO4 + K4[Fe(CN)6] Cu2[Fe(CN)6](chocolate brown) + 2K2SO4

5.3.4 Mercury (II)

HgS dissolves in aqua regia, giving HgCl2.
Confirmatory Test:
(a) When KI is added slowly to the salt solution, a scarlet red precipitate of HgI 2 is formed.
Hg2+ + 2I- HgI2
Adding excess KI dissolves the precipitate due to the formation of [HgI4]2-.
HgI2 + 2I- [HgI4]2-
Making the above solution alkaline with KOH gives Nessler's reagent, which is used to
confirm the ammonium ion.

5.3.5 Bismuth (III)

Confirmatory Test:
(a) Adding sodium tetrahydroxostannate(II) (Na2[Sn(OH)4]) to the salt solution along with
sodium hydroxide first forms a white precipitate of bismuth hydroxide and then the
tetrahydroxostannate(II) reduces the bismuth hydroxide to black bismuth metal.
Bi3+ + 3OH- Bi(OH)3
2Bi(OH)3 + 3[Sn(OH)4]2- 2Bi(black) + 3[Sn(OH)6]2-

5.4 Group IIB

The group cations give sulphide precipitate when H2S gas is passed through them in the
presence of HCl. The sulphides are soluble in yellow ammonium sulphide.

5.4.1 Arsenic (III)

Confirmatory Test:
(a) Arsenous sulphide (As2S3) dissolves in yellow ammonium sulphide, forming ammonium
thioarsenide ((NH4)3AsS4), which decomposes to arsenic sulphide (As 2S5) on treatment with
dilute HCl. Arsenic sulphide dissolves in concentrated HNO 3 on heating due to the formation
of arsenic acid (H3AsO4). Adding ammonium molybdate to the reaction mixture and heating
it gives a canary-yellow precipitate of ammonium-arsinomolybdate ((NH 4)3[As(Mo3O10)4]).
 As2S3 + 3(NH4)2S2 2(NH4)3AsS4 + S
2(NH4)3AsS4 + 6HCl As2S5 + 3H2S + 6NH4Cl
3As2S5 + 10HNO3 + 4H2O 6H3AsO4 + 10NO + 15S
H3AsO4 + 12(NH4)2MoO4 + 21HNO3 (NH4)3[As(Mo3O10)4](canary-yellow) + 21 NH4NO3 +
12H2O

5.4.2 Tin (II)

Confirmatory Test:
(a) Adding a large amount of mercuric chloride solution quickly to the salt solution gives a
white precipitate of calomel (tin reduces mercury).
Sn2+ + 2HgCl2 Hg2Cl2 + Sn4+ + 2Cl-
However, if Sn2+ are in excess, then the precipitate turns grey on warming due to the
formation of mercury.
Sn2+ + Hg2Cl2 2Hg + Sn4+ + 2Cl-

5.4.3 Tin (IV)

Confirmatory Tests:
(a) Sn4+ , unlike Sn2+, does not react with mercuric chloride as Sn 4+ is already at tin's
maximum possible oxidation state (+4).
(b) Adding NaOH solution to the salt solution produces a white precipitate of tin(IV)
hydroxide which dissolves when excess NaOH is added due to the formation of
Na2[Sn(OH)6].
Sn4+ + 4OH- Sn(OH)4
Sn(OH)4 + 2OH- [Sn(OH)6]2- (soluble)
With ammonia/sodium carbonate, similar precipitate is obtained but is insoluble in excess
reagent.

5.4.4 Antimony (III)

Confirmatory Test:
(a) Adding zinc to the salt solution leaves a black precipitate of antimony.
2Sb3+ + 3Zn 2Sb(black) + 3Zn2+
The antimony left behind can be verified by dissolving it in warm dilute nitric acid and
passing H2S through the solution; an orange precipitate of antimony trisulphide is obtained.
Some toxic stibine (SbH3) may be liberated when using zinc to reduce Sb 3+; it is preferable to
use tin as a reducing agent instead.
2Sb3+ + 3Sn 2Sb + 3Sn2+

