Detection and Systematic

Analysis of Cation
Step - 1 :
Preliminary Examination of the Salt for
Identification of Cation
1. Colour Test:
Observe the colour of the salt carefully, which may provide useful
information about the cations. Table 1 gives the characteristic colours of the
salts of some cations.

Colour Cations Indicated

Light green, Yellow, Brown Fe2+ , Fe3+

Blue Cu2+
Bright green Ni2+
Blue, Red, Violet, Pink Co2+
Light pin Mn2+

Table 1: Characteristic colours of some metal ions

2. Dry Heating Test:

(i) Take about 0.1 g of the dry salt in a clean and dry test tube.
(ii) Heat the above test tube for about one minute and observe the colour
of the residue when it is hot and also when it becomes cold.
Observation of changes gives indications about the presence of cations,
which may not be taken as conclusive evidence (see Table)

Colour when cold Colour when hot Inference

Blue White Cu2+

Green Dirty white or yellow Fe2+
White Yellow Zn2+
Pink Blue Co2+

Table 2: Inferences from the colour of the salt in cold and on heating.

3. Flame Test:
The chlorides of several metals impart characteristic colour to the flame
because they are volatile in non-luminous flame. This test is performed with
the help of a platinum wire as follows :
 (i) Make a tiny loop at one end of a platinum wire.
(ii) To clean the loop dip it into concentrated hydrochloric acid and hold it
in a non-luminous flame. (Fig.)
(iii) Repeat step (ii) until the wire imparts no colour to the flame.
(iv) Put 2-3 drops of concentrated hydrochloric acid on a clean watch glass
and make a paste of a small quantity of the salt in it.
(v) Dip the clean loop of the platinum wire in this paste and introduce the
loop in the non-luminous (oxidising) flame (Fig.).
(vi) Observe the colour of the flame first with the naked eye and then
through a blue glass and identify the metal ion with the help of Table
given below:

Platinum wire Platinum

loop
(a) Paste

(d)
(b)

(c)
(e)
Platinum loop

Fig. 1: Performing Flame test

Colour of the flame Colour of the flame Inference

observed by naked eye observed through
blue glass

Green flame with blue Same colour as observed Cu2+

centre without glass
Crimson red Purple Sr2+
Apple green Bluish Green Ba2+
Brick red Green Ca2+

Table 3: Inference from the flame test

4. Borax Bead Test:

This test is employed only for coloured salts because borax reacts with
metal salts to form metal borates or metals, which have characteristic
colours.
 (i) To perform this test make a loop at the end of the platinum wire and
heat it in a flame till it is red hot.
(ii) Dip the hot loop into borax powder and heat it again until borax forms a
colourless transparent bead on the loop.
Before dipping the borax bead in the test salt or mixture,confirm that
the bead is transparent and colourless. If it is coloured this means that,
the platinum wire is not clean.Then make a fresh bead after cleaning
the wire.
(iii) Dip the bead in a small quantity of the dry salt and again hold it in the
flame.
(iv) Observe the colour imparted to the bead in the non - luminous flame as
well as in the luminous flame while it is hot and when it is cold (Fig.).
(v) To remove the bead from the platinum wire, heat it to redness and
tap the platinum wire with your finger. (Fig.).

(a) Heating in (b) Heating in

reducing flame oxidising flame
Fig. 2: Borax bead test

Borax bead

Fig. 3: Removing borax bead

Heating in oxidising Heating in redusing

(non-luminous) flame (luminous) flame
Inference
Colour of the salt bead Colour of the salt bead
In cold In hot In cold In hot

Blue Green Red opaque Colourless Cu2+

Reddish brown Violet Grey Grey Sr2+
Light violet Light violet Colourless Colourless Ba2+
Yellow Yellowish brown Green Green Ca2+

