Salt Analysis

CHAPTER
4
Qualitative analysis is carried out through the reactions which are easily perceptible to our senses such as
sight and smell. Such reactions involve:
(a) Formation of a precipitate
(b) Change in colour
(c) Evolution of gas etc.

Systematic analysis of an inorganic salt involves the following steps:

(i) Preliminary examination of solid salt and its solution.
(ii) Determination of anions by reactions carried out in solution (wet tests) and confirmatory tests.
(iii) Determination of cations by reactions carried out in solution (wet tests) and confirmatory tests.

Preliminary examination of a salt often furnishes important information, which simplifies further course of
analysis. Although these tests are not conclusive but sometimes they give quite important clues for the
presence of certain anions or cations. These tests can be performed within 10-15 minutes. These involve
noting the general appearance and physical properties, such as colour, smell, solubility etc. of the salt. These
are named as dry tests.

Heating of dry salt, blow pipe test, flame tests, borax bead test, sodium carbonate bead test, charcoal cavity
test etc. come under dry tests.

Qualitative analysis involves identification of ions (cations and anion) of a salt or a mixture of salts through
their characteristic reactions. The process involves.
(i) Analysis of anions and
(ii) Analysis of cations.

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2 | Salt Analysis
ANALYSIS OF ANIONS (ACIDIC RADICALS)
Group I : Anions which liberate gases with dil. HCl or dil. H2SO4
(CO32–, HCO3–, SO32–, S2–, S2O32–, NO2–)

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3 | Salt Analysis
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 carbonate ion.
The gas turns lime water milky due to the formation of CaCO3 (Fig. 7.1)
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.
Na2S + H2SO4 Na2SO4 + H2S
(CH3COO)2Pb + H2S  PbS + 2CH3COOH
Lead sulphide
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.
Na 2S  Na 2 [Fe(CN)5 NO] 
 Na 2 [Fe(CN)5 NOS]
Sodium nitroprusside Complex of Purple colour

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.
Na2SO3 + H2SO4 Na2SO4 + H2O + SO2
The gas turns potassium dichromate paper acidified with dil. H2SO4, green.
K2Cr2O7 + H2SO4 + 3SO2  K2SO4 + Cr2 (SO4 )3  H2O
Chromium
sulphate (green)

(b) An aqueous solution or sodium carbonate extract of the salt produces a white precipitate of barium
sulphite on addition of barium chloride solution.
Na2SO3 + BaCl2 2NaCl + BaSO3
This precipitate gives following tests.

(i) This precipitate on treatment with dilute HCl, dissolves due to decomposition of sulphite by dilute
HCl. Evolved SO2 gas can be tested.
BaSO3 + 2HCl BaCl2 + H2O + SO2
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4 | Salt Analysis
(ii) Precipitate of sulphite decolourises acidified potassium permanganate solution.
BaSO3 + H2SO4 BaSO4 + H2O + SO2
2KMnO4 + 3H2SO4 K2SO4 + 2MnSO4 + 3H2O + 5 [O]
SO2 + H2O + [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 + H2SO4 Na2SO4 + 2HNO2
3HNO2 HNO3 + 2NO + H2O
2NO + O2 2NO2
Brown gas
(ii) NO2– + CH3COOH HNO2 + CH3COO–
2HNO2 + 2KI + 2CH3COOH 2CH3 COOK + 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.
NO2– + CH3COOH HNO2 + CH3COO–
+
NH3.CH3COO– N=N–OOCCH3

+HNO2 +2H2O

SO3H SO3H

N=N–OOCCH3

+ HO3S N=N NH2 + CH2COOH

SO3H NH2
1-Naphtyle amine Red azo-dye
The test solution should be very dilute. In concentrated solutions reaction does not proceed beyond
diazotisation.

