Systematic Analysis and

Detection of Anion
Aim
To detect one cation and one anion in the given salt from the following ions:
Cations -
Pb2+, Cu2+,As3+,Al3+,Fe3+,Mn2+,Ni2+,Zn2+,Co2+,Ca2+,Sr2+,Ba2+,Mg2+,NH4+
Anions :
2- 2- 2- 2- - - - - - 3- 2- -
CO3 , S , SO3 , SO4 , NO2, NO3, Cl , Br , I ,PO4 ,C2O4 ,CH3COO

Theory
Two basic principles of great use in the analysis are:
(i) the Solubility product; and
(ii) the Common ion effect.
When ionic product of a salt exceeds its solubility product, precipitation
takes place. Ionic product of salt is controlled by making use of common ion
effect which you have studied in the textbook of chemistry.

Material Required:
• Boiling tube : As per need
• Test tubes : As per requirement
• Measuring cylinder : One
• Test tube stand : One
• Test tube holder : One
• Delivery tube : One
• Corks : As per need
• Filter paper : As per need
• Reagents : As per need

Systematic Analysis of Anions

Step 01
Preliminary Test with Dilute Sulphuric Acid

In this test the action of dilute sulphuric acid (procedure is given below) on
the salt is noted at room temperature and on warming.
Carbonate , sulphide , sulphite,, nitrite , and acetate react with dilute
sulphuric acid to evolve different gases. Study of the characteristics of the
gases evolved gives information about the anions. Summary of characteristic
properties of gases is given in Table given below:
 Observations Gas evolved Possible Anion
A colourless, odourless gas CO2 Carbonate (CO32 -)
is evolved with brisk
effervescence, which turns
lime water milky.
Colourless gas with the H2S Sulphide (S2-)
smell of rotten eggs is
evolved which turns lead
acetate paper black

Colourless gas with a SO2 Sulphite (SO32 -)

pungent smell, like burning
sulphur which turns
acidified potassium
dichromate solution green.
Brown fumes which turn NO2 Nitrite (NO2- )
acidified potassium iodide
solution containing starch
solution blue.

Colourless vapours with CH3COOH Vapours Acetate (CH3COO-)

smell of vinegar. Vapours
turn blue litmus red.
Table 1
Procedure
(a) Take 0.1g of the salt in a test tube and add 1–2mL of dilute sulphuric acid.
Observe the change, if any, at room temperature. If no gas is evolved,
warm the content of the test tube. If gas is evolved test it by using the
apparatus shown in fig. and identify the gas evolved (See Table )

Reagent
Boiling
tube

Fig. 1

Confirmatory tests for CO32-, S2-, SO32-, NO2- and CH3COO-

Confirmatory (wet) tests for anions are performed by using water extract
when salt is soluble in water and by using sodium carbonate extract when
salt is insoluble in water. Confirmation of CO32- is done by using aqueous
solution of the salt or by using solid salt as such because sodium carbonate
extract contains carbonate ions.
Water extract is made by dissolving salt in water. Preparation of sodium
carbonate extract is given below.

Preparation of sodium carbonate extract

Take 1g of salt in a porcelain dish or boiling tube.
Mix about 3g of solid sodium carbonate and add 15mL of distilled water to it.
Stir and boil the content for about 10 minutes. Cool, filter and collect the
filtrate in a test tube and label it as sodium carbonate extract. Confirmatory
tests for acid radicals, which react with dilute sulphuric acid are given below
in Table

Anion Confirmation test

Carbonate (CO32 -) Take 0.1g of salt in a test tube, add dilute sulphuric
acid. CO2 gas is evolved with brisk effervescence
which turns lime water milky. On passing the gas
for some more time, milkiness disappears.

Sulphide (S2-) Take 1mL of water extract and make it alkaline by

adding ammonium hydroxide or sodium carbonate
extract. Add a drop of sodium nitroprusside
solution. Purple or violet colouration appears.

Sulphite (SO32 -) (a) Take 1mL of water extract or sodium carbonate

extract in a test tube and add barium chloride
solution. A white precipitate is formed which
dissolves in dilute hydrochloric acid and sulphur
dioxide gas is also evolved.
(b) Take the precipitate of step (a) in a test tube and
add a few drops of potassium permanganate
solution acidified with dil.H2SO4
Colour of potassium permanganate solution
gets discharged.