Table 4: Inference from borax bead Test

5. Charcoal Cavity Test:

Metallic carbonate when heated in a charcoal cavity decomposes to give

corresponding oxide. The oxide appears as a coloured residue in the
cavity. Sometimes oxide may be reduced to metal by the carbon of the
charcoal cavity. The test may be performed as follows:
(i) Make a small cavity in a charcoal block with the help of a charcoal
borer. Do not apply pressure otherwise it will crack [Fig. 4 (a)].
(ii) Fill the cavity with about 0.2 g of the salt and about 0.5 g of anhydrous
sodium carbonate.
(iii) Moisten the salt in the cavity with one or two drops of water, otherwise
salt/mixture will blow away.
(iv) Use a blowpipe to heat the salt in a luminous (reducing) flame and
observe the colour of oxide/ metallic bead formed in the cavity both
when hot and cold [ Fig. 5 ( b)]. Obtain oxidising and reducing flame as
shown in Fig. 5: a and b.
(v) Always bore a fresh cavity for testing the new salt.

(a) Making charcoal cavity (b) Heating salt in the cavity

Fig. 4: Charcoal cavity test - step 1

Air Air

(a) Oxidising flame (b) Reducing flame

Fig. 5: Obtaining oxidising and reducing flame

When test is performed with CuSO4 , the following change occurs:
Heat
Cu SO4 + Na2 CO3 Cu2 CO3 + Na 2 SO4

Heat
CuCO3 CuO + CO2

Heat
CuO + C Cu + CO
Red colour

In case of ZnSO4 :
Heat
Zn SO4 + Na2 CO3 Zn CO3 + Na 2 SO4

Heat
ZnCO3 ZnO + CO2

The metal ion can be inferred from Table

Observations Inference

Yellow residue when hot and grey metal when cold Pb2+
White residue with the odour of garlic As3+
Brown residue Cd2+
Yellow residue when hot and white when cold Zn2+

Table 5: Inference from the charcoal cavity test

5. Cobalt Nitrate Test

If the residue in the charcoal cavity is white, cobalt nitrate test is performed.
(i) Treat the residue with two or three drops of cobalt nitrate solution.
(ii) Heat it strongly in non-luminous flame with the help of a blow pipe and
observe the colour of the residue.

On heating, cobalt nitrate decomposes into cobalt (II) oxide, which gives a
characteristic colour with metal oxide present in the cavity.
Thus, with ZnO, Al2 O3 and MgO, the following reactions occur.

Heat
2Co( NO3)2 2CoO + 4Na 2 + O2

CoO + ZnO CoO. ZnO

Green

CoO + MgO CoO. MgO

Pink

CoO + Al2O3 CoO. Al2O3

Blue
Step - 2 :
Wet Tests for Identification of Cations
The cations indicated by the preliminary tests given above are confirmed by
systematic analysis given below.
The first essential step is to prepare a clear and transparent solution of the
salt. This is called original solution. It is prepared as follows:

1. Preparation of Original Solution (O.S.):

To prepare the original solution, following steps are followed one after the
other in a systematic order. In case the salt does not dissolve in a particular
solvent even on heating, try the next solvent.
The following solvents are tried:
1. Take a little amount of the salt in a clean boiling tube and add a few mL of
distilled water and shake it. If the salt does not dissolved, heat the content
of the boiling tube till the salt completely dissolves.
2. If the salt is insoluble in water as detailed above, take fresh salt in a clean
boiling tube and add a few mL of dil.HCl to it. If the salt is insoluble in
cold, heat the boiling tube till the salt is completely dissolved.
3. If the salt does not dissolve either in water or in dilute HCl even on
heating,try to dissolve it in a few mL of conc. HCl by heating.
4. If salt does not dissolve in conc. HCl, then dissolve it in dilute nitric acid.
5. If salt does not dissolve even in nitric acid then a mixture of conc. HCl
and conc. HNO3 in the ratio 3:1 is tried. This mixture is called aqua regia.
A salt not soluble in aqua regia is considered to be an insoluble salt.

2. Group Analysis:
(I) Analysis of Zero group cation (NH4+)
(a) Take 0.1g of salt in a test tube and add 1-2 mL of NaOH solution to it
and heat. If there is a smell of ammonia, this indicates the presence of
ammonium ions. Bring a glass rod dipped in hydrochloric acid near the
mouth of the test tube. White fumes are observed.
(b) Pass the gas through Nessler’s reagent. Brown precipitate is obtained.