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5 | Salt Analysis
5. 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 0.1 g of salt in a china dish and add 1 mL of ethanol. Then add about 0.2 mL of conc. H2SO4
and heat. Fruity odour of ethyl acetate indicates the presence of CH3COO– ion.
2 CH3COONa + H2SO4 Na2SO4 + 2 CH3COOH
CH3COOH + C2H5OH  CH3COOC2 H5 + H2O
Ethylacetate
(Fruity odour)

(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+ + 2H2O [Fe3(OH)2 (CH3COO)6]+ + 2H+
[Fe3(OH)2 (CH3COO)6]+ + 4H2O  3[Fe  OH 2 (CH 3COO)] + 3CH3COOH+ H+
Iron  III dihydroxyacetate
 Brown  red precipitate 

Group II : Gases or acid vapours evolved with conc. H2SO4 (Cl–, Br–, I–, NO3– )

Conc. H2 SO4
NH4OH
White fumes of NH4Cl
(pungent)

KI + starch
MnO2 + H2SO4 Blue

(yellowish green)
Cl
–
Moist litmus paper
AgNO3
Bleached
NH4OH
(white)
[Ag(NH3)2] Cl
(soluble)
K2Cr2O7 + H2SO4 NaOH CH3COOH + (CH3COO)2Pb
Na2CrO4
(red) (yellow solution) (yellow ppt.)

Conc. H2SO4
Br2
(Brown)

MnO2 + H2SO4 starch paper

Br2 Orange red
Br
–

AgNO3
AgBr Partially soluble in NH4OH
(yellow)

K2Cr2O7 + H2SO4
CCl4 layer turns brown due to evolution of Br2

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6 | Salt Analysis
Conc. H2SO4
I2
(violet)

MnO2 + H2SO4
I2

AgNO3
I– AgI Insoluble in NH4OH
(yellow)
CCl4 + Cl 2(H 2O)
CCl4 layer turns violet due to evolution of I2

HgCl2 KI
HgI2 K2[HgI4]
(scarlet ppt.) (excess) (soluble)

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 + H2SO4  NaHSO4  HCl 
Sodium Hydrogen chloride
hydrogen sulphate Colourless gas

HCl + NH3  NH4Cl

Ammonium chloride
White fumes

(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 + 2H2SO4 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
Silver chloride
 White precipitate 
AgCl + 2NH4OH  [Ag( NH3 )2 ]Cl + 2H2O
Diammine silver  I 
chloride

(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 + 2CrO2 Cl2 + 4NaHSO4 + 3H2O
( Chromyl
chloride )

CrO2Cl2 + 4NaOH Na2CrO4 + 2NaCl + 2H2O

(CH3COO)2Pb + Na 2 CrO4 
 PbCrO + 2CH3COONa
Sodium Lead chromate
chromate (yellow precipitate)

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7 | Salt Analysis
Acidify the second part with dilute sulphuric acid and add small amounts
of amyl alcohol and then 1 mL of 10% hydrogen peroxide solution. On
gentle shaking organic layer turns blue. CrO 2–
4 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.
4 + 2H+ + 2H2O2  CrO5 + 3H2O
CrO 2–
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 + 2H2SO4 Br2 + SO2 + Na2SO4 + 2H2O
2NaBr + MnO2 + 2H2SO4 Na2SO4 + MnSO4 + 2H2O + Br2

(a) Add 1 mL 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 with difficulty.
NaBr + AgNO3 NaNO3 + AgBr
Silver bromide
Pale yellow precipitate

3. Test for Iodide ion (I–)

(a) If on heating the salt with conc. H2SO4, 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 + 2H2SO4 Na2SO4 + SO2 + 2H2O + I2
I2 + Starch solution Blue colour
NaI + H2SO4 NaHSO4 + HI
2HI + H2SO4 2H2O + I2 + SO2
6NaI + 4H2SO4 3I2 + 4H2O +S + 3Na2SO4
8NaI + 5 H2SO4 4I2 + H2S + 4Na2SO4 + 4H2O
On adding MnO2 to the reaction mixture, the violet vapours become dense.
2NaI + MnO2 + 2H2SO4 I2 + MnSO4 + Na2SO4 + 2H2O

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8 | Salt Analysis
(b) Add 1 mL 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
Iodine dissolves in the organic solvent and the solution becomes violet.
(c) 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 Nitrate ion  NO3– 

(a) If on heating the salt with conc. H2SO4 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 + H2SO4 NaHSO4 + HNO3
4HNO3 4NO2 + O2 + 2H2O
2NaNO3 + 4H2SO4 + 3Cu  3CuSO4 + Na2SO4 + 4H2O + 2NO
Copper sulphate
(Blue)

2NO  O2 
 2NO2
(Brown fumes)

(b) Take 1 mL of an aqueous solution of the salt and add 2 mL 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. 7.2). Alternatively first ferrous sulphate is added and then concentrated
sulphuric acid is added.