Nitrite (NO2- ) (a) Take 1mL of water extract in a test tube.

Add a few drops of potassium iodide solution
and a few drops of starch solution, acidify with
acetic acid. Blue colour appears.
Acidify 1mL of water extract with acetic acid.
Add 2-3 drops of sulphanilic acid solution follow
-ed by 2-3 drops of 1-naphthylamine reagent.
Appearance of red colour indicates the presence
of nitrite ion.

Acetate (CH3COO-) (a) Take 0.1 g of salt in a china dish. Add 1 mL of

ethanol and 0.2 mL conc.H2SO4 and heat. Fruity
odour confirms the presence of acetate ion.
(b) Take 0.1 g of salt in a test tube, add 1-2 mL
distilled water, shake well filter if necessary.
Add 1 to 2mL neutral** ferric chloride solution
to the filtrate.
Deep red colour appears which disappears on
boiling and a brown-red precipitate is formed.

Table 2
Chemistry of Confirmatory Tests
1. Test for Carbonate ion [CO32-]
If there is effervescence with the evolution of a colourless and odourless gas
on adding dil. H2SO4 to the solid salt, this indicates the presence of carbona
-te ion. The gas turns lime water milky due to the formation of CaCO3

Na2CO3 + H2SO4 Na2SO4 + H2O + CO2 Ca(OH)2+ CO2 CaCO3 + H2O

If CO2 gas is passed in excess through lime water, the milkiness produced
disappears due to the formation of calcium hydrogen carbonate which is
soluble in water.
CaCO3 + CO2 + H2O Ca(HCO3)2

2. Test for Sulphide ion [S2-]

(a) With warm dilute H2SO4 a sulphide gives hydrogen sulphide gas which
smells like rotten eggs. A piece of filter paper dipped in lead acetate
solution turns black on exposure to the gas due to the formation of lead
sulphide which is black in colour.

Na2 S + H2 SO4 Na2 SO4 + H2 S

(CH3COO)2 Pb + H2S PbS + 2CH3COOH

Lead Suphide
Black Precipitate

(b) If the salt is soluble in water, take the solution of salt in water make it
alkaline with ammonium hydroxide and add sodium nitroprusside solution.
If it is insoluble in water take sodium carbonate extract and add a few
drops of sodium nitroprusside solution. Purple or violet colouration due
to the formation of complex compound Na4 [Fe(CN)5NOS] confirms the
presence of sulphide ion in the salt.

Na2 S + Na2 [Fe(CN)5NO] Na4 [Fe(CN)5NOS]

(Sodium Nitroprusside) (Purple Colour Complex)

3. Test for Sulphite ion [ SO32 - ]

(a) On treating sulphite with warm dil. H2SO4 , SO2 gas is evolved which is
suffocating with the smell of burning sulphur.
Na2 SO3 + H2 SO4 Na2 SO4 + H2 O + SO2
The gas turns potassium dichromate paper acidified with dil. H2SO4 ,
green
K2Cr2O7 + H2 SO4 + 3SO2 K2 SO4 + Cr2 (SO4 )3 + H2 O
(Chromium sulphate)
(b )An aqueous solution or sodium carbonate extract of the salt produces a
white precipitate of barium sulphite on addition of barium chloride
solution.
Na2 SO3 + BaCl2 2NaCl + BaSO3
This precipitate gives following tests.

(i) This precipitate on treatment with dilute HCl, dissolves due to decom
-position of sulphite by dilute HCl. Evolved SO2 gas can be tested.
BaSO3 + 2HCl BaCl2 + H2O + SO2

(ii)Precipitate of sulphite decolourises acidified potassium permanganate

solution.
BaSO3 + H2 SO4 BaSO4 + H2O + SO2

2KMnO4 + 3H2 SO4 K2SO4 + 2MnSO4 + 3H2O + 5[O]

SO2 + H2 O + [O] H2SO4

-
4. Test for Nitrite ion [ NO2 ]
(a) On treating a solid nitrite with dil. H2SO4 and warming , reddish brown
fumes of , NO2 gas are evolved. Addition of potassium iodide solution to
the salt solution followed by freshly prepared starch solution and
acidification with acetic acid produces blue colour. Alternatively, a filter
paper moistened with potassium iodide and starch solution and a few
drops of acetic acid turns blue on exposure to the gas due to the
interaction of liberated iodine with starch.