5.5 Group III

Before testing for Group III ions, conc. HNO3 is added and the solution is heated to oxidize
Fe2+ to Fe3+. The group cations give hydroxide precipitate when solid NH 4Cl and NH4OH
solution are added to their salt solution.
5.5.1 Iron (III)
Before performing the confirmatory tests, ferric hydroxide is converted to ferric chloride by
dissolving it in HCl.
Fe(OH)3 + 3HCl FeCl3 + 3H2O
Confirmatory Tests:
(a) Treating ferric chloride solution with potassium ferrocyanide gives a blue precipitate of
Prussian Blue or ferric ferrocyanide (Fe4[Fe(CN)6]3).
4FeCl3 + 3K4[Fe(CN)6] Fe4[Fe(CN)6]3(blue) + 12KCl
If potassium ferrocyanide is added in excess, then a colloidal solution of soluble prussian
blue (KFe[Fe(CN)6]) is formed and it cannot be separated.
FeCl3 +K4[Fe(CN)6] KFe[Fe(CN)6] + 3KCl
(b) Treating ferric chloride solution with potassium thiocyanate gives the solution a blood
red colour due to the formation of [Fe(SCN)]2+.
Fe3+ + SCN- [Fe(SCN)]2+ (blood red colour)

5.5.2 Chromium (III)

Confirmatory Test:
(a) Adding NaOH solution to chromium salt solution gives green precipitate of chromium
hydroxide and excess NaOH solution dissolves the precipitate due to the formation of
[Cr(OH)4]-.
Cr3+ + 3OH- Cr(OH)3
Cr(OH)3 + OH- [Cr(OH)4]- [green solution is formed]
The above (alkaline) solution is oxidized with hydrogen peroxide to yellow chromate
solution.
2[Cr(OH)4]- + 3H2O2 +2OH- 2CrO42- + 8H2O
After decomposing excess hydrogen peroxide by boiling, the chromate ion is confirmed by
the addition of barium chloride which results in a yellow precipitate of barium chromate.
CrO42- + Ba2+ BaCrO4
If chromate is confirmed this way, then chromium (III) is confirmed.

5.5.3 Aluminium (III)

Confirmatory Tests:
(a) Adding NaOH solution to aluminium salt solution gives gelatinous white precipitate of
aluminium hydroxide and excess NaOH solution dissolves the precipitate due to the
formation of [Al(OH)4]-.
Al3+ + 3OH- Al(OH)3
Al(OH)3 + OH- [Al(OH)4]-
[Al(OH)4]- is sometimes written as AlO2-, called aluminate.
(b) No precipitate is obtained if aluminium salt solution is treated with sodium acetate in
 cold conditions. If excess sodium acetate is added and the mixture is boiled, a voluminous
precipitate of basic aluminium acetate Al(OH)2CH3COO is formed.
Al3+ + 3CH3COO- + 2H2O Al(OH)2CH3COO + 2CH3COOH

5.6 Group IV
The group cations give sulphide precipitate when H2S gas is passed through them in the
presence of NH4Cl and NH4OH i.e. H2S gas is passed through the solution after testing for
Group III ions and no Group III ion was detected.

5.6.1 Manganese (II)

Confirmatory Test:
(a) Manganese sulphide dissolves in hydrochloric acid on boiling, giving manganese
chloride. After adding NaOH solution to manganese chloride solution in excess, a white
precipitate of manganese hydroxide is formed which on standing gets atmospherically
oxidized to brown coloured hydrated manganese dioxide, MnO.(OH)2.
MnS + 2HCl MnCl2 + H2S
MnCl2 + 2NaOH Mn(OH)2 + 2NaCl
Mn(OH)2 + [O] MnO.(OH)2(brown)

5.6.2 Nickel (II)

Confirmatory Test:
(a) Nickel sulphide dissolves in aqua regia to form nickel chloride which is soluble in water.
When dimethylglyoxime (dmg) is added to the aqueous solution of NiCl 2, and the solution is
made alkaline with NH4OH, a red precipitate of [Ni(dmg)2] is obtained. Dimethylglyoxime is
a bidentate ligand with -1 unit of charge when bound to nickel (due to the loss of one of the
oxime hydrogen atoms which is taken by basic NH4OH).
3NiS + 2HNO3 + 6HCl 3NiCl2 + 2NO + 4H2O + 3S
NiCl2 + 2NH4OH + 2dmg [Ni(dmg)2](red) + 2NH4Cl + 2H2O

The red-coloured nickel-dmg complex

Dimethylglyoxime (dmg).
that is precipitated out after
performing nickel's confirmatory test.