Chemistry of Confirmatory Tests for NH4+ :

a) Ammonia gas evolved by the action of sodium hydroxide on ammonium
salts reacts with hydrochloric acid to give ammonium chloride, which is
visible as dense white fume.
(NH4)2 SO4 + 2NaOH NH2 SO4 + 2NH3 + 2H2 O
NH3 + HCl NH4 Cl

On passing the gas through Nessler’s reagent, a brown colouration or a

precipitate of basic mercury(II) amido-iodine is formed.

2K2HgI4 + NH3 + 3KOH HgO.Hg(NH2)I + 7KI + 2H2 O

For the analysis of cations belonging to groups I-VI, the cations are
precipitated from the original solution by using the group reagents
(see Table) according to the scheme shown in the flow chart given below:
The separation of all the six groups is represented as below:

Original Solutions
Dil HCl

Precipitate, Group I If no precipitate is formed

(Pb2+) as Chloride Pass H2 S gas

Precipitate, Group II If no precipitate, take original solution

2+ 2+ 3+
(Pb , Cu , As ) Heat (0.S.) with conc. HNO3 ,
as sulphate cool and add solid NH4 CI + NH4 OH
solution in excess

Precipitate, Group III If no precipitate

( Fe3+ , Al3+ ) Pass H2 S
as hydroxides

Precipitate, Group IV If no precipitate take original solution

( Co2+ , Ni2+ , Mn2+ , Zn2+ ) Add NH4 OH and solid (NH4 )2 CO3
as sulphides

Precipitate, Group V If no precipitate take original solution

to test Group VI, Mg2+
( Ba2+ , Sr2+ , Ca2+ )
as carbonates

Flow Chart
 Group Cation Group Reagent

Group zero NH4+ None

Group - I Pb2+ Dilute HCl
Group - II Pb2+, Cu2+, As3+ H2 S gas in presence of dil.HCl
Group - III Al3+ , Fe3+ NH4OH in presence of NH4Cl
Group - IV Co2+, Ni2+, Mn2+ , Zn2+ H2 S in presence of NH4OH
Group - V Ba2+, Sr2+, Ca2+ (NH4)2CO3 in presence of
NH4OH
Group - VI Mg2+ None

Table 6: Group reagents for precipitating ions

(II) Analysis of Group-I cations

Take a small amount of original solution ( if prepared in hot conc. HCl) in a
test tube and add cold water to it and cool the test tube under tap water.
If a white precipitate appears, this indicates the presence of Pb2+ ions in
group – I. On the other hand, if the original solution is prepared in water
and on addition of dil.HCl, a white precipitate appears, this may also be Pb2+.
Confirmatory tests are described below in Table

Experiment Observations

Dissolve the precipitate in hot water A yellow precipitate is obtained

and divide the hot solution into three which is soluble in NaOH and
parts. insoluble in ammonium acetate
1. Add potassium iodide solution to solution.
the first part. A white precipitate is obtained
2. To the second part add potassium
chromate solution. which is soluble in ammonium
3. To the third part of the hot acetate solution.
solution add few drops of alcohol
and dilute sulphuric acid.

Table 7: Confirmatory tests for Group-I cation (Pb2+)

Chemistry of Confirmatory Tests of Pb2+ ions :

Lead is precipitated as lead chloride in the first group.
The precipitate is soluble in hot water.
1. On adding potassium iodide (KI) solution, a yellow precipitate of lead
iodide is obtained which confirms the presence of Pb2+ ions

PbCl2 + 2KI PbI2 + 2KCl

This yellow precipitate (PbI2 ) is soluble in boiling water and reappears on

cooling as shining crystals.
2. On addition of potassium chromate (K2 CrO4 ) solution a yellow
precipitate of lead chromate is obtained. This confirms the presence of
Pb2+ ions.