NaNO3 + H2SO4 Na HSO4 + HNO3

6 FeSO4 + 3H2SO4 + 2HNO3 3Fe2 (SO4)3 + 4H2O + 2NO
FeSO4  NO 
 [Fe(NO)]SO4
Nitroso ferrous sulphate
(Brown)

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9 | Salt Analysis

5. Test for Oxalate ion C2 O2–

4 


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. H2SO4Na2SO4 + 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  CaC2 O4 + 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  CaSO 4  H 2 C 2 O 4 
Calcium sulphate Oxalic acid

2 KMnO4 + 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.

Group III : Anions which do not liberate any gas with dil HCl or conc. H2SO4. They are detected by
precipitation (SO42–, PO43–).

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10 | Salt Analysis
Chemistry of Confirmatory Tests
1. Test of Sulphate ions SO 2– 
4 

(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.
Na2SO4 + 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.
Na2SO4 + (CH3COO)2Pb  PbSO4 + 2CH3COONa
Lead sulphate
 White precipitate 

2. Test for Phosphate ion  PO3– 

4 

(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)2 MoO4 + 23HNO3  (NH4 )3[P(Mo3O10 )4 ] + 2NaNO3 + 21NH4NO3 + 12H2O
Canary yellow
Precipitate
The tests for cations may be carried out according to the following scheme.

Step - I : 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 7.6
gives the characteristic colours of the salts of some cations.

Table 7.6 : Characteristic colours of some metal ions

Colour Cations Indicated
Light green, Yellow, Brown Fe2+, Fe3+
Blue Cu2+
Bright green Ni2+
Blue, Red, Violet, Pink Co2+
Light pink Mn2+

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 7.7).

Table 7.7 : Inferences from the colour of the salt in cold and on heating
Colour when cold Colour when hot Inference
Blue White Cu2+
Green Dirty white or yellow Fe2+
White Yellow Zn2+
Pink Blue Co2+

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11 | Salt Analysis
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. 7.3).
(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. 7.3).
(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 7.8.

Table 7.8 : Inference from the flame test

Colour of the flame Colour of the flame observed
Inference
observed by naked eye through blue glass
Green flame with blue centre Same colour as observed without glass Cu2+
Crimson red Purple Sr2+
Apple green Bluish green Ba2+
Brick red Green Ca2+

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12 | Salt Analysis
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. 7.4).
(v) To remove the bead from the platinum wire, heat it to redness and tap the platinum wire with your
finger. (Fig. 7.5).
On heating, borax loses its water of crystallisation and decomposes to give sodium metaborate and boric
anhydride.
Na 2 B4 O7 .10H2O Na2B4O7 + 10H2O
Borax

Na 2 B4O7 
 2NaBO2  B2O3
Sodium metaborate Boric anhydride

On treatment with metal salt, boric anhydride forms metaborate of the metal which gives different colours
in oxidising and reducing flame. For example, in the case of copper sulphate, following reactions occur.
Non lu min ousflame
CuSO4 + B2O3   Cu(BO2 ) 2  SO3
Cupric metaborate
Blue-green

Two reactions may take place in the reducing flame:

(i) The blue Cu (BO2)2 is reduced to colourless cuprous metaborate as follows:
2Cu(BO2)2 + 2NaBO + C 
Lu minousflame
 2Cu(BO2) + Na2B4O7 + CO
or
(ii) Cupric metaborate may be reduced to metallic copper and the bead appears red and opaque.
2Cu(BO2)2 + 4NaBO2 + 2C 
Lu minousflame
 2Cu + 2Na2B4O7 + 2CO
The preliminary identification of metal ion can be made from Table 7.9.

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13 | Salt Analysis
Table 7.9 : Inference from the borax bead test
Heating in oxidising Heating in reducing
(non-luminous) flame (luminous) flame
Colour of the salt bead Colour of the salt bead Inference
In cold In hot In cold In hot
Blue Green Red opaque Colourless Cu2+
Reddish brown Violet Grey Grey Ni2+
Light violet Light violet Colourless Colourless Mn2+
Yellow Yellowish brown Green Green Fe2+

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.7.6 (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. (7.6 b)]. Obtain oxidising and reducing flame
as shown in Fig. 7.7 a and b.