(i) 2NaNO2 + H2 SO4 Na2 SO4 + 2HNO2

3HNO2 HNO3 + 2NO + H2O
2NO + O2 2NO2 (Brown gas)
HNO2 + CH3COO-
-
(ii) NO2 + CH3COOH
2HNO2 + 2KI + 2CH3COOH 2CH3COOK + 2H2O + 2NO + I2
I2 + Starch Blue complex

(b) Sulphanilic acid — 1-naphthylamine reagent test (Griss-Ilosvay test)

On adding sulphanilic acid and 1-naphthylamine reagent to the water
extract or acidified with acetic acid, sulphanilic acid is diazotised in the
reaction by nitrous acid formed. Diazotised acid couples with
1-naphthylamine to form a red azo-dye. The test solution should be very
dilute. In concentrated solutions reaction does not proceed beyond
diazotisation.
4. Test for Acetate ion [ CH3COO- ]
(a) If the salt smells like vinegar on treatment with dil. H2SO4, this indicates
the presence of acetate ions. Take 0.1g of salt in a china dish and add 1mL
of ethanol.
Then add about 0.2 mL of conc. H2SO4 and heat. Fruity odour of ethyl
acetate indicates the presence of CH3COO- ion.

2CH3COONa + H2 SO4 Na2 SO4 + 2CH3COOH

CH3COOH + C2H5OH CH3COOC2 H5 + H2O

(b) Acetate gives deep red colour on reaction with neutral ferric chloride
solution due to the formation of complex ion which decomposes on
heating to give Iron (III) dihydroxyacetate as brown red precipitate.

6CH3COO- + 3Fe3+ + 2H2 O [Fe3(OH)2 (CH3COO)6 ]+ + 2H+

[Fe3(OH)2 (CH3COO)6 ]+ + 4H2O 3[Fe(OH)2 (CH3COO)] + 3CH3COOH + H+

Iron (III) dihydroxyacetate
(Brown-red precipitate)

Step 02
Preliminary Test with Concentrated Suphuric Acid

If no positive result is obtained from dil. H2SO4 test, take 0.1g of salt in a
test tube and 3-4 drops of conc.H2SO4. Observe the change in the reaction
mixture in cold and then warm it. Identify the gas evolved on heating.

Table 3

Anion Gas/ Vapours Possible Anions

Evolved
A colourless gas with pungent HCl Chloride (Cl -)
smell, which gives dense white
fumes when a rod dipped in
ammonium hydroxide is brought
near the mouth of the test tube.
Reddish brown gas with a Br2 vapours Bromide (Br-)
pungent odour is evolved.
Intensity of reddish gas increases
on heating the reaction mixture
after addition of solid MnO2 to
the reaction mixture. Solution
also acquires red colour.
Violet vapours, which turn starch I2 vapours Iodide (I-)
paper blue and a layer of violet
sublimate is formed on the sides
of the tube. Fumes become
dense on adding MnO2 to the
reaction mixture.
 Brown fumes evolve which become NO2 -
Nitrate (NO ) 3
dense upon heating the reaction
mixture after addition of copper
turnings and the solution acquires
blue colour.

Colourless, odourless gas is evolved CO and CO2 2-

Oxalate (C2O4 )
which turns lime water milky and
the gas coming out of lime water
burns with a blue flame, if ignited.

Confirmatory tests for the anions which react with concentrated sulphuric
- - - - 2-
acid are given in Table Confirmatory tests for Cl , Br , I , NO3 and C2O4