PbCl2 + K2 CrO4 PbCrO4 + 2KCl

The yellow precipitate (PbCrO4 ) is soluble in hot NaOH solution.

PbCrO4 + 4NaOH Na2 [Pb(OH)4 ] + Na2 CrO4

Sodium tetra
hydroxoplumbate (II)

3. A white precipitate of lead sulphate (PbSO4 ) is formed on addition of

alcohol followed by dil. H2 SO4

PbCl2 + H2 SO4 PbSO4 + 2HCl

(White
precipitate)

Lead sulphate is soluble in ammonium acetate solution due to the formation

of tetraacetoplumbate(II) ions. This reaction may be promoted by addition of
few drops of acetic acid.

PbSO4 + 4CH3 COONH4 (NH4 )2 [Pb(CH3 COO)4 ] + (NH4 )2 SO4

(III) Analysis of Group-II cations

If group-I is absent, add excess of water to the same test tube.
Warm the solution and pass H2 S gas for 1-2 minutes (Fig.).

Shake the test tube. If a precipitate appears, this indicates the presence of
group-II cations.
Pass more H2 S gas through the solution to ensure complete precipitation
and separate the precipitate.

If the colour of the precipitate is black, itindicates the presence of Cu2+ or

Pb2+ ions.
If it is yellow in colour, then presence of As3+ ions is indicated.

Take the precipitate of group-II in atest tube and add excess of yellow
ammonium sulphide solution to it. Shake the test tube. If the precipitate is
insoluble, group II-A (copper group) is present.

If the precipitate is soluble, this indicates the presence of group-II B

(arsenic group).
Confirmatory tests for the groups - II A and II B are given in Table.
 Rubber
cork
Stop cock

H2S
Gas
H2S Gas
Iron
sulphide

Sulphuric
acid

Fig. Kipp’s apparatus for preparation of H2S gas

Black precipitate of GroupII A ions If a yellow precipitate soluble

(Pb2+, Cu2+) insoluble in yellow ammonium in yellow ammonium sulphide
sulphide is formed. is formed then As3+ ion is
present.
Boil the precipitate of GroupII A with Acidify this solution with
dilute nitric acid and add a few drops of dilute HC1. A yellow
alcohol and dil. H2 SO4 . precipitate is formed. Heat
the precipitate with
White precipitate If no precipitate concentrated nitric acid and
confirms the Apresence is formed, add add ammonium molybdate
of Pb2+ ions. Dissolve excess of solution.
the precipitate in ammonium A canary yellow precipitate
ammonium acetate hydroxide is formed.
solution. Acidify with solution. A blue
acetic acid and divide solution is
the solution into two obtained, acidify
parts. it with acetic
(i) To the first part add acid and add
potassium chromate potassium
solution, a yellow ferrocyanide
precipitate is formed. solution.
(ii)To the second part, A chocolate
add potassium iodide brown
solution, a yellow precipitate is
precipitate is formed. formed.

Table 8: Confirmatory tests for Group-II A and II B cations

Group-II A (Copper Group)
Chemistry of Confirmatory Tests for NH4+ :
1. Test for Lead ion (Pb2+)
Lead sulphide precipitate dissolves in dilute HNO3 . On adding dil. H2 SO4
and a few drops of alcohol to this solution a white precipitate of lead
sulphate appears.This indicates the presence of lead ions.

3PbS + 8HNO3 3Pb(NO3 )2 + 2NO + 4H2 O + 3S

Pb(NO3 )2 + H2 SO4 PbSO4 + 2HNO3

The white precipitate dissolves in ammonium acetate solution on boiling.

When this solution is acidified with acetic acid and potassium chromate
solutionis added, a yellow precipitate of PbCrO4 is formed.
On adding potassium iodide solution, a yellow precipitate of lead iodide
is formed.

PbSO4 + 4CH3 COONH4 (NH4 )2 [Pb(CH3 COO)4 ] + (NH4 )2 SO4

Pb2+ + CrO 2 - PbCrO
4 4
(Yellow precipitate)

Pb2+ + 2I - PbI2
(Yellow precipitate)

2. Test for Copper ion (Cu2+)

(a) Copper sulphide dissolves in nitric acid due to the formation of copper
nitrate.