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14 | Salt Analysis

Fig. 7.7 : Obtaining oxidising and reducing flame (a) Oxidising flame (b) Reducing Flame
(v) Always bore a fresh cavity for testing the new salt.
When test is performed with CuSO4, the following change occurs.
CuSO4 +Na2CO3  Heat
 CuCO3 +Na2SO4
CuCO3 
Heat
 CuO + CO2
CuO + C 
Heat
 Cu + CO
Red colour
In case of ZnSO4 :
ZnSO4 + Na2CO3  Heat
 ZnCO3 +Na2SO4
ZnCO3 
Heat
 ZnO + CO2
Yellow when hot,
White when cold
The metal ion can be inferred from Table 7.10.

Table 7.10 : Inference from the charcoal cavity test

Observations Inference
Yellow residue when hot and grey metal when cold Pd2+
White residue with the odour of garlic As3+
Brown residue Cd2+
Yellow residue when hot and white when cold Zn2+

6. 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, Al2O3 and MgO, the following reactions occur.
2Co(NO3)2  Heat
 2CoO+4NO2 +O CoO + ZnO  CoO.ZnO
Green

CoO + MgO 
 CoO. MgO  CoO + Al2O3 
 CoO. Al2O3
Pink Blue

Step-II : 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:
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15 | Salt Analysis
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.

Classification of Cations
For the purpose of systematic qualitative analysis, cations are classified into five groups on the basis of their
behaviour with some reagents and classification is based on whether a cation reacts with these reagents by
the formation of precipitate or not (solubility difference).

Group reagent : Hydrocholoric acid, hydrogen sulphide, ammonium sulphide and ammonium carbonate.

Group Group Reagent Ions Colour & ppt.

Group I dil. HCl Pb2+, Hg+, Ag+ PbCl2, Hg2Cl2, AgCl - white
Yellow - CdS
Cu2+, Cd2+, Hg2+,
Group II A H2S in dil. HCl Black - HgS, CuS, PbS
Pb2+, Bi3+ Brown - Bi2S3
Yellow - As2S3, As2S5, SnS2
As3+, As5+, Sb3+, Sb5+, Sn2+,
Group II B H2S in dil. HCl Orange - Sb2S3, Sb2S5
Sn4+
Brown - SnS
NH4OH in presence of Fe(OH)3, Al(OH)3, Cr(OH)3
Group III A Fe3+, Al3+, Cr3+
NH4Cl Brown White Green
ZnS - white or grey
H2S in presence of NH3 2+ +2 +2 +2s
Group III B Ni , Co , Mn , Zn Black - CoS, NiS
& NH4Cl or NH4S
MnS Buff (light pink)

(NH4)2CO3 in presence
Group IV Ba+2, Sr2+, Ca+2 BaCO3, SrCO3, CaCO3 - white
of NH4Cl & NH4OH

No common group
Group V Mg+2, Na+, K+, NH4+ __
reagent
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16 | Salt Analysis
Points to Remember

1. Group I radicals (Ag+, Pb+2, Hg22+) are precipitated as chlorides because the solubility product of these
chlorides (AgCl, PbCl2, Hg2Cl2) is less than the solubility products of all other chlorides which remain
in solution.
2. Group II radicals are precipitated as sulphides because sulphides of other metals remain in solution
because of their high solubility products, HCl acts as a source of H+ and thus decreases the conc. of S2-
due to common ion effect. Hence decreased conc. of S2- is only sufficient to precipitate the Group II
radicals only.
3. Group III A radicals are precipitated as hydroxides and the NH4Cl suppresses the ionisation of NH4OH
so that only the group III A radicals are precipitated because of their low solubility product.
Note:
(i) Excess of NH4Cl should be added otherwise manganese will be precipitate as MnO2.H2O.
(ii) (NH4)2SO4 can’t be used in place of NH4Cl because the SO42- will precipitate barium as BaSO4.
(iii) NH4NO3 can’t be used in place of NH4Cl because NO3- ions will oxidise Mn2+ to Mn3+ and thus
Mn(OH)3 will be precipitated in III A group.
(iv) Only Al(OH)3 is soluble in excess of NaOH followed by boiling to form sodium metaluminate while
Fe(OH)3 and Cr(OH)3 are insoluble.
4. Ammonium hydroxide increases the ionisation of H2S by removing H+ from H2S as unionised water
H2S 2H+ + S2-. H+ + OH-  H2O
2-
Now excess of S ions are available and hence the ionic product of hydroxides of Group III B exceed
their solubility product and ppt. will be obtained.In case H2S is passed through a neutral solution,
incomplete precipitation will take place due to the formation of HCl which decreases the ionization of
H2S.
MnCl2 + H2S  MnS + 2HCl

Identification of Basic Radicals

All confirmatory tests for basic radicals are performed with the salt solution.