Table 4
Anion Confirmatory Test
-
Chloride (Cl ) (a) Take 0.1g of salt in a test tube, add a pinch of
manganese dioxide and 3-4 drops of conc.
sulphuric acid. Heat the reaction mixture.
Greenish yellow chlorine gas is evolved which
is detected by its pungent odour and bleaching
action.
(b) Take 1mL of sodium carbonate extract in a test
tube, acidfy it with dil. HNO3 or take water
extract and add silver nitrate solution. A curdy
white precipitate is obtained which is soluble in
ammonium hydroxide solution.
(c) Take 0.1g salt and a pinch of solid potassium
dichromate in a test tube, add conc. H2SO4 ,
heat and pass the gas evolved through sodium
hydroxide solution. It becomes yellow.
Divide the solution into two parts. Acidify one
part with acetic acid and add lead acetate
solution. A yellow precipitate is formed.
Acidify the second part with dilute sulphuric
acid and add 1mL of amyl alcohol followed by
1mL of 10% hydrogen peroxide. After gentle
shaking the organic layer turns blue.
-
Bromide (Br ) (a) Take 0.1g of salt and a pinch of MnO2 in a test
tube. Add 3-4 drops conc.sulphuric acid and
heat. Intense brown fumes are evolved.
(b) Neutralise 1mL of sodium carbonate extract
with hydrochloric acid (or take the water
extract). Add 1mL carbon tetrachloride (CCl4 )
/chloroform (CHCl3 )/ carbon disulphide.
Now add an excess of chlorine water dropwise
and shake the test tube. A brown colouration
in the organic layer confirms the presence of
bromide ion.
(c) Acidify 1mL of sodium carbonate extract with
dil. HNO3 (or take 1mL water extract) and
add silver nitrate solution. A pale yellow
precipitate soluble with difficulty in ammonium
hydroxide solution is obtained.
 Iodide (I-) (a) Take 1mL of salt solution neutralised with HCl
and add 1mL chloroform/carbon tetrachloride/
carbon disulphide. Now add an excess of
chlorine water drop wise and shake the test
tube.
A violet colour appears in the organic layer.
(b) Take 1mL of sodium carbonate extract acidify
it with dil. HNO3 (or take water extract).
Add, silver nitrate solution. A yellow precipitate
insoluble in NH4OH solution is obtained.

Nitrate (NO3-) (a) Take 1mL of salt solution in water in a test

tube. Add 2mL conc. of H2SO4 and mix
thoroughly. Cool the mixture under the tap.
Add freshly prepared ferrous sulphate along the
sides of the test tube without shaking.
A dark brown ring is formed at the junction of
the two solutions.

Oxalate (C2O42 -) (a) Take 1mL of water extract or sodium carbonate

extract acidified with acetic acid and add calcium
chloride solution. A white precipitate insoluble
in ammonium oxalate and oxalic acid solution
but soluble in dilute hydrochloric acid and dilute
nitric acid is formed.
(b) Take the precipitate from test (a) and dissolve it
in dilute H2SO4. Add very dilute solution of
KMnO4 and warm. Colour of KMnO4 solution
is discharged. Pass the gas coming out through
lime water. The lime water turns milky.
Table 4

Chemistry of Confirmatory Tests

–
1. Test for Chloride ion [Cl ]
(a) If on treatment with warm conc. H2SO4 the salt gives a colourless gas
with pungent smell or and if the gas which gives dense white fumes with
ammonia solution, then the salt may contain Cl– ions and the following
reaction occurs.
NaCl + H2 SO4 NaHSO4 + HCl
HCl + NH3 NH4Cl

(b) If a salt gives effervescence on heating with conc. H2SO4 and MnO2 and
a light greenish yellow pungent gas is evolved, this indicates the presence
of Cl– ions.

MnO2 + 2NaCl + 2H2 SO4 Na2SO4 + MnSO4 + 2H2O + Cl2

(c) Salt solution acidified with dilute HNO3 on addition of silver nitrate
solution gives a curdy white precipitate soluble in ammonium hydroxide
solution. This indicates the presence of Cl– ions in the salt.
 NaCl + AgNO3 NaNO3 + AgCl
AgCl + 2NH4OH [Ag(NH3 )2 ] Cl + 2H2O

(d) Mix a little amount of salt and an equal amount of solid potassium
dichromate (K2Cr2O7) in a test tube and add conc. H2SO4 to it.
Heat the test tube and pass the evolved gas through sodium hydroxide
solution. If a yellow solution is obtained, divide the solution into two
parts. Acidify the first part with acetic acid and then add lead acetate
solution. Formation of a yellow precipitate of lead chromate confirms
the presence of chloride ions in the salt. This test is called chromyl
chloride test.