3CuS + 8HNO3 3Cu(NO3 )2 + 2NO + 3S + 4H2 O

On heating the reaction mixture for long time, sulphur is oxidised tosulphate
and copper sulphate is formed and the solution turns blue. A small amount
of NH4 OH precipitates basic copper sulphate which is solublein excess of
ammonium hydroxide due to the formation of
tetraamminecopper (II) complex.

S + 2HNO3 H2 SO4 + 2NO

2-
2Cu2+ + SO4 + 2NH3 +2H2 O Cu(OH)2 .CuSO4 + NH4+
Cu(OH)2 CuSO4 + 8NH3 2[Cu(NH3 )4 ]SO4 + 2OH- + SO42 -

The blue solution on acidification with acetic acid and then adding potassium
ferrocyanide [K4Fe(CN)6] solution gives a chocolate colouration due to the
formation of copper ferrocyanide i.e.Cu2 [Fe(CN)6 ].

[Cu(NH3 )4 ]SO4 + 4CH3 COOH CuSO4 + 4CH3 COONH4

2CuSO4 + K4 [Fe(CN)6 ] Cu2 [Fe(CN)6 ] +2K2 SO4

Group-II B (Arsenic Group)
Chemistry of Confirmatory Tests for NH4+ :
1. Test for Lead ion (Pb2+)
group- II precipitate dissolves in yellow ammonium sulphide and the colour
of the solution is yellow, this indicates the presence of As3+ ions.
Ammonium thioarsenide formed on dissolution of As2 S3 decomposes with
dil. HCl, and a yellow precipitate of arsenic (V) sulphide is formed which
dissolves in concentrated nitric acid on heating due to the formation of
arsenic acid. On adding ammonium molybdate solution to the reaction
mixture and heating, a canary yellow precipitate is formed. This confirms
the presence of As3+ ions.
As2 S3 + 3(NH4 )2 S2 2(NH4 )3 As S4 + S
(Yellow ammonium
sulphide)
2(NH4 )3 AsS4 + 6HCl As2 S5 + 3H2 S + 6NH4 Cl

3As2 S5 + 10HNO3 + 4H2 O 6H3 AsO4 + 10NO + 15S

(Arsenic acid)

H3 AsO4 + 12(NH4 )2 MoO4 + 21HNO3 (NH4 )3 [As(Mo3 O10 )4 ]

(Arsenic (Ammonium + 21NH4 NO3 + H2 O
acid) molybdate) (Ammonium arsinomolybdate
yellow precipitate)

(IV) Analysis of Group-III cations

If group-II is absent, take original solution and add 2-3 drops of conc. HNO3
to oxidise Fe2+ ions to Fe3+ ions. Heat the solution for a few minutes.
After cooling add a small amount of solid ammonium chloride (NH4Cl) and
an excess of ammoniumhydroxide (NH4OH) solution till it smells of
ammonia. Shake the test tube. If a brown or white precipitate is formed, this
indicates the presence of group-III cations.
Confirmatory tests of group-III cations are summarised in Table Observe the
colour and the nature of the precipitate. A gelatinous white precipitate
indicates the presence of aluminium ion (Al3+). If the precipitate is brown in
colour, this indicates the presence of ferric ions (Fe3+).

Brown Precipitate Fe3+ White precipitate Al3+

Dissolve the precipitate in dilute Dissolve the white precipitate in dilute
HCl and divide the solution into HCl and divide into two parts.
two parts. (a) To the first part add sodium hydrox
(a) To the first part add potassium -ide solution and warm. A white
ferrocyanide solution [Potasium gelatinous precipitate soluble in
hexacyanoferrate (II)]. A blue excess of sodium hydroxide solution.
precipitate/colouration appears. (b) To the second part first add blue
(b) To the second part add litmus solution and then ammonium
potassium thiocyanate solution. hydroxide solution drop by drop
A blood red colouration along the sides of the test tube. A
appears. blue floating mass in the colourless
solution is obtained.
Table 9: Confirmatory test for Group-III cations
Chemistry of confirmatory tests of Group-III cations
When original solution is heated with concentrated nitric acid, ferrous ions are
oxidised to ferric ions.