5.6.3 Cobalt (II)

Confirmatory Test:
 (a) Cobalt sulphide dissolves in aqua regia giving cobalt chloride. The resulting solution is
first neutralized with NH4OH, then acidified with acetic acid and a concentrated solution of
potassium nitrite is added. A yellow precipitate of potassium hexanitritocobaltate(III),
K3[Co(NO2)6] is obtained.
CoS + HNO3 + 3HCl CoCl2 + NOCl + S + 2H2O
CoCl2 + 7KNO2 + 2CH3COOH K3[Co(NO2)6](yellow) + NO + 2KCl + 2CH3COOK

5.6.4 Zinc (II)

Before performing the confirmatory tests, zinc sulphide is dissolved in HCl to form soluble
zinc chloride.
ZnS + 2HCl ZnCl2 + H2S
Confirmatory Tests:
(a) Adding NaOH solution to the zinc chloride solution gives a white precipitate of zinc
hydroxide which dissolves in excess NaOH on heating due to the formation of sodium
zincate (Na2ZnO2).
ZnCl2 + 2NaOH Zn(OH)2 + 2NaCl
Zn(OH)2 + 2NaOH Na2ZnO2 + 2H2O
(b) Adding potassium ferrocyanide to the zinc chloride solution neutralized with NH 4OH
gives a white or bluish-white precipitate of zinc ferrocyanide.
2ZnCl2 + K4[Fe(CN)6] Zn2[Fe(CN)6] + 4KCl

5.7 Group V
The group cations give carbonate precipitate when solid (NH 4)2CO3 and NH4OH solution are
added to their salt solution. The group cations can be confirmed by performing the flame
test on the carbonate precipitates.

5.7.1 Barium (II)

Confirmatory Test:
(a) Barium carbonate is dissolved in acetic acid to give barium acetate and potassium
chromate is added to the solution. A yellow precipitate of barium chromate is formed
which confirms barium ion.
BaCO3 + 2CH3COOH Ba(CH3COO)2 + CO2 + H2O
Ba(CH3COO)2 + K2CrO4 BaCrO4 + 2CH3COOK

5.7.2 Strontium (II)

Confirmatory Test:
(a) Strontium carbonate is dissolved in acetic acid to give strontium acetate and ammonium
sulphate is added to the solution. The test tube containing the reaction mixture is heated
and the sides of the test tubes are scratched with a glass rod. After the test tube cools, a
white precipitate of strontium sulphate is formed which confirms strontium ion.
SrCO3 + 2CH3COOH Sr(CH3COO)2 + CO2 + H2O
 Sr(CH3COO)2 + (NH4)2SO4 SrSO4 + 2CH3COONH4

5.7.3 Calcium (II)

Confirmatory Test:
(a) Calcium carbonate is dissolved in acetic acid to give calcium acetate and ammonium
oxalate is added to the solution. A white precipitate of calcium oxalate is formed which
confirms calcium ion.
CaCO3 + 2CH3COOH Ca(CH3COO)2 + CO2 + H2O
Ca(CH3COO)2 + (NH4)2C2O4 CaC2O4 + 2CH3COONH4

5.8 Group VI
This group contains Mg2+, Na+ and K+. There is no group reagent and confirmatory tests are
performed directly.

5.8.1 Magnesium (II)

Confirmatory Test:
(a) Adding disodium hydrogenphosphate to the magnesium salt solution (having group V
reagents) and scratching the inner walls of the test tube containing the reaction mixture
gives a white crystalline precipitate of magnesium ammonium phosphate confirming
magnesium ion.
Mg2+ + HPO42- + NH3 MgNH4PO4

5.8.2 Sodium (I)

Confirmatory Test:
(a) Adding uranyl magnesium acetate solution to the sodium salt solution gives a yellow
crystalline precipitate of sodium magnesium uranyl acetate NaMg(UO2)3(CH3COO)9.
Na+ + Mg2+ + 3UO22+ + 9CH3COO- NaMg(UO2)3(CH3COO)9(yellow)

5.8.3 Potassium (I)

Confirmatory Tests:
(a) To the potassium salt solution, sodium hexanitritocobaltate(III) solution is added. A
yellow precipitate of potassium hexanitritocobaltate(III) is formed.
3K+ + [Co(NO2)6]3- K3[Co(NO2)6]
(b) To the potassium salt solution, perchloric acid is added. A white crystalline precipitate of
potassium perchlorate is formed.
K+ + ClO4- KClO4

6 References
1. Vogel's Qualitative Inorganic Analysis, 7th edition (2006)
2. NCERT Chemistry Lab Manual for Class XII