4NaCl + K2Cr2O7 + 6H2SO4 2KHSO4 + 2CrO2Cl2 + 4NaHSO4

(Chromyl chloride) + 3H2O

CrO2Cl2 + 4NaOH Na2CrO4 + 2NaCl + 2H2O

(CH3COO)2Pb + Na2CrO4 PbCrO4 + 2CH3COONa

Acidify the second part with dilute sulphuric acid and add small amounts
of amyl alcohol and then 1mL of 10% hydrogen peroxide solution.
On gentle shaking organic layer turns blue. C2O42 - ion formed in the
reaction of chromyl chloride with sodium hydroxide reacts with
hydrogen peroxide to form chromium pentoxide (CrO5 ) (See structure)
which dissolves in amyl alcohol to give blue colour.

2-
C2O4 + 2H+ + 2H2O2 CrO5 + 3H2O
(Chromium pentoxide)

2. Test for Bromide ion [Br– ]

If on heating the salt with conc.H2SO4 reddish brown fumes of bromine
are evolved in excess, this indicates the presence of Br- ions. The fumes
get intensified on addition of MnO2. Bromine vapours turn starch paper
yellow.
2NaBr + 2H2 SO4 Br2 + SO2 + Na2 SO4 + 2H2O
2NaBr + MnO2 + 2H2 SO4 Na2 SO4+ MnSO4 + 2H2O + Br2

(a) Add 1mL of carbon tetrachloride (CCl4)/chloroform (CHCl3 )** and

excess of freshly prepared chlorine water dropwise to the salt solution
in water or sodium carbonate extract neutralised with dilute HCl.
Shake the test tube vigorously. The appearance of an orange brown
colouration in the organic layer due to the dissolution of bromine in it,
confirms the presence of bromide ions.

2NaBr + Cl2 2NaCl + Br2

 (b) Acidify the sodium carbonate extract of the salt with dil. HNO3 .
Add silver nitrate (AgNO3) solution and shake the test tube.
A pale yellow precipitate is obtained which dissolves in ammonium
hydroxide

NaBr + AgNO3 NaNO3 + AgBr

(Silver bromide - Pale yellow precipitate)

3. Test for Iodide ion [I– ]

(a) If on heating the salt with conc. H2 SO4 , deep violet vapours with a
pungent smell are evolved. These turns starch paper blue and a violet
sublimate is formed on the sides of the test tube, it indicates the
presence of I- ions. Some HI, sulphur dioxide, hydrogen sulphide, and
sulphur are also formed due to the following reactions.

2NaI + 2H2 SO4 Na2 SO4 + SO2 + 2H2 O + I2

I2 + Starch Blue colour
NaI + H2 SO4 NaHSO4 + HI
2HI + H2 SO4 2H2O + I2 + SO2
6NaI + 4H2 SO4 3I2 + 4H2O + S + 3Na2 SO4
8NaI + 5H2 SO4 4I2 + H2 S + 4Na2 SO4 + 4H2O

On adding MnO2 to the reaction mixture, the violet vapours become

dense.
2NaI + MnO2 + 2H2 SO4 I2 + MnSO4 + Na2 SO4 + 2H2O

(b) Add 1mL of CHCl3 or CCl4 and chlorine water in excess to the salt
solution in water or sodium carbonate extract neutralised with dil.HCl
and shake the test tube vigorously. Presence of violet colouration in the
organic layer confirms the presence of iodide ions.

2NaI + Cl2 2NaCl + I2

(c) Iodine dissolves in the organic solvent and the solution becomes violet.
Acidify sodium carbonate extract of the salt with dil.HNO3 and add
AgNO3 solution. Appearance of a yellow precipitate insoluble in excess
of NH4OH confirms the presence of iodide ions.

NaI + AgNO3 AgI + NaNO3

Silver iodide
(Yellow precipitate)
 –
4. Test for Iodide ion [NO3 ]
(a) If on heating the salt with conc. H2 SO4 light brown fumes are evolved
then heat a small quantity of the given salt with few copper turnings or
chips and conc. H2SO4. Evolution of excess of brown fumes indicates
the presence of nitrate ions. The solution turns blue due to the
formation of copper sulphate.