2FeCl2 + 2HCl + [O] 2FeCl3 + H2 O

1. Test for Aluminium ions (Al3+)

(a) When the solution containing aluminium chloride is treated with sodium
hydroxide, a white gelatinous precipitate of aluminium hydroxide is
formed which is soluble in excess of sodium hydroxide solution due to
the formation of sodium meta aluminate.

AlCl3 + 3NaOH Al(OH)3 + 3NaCl

Al(OH)3 + NaOH NaAlO2 + 2H2 O
(White gelatinous
precipitate)
(b) In the second test when blue litmus is added to the solution, a red
colouration is obtained due to the acidic nature of the solution.
On addition of NH4 OH solution drop by drop the solution becomes
alkaline and aluminium hydroxide is precipitated. Aluminium hydroxide
adsorbs blue colour from the solution and forms insoluble adsorption
complex named ‘lake’. Thus a blue mass floating in the colourless solution
is obtained. The test is therefore called lake test.

2. Test for ferric ions (Fe3+)

Reddish brown precipitate of ferric hydroxide dissolves in hydrochloric acid
and ferric chloride is formed.

Fe(OH)3 + 3HCl FeCl3 + 3H2 O

(a) When the solution containing ferric chloride is treated with potassium
ferrocyanide solution a blue precipitate/colouration is obtained.
The colour of the precipitate is Prussian blue. It is ferric ferro-cyanide.
The reaction takes place as follows:

4FeCl3 + 3K4 [Fe(CN)6 ] Fe4 [Fe(CN)6 ]3 + 12KCl

If potassium hexacyanoferrate (II) (i.e. potassium ferrocyanide) is added in

excess then a product of composition KFe[Fe(CN)6 ] is formed.
This tends to form a colloidal solution (‘soluble Prussian blue’) and cannot
be filtered.

FeCl3 + K4 [Fe(CN)6 ] KFe[Fe(CN)6 ] + 3KCl

(b) To the second part of the solution, add potassium thiocyanate

(potassium sulphocyanide) solution. The appearance of a blood red
colouration confirms the presence of Fe3+ ions.
(V) Analysis of Group-IV cations
If group-III is absent, pass H2 S gas in the solution of group-III for a few
minutes. If a precipitate appears (white, black or flesh coloured), this
indicates presence of group-IV cations. Table gives a summary of
confirmatory tests of group-IV cations.

White Precipitate White Precipitate Black Precipitate

Zn2+ Mn2+ Ni2+ , Co2+
Dissolve the precipitate Dissolve the Dissolve the precipitate in
in dilute HCl by boiling. precipitate in dilute aqua regia. Heat the
Divide the solution into HCl by boiling, solution to dryness and
two parts. then add sodium cool. Dissolve the residue
(a) To the first part add hydroxide solution in water and divide the
sodium hydroxide in excess. A white solution into two parts.
solution. precipitate is formed (a) To the first part of the
A whiteprecipitate which turns brown solution add ammonium
solublein excess of on keeping. hydroxide solution till it
sodiumhydroxide becomes alkaline. Add
solution confirms a few drops of dimethyl
theions presence of glyoxime and shake the
Zn2+ions. test tube. Formation of
(b) Neutralise the a bright red precipitate
second part with confirms the presence
ammonium hydroxide of Ni2+ ions.
solution and add (b) Neutralise the second
potassium part with ammonium
ferrocyanide solution. hydroxide solution.
A bluish white Acidify it with dilute
precipitate appears. acetic acid and add
solid potassium nitrite.
A yellow precipitate
confirms the presence
of Co2+ ions.
Table 10: Confirmatory test for Group-IV cations

Chemistry of confirmatory tests of Group–IV cations

Fourth group cations are precipitated as their sulphides. Observe the colour
of the precipitate. A white colour of the precipitate indicates the presence
of zinc ions, a flesh colour indicates the presence of manganese ions and a
black colour indicates the presence of Ni2+ or Co2+ ions.
1. Test for Zinc ion (Zn2+)
Zinc sulphide dissolves in hydrochloric acid to form zinc chloride.