1. Group I (Pb2+, Ag+, Hg+)

(a) PbCl2 gives a yellow ppt. with K2CrO4. The ppt. is insoluble in acetic acid but soluble in NaOH
Pb(NO3)2 + K2CrO4  PbCrO4  + 2KNO3
Yellow ppt.
PbCrO4 + 4NaOH  Na2[PbO2] + Na2CrO4 + 2H2O
(b) Pb(NO3)2 + 2KI  PbI2  + 2KNO3
(Yellow)
PbCl2 + 2KI (excess)  K2[PbI4]

2. AgCl is soluble in NH4OH forming a complex while Hg2Cl2 forms a black ppt. with NH4OH.
AgCl + 2NH4OH  Ag(NH2)2Cl + 2H2O
Hg2Cl2 + 2NH4OH  H2N  Hg  Cl + Hg + NH4Cl + 2H2O
Amino mercuric chloride
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17 | Salt Analysis
2. Group II A (Hg2+, Cu2+, Bi3+, Cd2+)
(i) Hg+2ions in solution, on addition of SnCl2, give white precipitate turning black.
2Hg+2 + 2SnCl  2Sn+4 + Hg2Cl2 
White
Hg2Cl2 + SnCl2  SnCl4 + 2Hg 
Black
+2
(ii) Cu ions in solution gives a pale blue precipitate which gives a deep blue colour with excess of
NH4OH
Cu+2 + 4NH4OH  [Cu(NH3)4 ]+2 + 4H2O
Deep blue in colour
Cu+2 ions give chocolate precipitate with K4Fe(CN)6.
2Cu+2 + K4Fe(CN)6  Cu2[Fe(CN)6] + 4K+
(iii) Bi+3 ions in solution of HCl on addition of water give white cloudy precipitate.
BiCl3 + H2O  BiOCl  + 2HCl
White ppt.
When treated with sodium stannite a black ppt. is obtained.
2BiCl3 + 3Na2SnO2 + 6NaOH  2Bi  + 3Na2SnO3 + 6NaCl + 3H2O
black
+2
(iv) Cd ions in solution, with ammonium hydroxide gives a white precipitate which dissolves .
Cd+2 + 2NH4OH  Cd(OH)2  + 2NH4+
Yellow
Cd(OH)2 + 4NH4OH [Cd(NH3 )4](OH)2 + 4H2O

3. Group II B (As3+, As5+, Sb3+, Sb5+, Sn3+, Sn4+)

(v) As+3 ions in solution give yellow precipitate with ammonium molybadate and HNO3.
As 3 
HNO3
Oxidation
 As 5  as H 3 AsO 4 
H3AsO4 +12(NH4)2MoO4 +21HNO3 (NH4)3 AsMo12O40 + 21NH4NO3 + 12H2O
Yellow ppt.
2+
(vi) Sn ions in solution as SnCl2 give white ppt. with HgCl2 ,which turns black on standing.
SnCl2 + 2HgCl2  SnCl4 + Hg2Cl2 
White
Hg2Cl2 + SnCl2 SnCl4 + 2Hg 
Black
(vii) Sb+3 ions in solution as SbCl3 , on addition of water give white precipitate.
SbCl3 + H2O  SbOCl + 2HCI
White

4. Group III A (Al3+, Fe3+, Cr3+)

(i) White precipitate of Al(OH)3 is soluble in NaOH
Al(OH)3 + NaOH  NaAlO2 + 2H2O

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18 | Salt Analysis
(ii) Precipitate of Cr(OH)3 is soluble in NaOH + Br2 water and addition of BaCl2 to this solution gives
yellow precipitate.
Br2 + H2O  2HBr + (O)
2Cr(OH)3 + 4NaOH + 3(O)  2Na2CrO4 + 5H2O
Na2CrO4 + BaCl2  BaCrO4  + 2NaCl
Yellow ppt.
Fe(OH)3 is insoluble in NaOH
(iii) Brown precipitate of Fe(OH)3 is dissolved in HCl and addition of KCNS to this solution gives
blood red colour.
Fe(OH)3 + 3HCl  FeCl3 + 3H2O
FeCl3 + 3KCNS  Fe(CNS)3 + 3KCl
blood red
Also on addition of K4Fe(CN)6 to this solution, a prussian blue colour is obtained.
4FeCl3 + 3K4Fe(CN)6  Fe4[Fe(CN)6]3 + 12KCl
prussian blue colour