NaNO3 + H2 SO4 NaHSO4 + HNO3

4HNO3 4NO2 + O2 + 2H2O
2NaNO3 + 4H2 SO4 + 3Cu 3CuSO4 +Na2 SO4+ 4H2O + 2NO
2NO + O2 2NO2
(Brown fumes)
(b) Take 1mL of an aqueous solution of the salt and add 2mL conc. H2SO4
slowly. Mix the solutions thoroughly and cool the test tube under the
tap. Now, add freshly prepared ferrous sulphate solution along the sides
of the test tube dropwise so that it forms a layer on the top of the liquid
already present in the test tube. A dark brown ring is formed at the
junction of the two solutions due to the formation of nitroso ferrous
sulphate (Fig.). Alternatively first ferrous sulphate is added and then
concentrated sulphuric acid is added.

FeSO4

Dark brown ring

Fig. 2

Formation of Dark Brown Ring

NaNO3 + H2 SO4 NaH SO4+ HNO3
6 FeSO4 + 3H2 SO4 + 2HNO3 3Fe2(SO4 )3 + 4H2O + 2NO
FeSO4 + NO [Fe(NO)]SO4
Nitroso ferrous sulphate
(Brown)

5. Test for Oxalate ion [C2O42 – ]

If carbon dioxide gas along with carbon monoxide gas is evolved in the
preliminary examination with concentrated sulphuric acid,this gives
indication about the presence of oxalate ion.

(COONa)2 + Conc. H2 SO4 Na2 SO4 + H2O +CO2 + CO

Oxalate is confirmed by the following tests:

(a) Acidify sodium carbonate extract with acetic acid and add calcium
chloride solution. A white precipitate of calcium oxalate, insoluble in
ammonium oxalate and oxalic acid solution indicates the presence of
oxalate ion.

CaCl2 + Na2C2O4 CaC2O4 + 2NaCl

Calcium oxalate
(White precipitate)

(b) KMnO4 test

Filter the precipitate from test (a). Add dil.H2SO4 to it followed by dilute
KMnO4 solution and warm. Pink colour of KMnO4 is discharged:

CaC2O4 + H2SO4 CaSO4 + H2C2O4

Calcium Oxalic
sulphate acid

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

Pass the gas evolved through lime water. A white precipitate is formed
which dissolves on passing the gas for some more time.

Step 03
Test for Sulphate and Phosphate

If no positive test is obtained in Steps-I and II, then tests for the presence of
sulphate and phosphate ions are performed. These tests are summarised in
Table - Confirmatory tests for Sulphate and Phosphate.

Table 5
Ion Confirmatory Test

Sulphate (SO42 -) (a) Take 1mL water extract of the salt in water
or sodium carbonate and after acidifying with
dilute hydrochloric acid add BaCl2 solution.
White precipitate insoluble in conc. HCl or
conc. HNO3 is obtained.
(b) Acidify the aqueous solution or sodium
carbonate extract with acetic acid and add lead
acetate solution.
Appearance of white precipitate confirms the
presenceof SO42 - ion.

Phosphate (PO43-) (a) Acidify sodium carbonate extract or the

solution of the salt in water with conc. HNO3
and add ammonium molybdate solution and
heat to boiling. A canary yellow precipitate is
formed.
Chemistry of Confirmatory Tests
1. Test for Sulphate ion [ SO42 - ]
(a) Aqueous solution or sodium carbonate extract of the salt acidified with
acetic acid on addition of barium chloride gives a white precipitate of
barium sulphate insoluble in conc. HCl or conc. HNO3

Na2 SO4 + BaCl2 BaSO4 + 2NaCl

Barium sulphate
(White precipitate)

(b) Sulphate ions give white precipitate of lead sulphate when aqueous
solution or sodium carbonate extract neutralised with acetic acid is
treated with lead acetate solution.

Na2 SO4 + (CH3COO)2 Pb PbSO4 +2CH3 COONa

2. Test for Phosphate ion [ PO43 - ]

(a) Add conc. HNO3 and ammonium molybdate solution to the test
solution containing phosphate ions and boil.
A yellow colouration in solution or a canary yellow precipitate of
ammonium-phosphomolybdate,

(NH4)3 [P (Mo3O10 )4 ] is formed. Each oxygen of phosphate has been

replaced by Mo3O10 group.

Na2HPO4 + 12(NH4)2MoO4 (NH4)3 [P (Mo3O10 )4 ] + 2NaNO3

MoO4 + 23 HNO3 + 21NH4NO3 + 12H2O