ZnS + 2HCl ZnCl2 + H2 S

(a) On addition of sodium hydroxide solution it gives a white precipitate of
zinc hydroxide, which is soluble in excess of NaOH solution on heating.
This confirms the presence of Zn2+ ions.
ZnCl2 + 2NaOH Zn(OH)2 + 2NaCl
Zn(OH)2 + 2NaOH Na2 ZnO2 + 2H2 O
Sodium Zincate
(b) When potassium ferrocyanide K4 Fe(CN)6 solution is added to the
solution after neutralisation by NH4 OH solution, a white or a bluish
white precipitate of zinc ferrocyanide appears.

2ZnCl2 + K4 [Fe(CN)6 ] Zn2 [Fe(CN)6 ] + 4KCl

(Zinc ferrocyanide)

2. Test for Zinc ion (Mn2+)

Manganese sulphide precipitate dissolves in dil. HCl on boiling. On addition
of NaOH solution in excess, a white precipitate of manganese hydroxide is
formed which turns brown due to atmospheric oxidation into hydrated
manganese dioxide..

MnS + 2HCl MnCl2 + H2 S

MnCl2 + 2NaOH Mn(OH)2 + 2NaCl
(White precipitate)
Mn(OH)2 + [O] MnO(OH)2
Hydrated manganese dioxide
(Brown colour)

3. Test for Zinc ion (Ni2+)

The black precipitate of nickel sulphide dissolves in aqua regia and the reaction
takes place as follows:

3NiS + 2HNO3 + 6HCl 3NiCl2 + 2NO + 3S + 4H2 O

After treatment with aqua regia nickel-chloride is obtained which is soluble

in water. When dimethyl glyoxime is added to the aqueous solution of nickel
chloride, made alkaline, by adding NH4 OH solution, a brilliant red
precipitate is obtained.
H
O O

H3C N N CH3
H3 C – C = N – OH C C
Ni + 2NH4 Cl + 2H2 O
NiCl2 + 2NH4 OH + H3 C – C = N – OH C C
N N
H3C CH3

O O
H
Complex of red colour
(Stable form of complex)
4. Test for Cobalt ion (Co2+)
Cobalt sulphide dissolves in aqua regia in the same manner as nickel sulphide.
When the aqueous solution of the residue obtained after treatment with
aqua regia is treated with a strong solution of potassium nitrite after
neutralisation with ammonium hydroxide and the solution is acidified with
dil. acetic acid, a yellow precipitate of the complex of cobalt named
potassium hexanitritocobaltate (III) is formed.
CoS + HNO3 + 3HCl CoCl2 + NOCl + S + 2H2 O

CoCl2 + 7KNO2 + 2CH3 COOH K3 [Co(NO2 )6 ] + 2KCl + 2CH3 COOK + NO + H2 O

Potassium
hexanitritocobaltate(III)
(Yellow precipitate)

(VI) Analysis of Group- V cations

If group-IV is absent then take original solution and add a small amount
of solid NH4 Cl and an excess of NH4 OH solutionfollowed by solid
ammonium carbonate (NH4 )2 CO3 . If a white precipitate appears, this
indicates the presence of group–V cations. Dissolve the white
precipitate by boiling with dilute acetic acid and divide the solution into
three parts one each for Ba2+, Sr2+ and Ca2+ ions.
Preserve a small amount of the precipitate for flame test. Summary of
confirmatory tests is given in Table:

Dissolve the precipitate by boiling with dilute acetic acid and

divide the solution into three parts one each for
Ba2+, Sr2+ and Ca2+ ion
Ba2+ ions Sr2+ ions Ca2+ ions
(a) To the first part (a) If barium is absent, (a) If both barium and
add potassium take second part of strontium are absent,
chromate solution. the solution and add take the third part of
A yellow precipita ammonium sulphate the solution. Add
-te appears. solution. Heat and ammonium oxalate
scratch the sides of solution and shake well.
(b) Perform the flame the test tube with a A white precipitate of
test with the glass rod and cool. calcium oxalate is
preserved A white precipitate obtained.
precipitate. is formed.
A grassy green (b) Perform the flame test
flame is obtained. (b) Perform the flame with the preserved
test with the precipitate. A brick red
preserved precipitate. flame, which looks
A crimson-red flame greenish-yellow through
confirms the presence blue glass, confirms the
of Sr2+ ions. presence of Ca2+ ions.

Table 11: Confirmatory test for Group–V cations

Chemistry of confirmatory tests of Group– V cations

The Group–V cations are precipitated as their carbonates which dissolve in
acetic acid due to the formation of corresponding acetates.

1. Test for Barium ion (Ba2+)

(a) Potassium chromate (K2 CrO4 ) solution gives a yellow precipitate of
barium chromate when the solution of fifth group precipitate in acetic
acid is treated with it.
 BaCO3 + 2CH3 COOH (CH3 COOH)2 Ba + H2 O + CO2

(CH3 COO)2 Ba + K2 CrO4 BaCrO4 + 2CH3 COOK

Barium chromate
(Yellow precipitate)

(b) Flame test : Take a platinum wire and dip it in conc. HCl. Heat it strongly
until the wire does not impart any colour to the non-luminous flame.
Now dip the wire in the paste of the (Group–V) precipitate in conc. HCl.
Heat it in the flame. A grassy green colour of the flame confirms the
presence of Ba2+ ions.

2. Test for Strontium ion (Sr2+)

(a) Solution of V group precipitate in acetic acid gives a white precipitate of
strontium sulphate with ammonium sulphate, (NH4 )2 SO4 , solution on
heating and scratching the sides of the test tube with a glass rod.
SrCO3 + 2CH3 COOH (CH3 COOH)2 Sr + H2 O + CO2

(CH3 COO)2 Sr + [NH4 ]2 SO4 SrSO4 + 2CH3 COONH4

Strontium sulphate
(White precipitate)

(b) Flame test : Perform the flame test as given in the case of Ba2+.
A crimson red flame confirms the presence of Sr2+ ions.

3. Test for Calcium ion (Ca2+)

(a) Solution of the fifth group precipitate in acetic acid gives a white
precipitate with ammonium oxalate solution.
CaCO3 + 2CH3 COOH (CH3 COO)2 Ca + H2 O + CO2

(CH3 COO)2 Ca + [NH4 ]2 C2 O4 (COO)2 Ca + 2CH3 COONH4

Ammonium Calcium oxalate
oxalate (White precipitate)

(b) Flame test : Perform the flame test as mentioned above. Calcium imparts
brick red colour to the flame which looks greenish-yellow through blue glass.

(VII) Analysis of Group- VI cations

If group–V is absent then perform the test for Mg2+ ions as given below.

Chemistry of Confirmatory Tests of Group–VI cations

1. Test for Magnesium ion (Mg2+)

(a) If group–V is absent the solution may contain magnesium carbonate,

which is soluble in water in the presence of ammonium salts because the
equilibrium is shifted towards the right hand side.

+ 2- -
NH + CO
4 3 NH3 + HCO3
The concentration of carbonate ions required to produce a precipitate is
not attained. When disodium hydrogenphosphate solution is added and
the inner walls of the test tube are scratched with a glass rod, a white
crystalline precipitate of magnesium ammonium phosphate is formed which
indicates the presence of Mg2+ ions.

Mg2+ + Na2 HPO4 Mg[NH4 ]PO4 + NH4 OH + 2Na+ + H2 O

Magnesium ammonium
phosphate
(White precipitate)

Note down the observations and the inferences of the qualitative analysis in
tabular form.