5. Group III B (Ni2+, Co2+, Mn2+, Zn2+)

(i) Ni+2 and Co+2 ions in solution, on addition of KHCO3 and Br2 water give apple green colour if Co+2
is present and black precipitate if Ni+2 is present.
CoCl2 + 6KHCO3  K4[Co(CO3)3] + 2KCl + 3CO2 + 3H2O
2K4[Co(CO3)3] + 2KHCO3 + [O]  2K3[Co(CO3)3] + 2K2CO3 + H2O
Apple green colour

NiCl2 + 2KHCO3  NiCO3 + 2KCl + H2O + CO2

2NiCO3 + 4NaOH + [O]  Ni2O3  + 2Na2CO3 + 2H2O
Black ppt.
(ii) Zn+2 ions in solution give a white precipitate with NaOH, which dissolves in excess of NaOH.
Zn+2 + 2NaOH  Zn(OH)2  + 2Na+
White
Zn(OH)2 + 2NaOH  Na2ZnO2 + 2H2O
Soluble
+2
(iii) Mn ions in solution give pink precipitate with NaOH turning black or brown on heating.
Mn+2 + 2NaOH  Mn(OH)2 + 2Na+
Pink

Mn(OH)2 + [O]   MnO2 + H2O
Brown or black

6. Group IV (Ba2+, Sr2+, Ca2+)

(i) Ba+2 ions in solution give
(a) Yellow precipitate with K2CrO4
Ba+2 + K2CrO4 BaCrO4  + 2K+
Yellow
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19 | Salt Analysis
(b) White precipitate with (NH4)2SO4
Ba+2 + (NH4)2SO4  BaSO4 + 2NH4
White
(c) White precipitate with (NH4)2 C2O4
Ba+2 + (NH4)2C2O4  BaC2O4 + 2NH4
White
(ii) Sr+2 ions give white precipitate with (NH4)2SO4 and (NH4)2C2O4
Sr+2 + (NH4)2SO4  SrSO4 + 2NH4
White ppt.
Sr + (NH4)2C2O4  SrC2O4 + 2NH4
+2

White
(iii) Ca+2 ions give white precipitate with (NH4)2C2O4 only.
Ca+2 + (NH4)2C2O4  CaC2O4  + 2NH4
White
7. Group V (NH4 , Na , K+, Mg+2)
+ +

(i) All ammonium salts on heating with alkali say NaOH give a colourless, pungent smelling gas (NH3).
NH4Cl + NaOH NaCl + NH3  + H2O
(a) Gas evolved gives white fumes with a rod dipped in conc. HCl
NH3 + HCl  NH4Cl 
White fumes
(b) Paper soaked in CuSO4 solution, becomes deep blue due to complex formation with NH3.
CuSO4 + 4NH3  [Cu(NH3)4]SO4 deep blue

(c) With Hg2 (NO3)2 , a black colour is obtained

Hg2(NO3)2 + 2NH3  Hg(black)  + Hg(NH2)NO3  + NH4NO3

(d) An aqueous solution of an ammonium gives a brown ppt. with Nessler’s reagent(alkaline solution
of potassium tetraiodomercurate(II) ).
Hg

NH4OH + 2K 2HgI 4 + 3 NaOH  O NH 2I + 4KI + 3H2 O + 3NaI

Hg
(Brown)
(Iodide of Millon's base)
(ii) Potassium salts give a yellow ppt. with sodium cobaltinitrite
Na3[Co(NO2)6] + 3KCl  K3[Co(NO2)6] + 3NaCl
yellow
(iii) Sodium salts give a heavy white ppt. with potassium dihydrogen antimonate
KH2SbO4 + NaCl  NaH2SbO4  + KCl
White ppt.
(iv) Mg2+ gives white ppt. of magnesium hydroxide with sodium hydroxide
Mg2+ + 2NH3 + 2H2O  Mg(OH)2  + 2NH4+
The ppt. obtained is sparingly soluble in water but readily soluble in ammonium salt.

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20 | Salt Analysis

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21 | Salt Analysis

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22 | Salt Analysis

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23 | Salt Analysis

Principles of qualitative analysis group I to V excluding interfering radicals.

The detection of cations (basic radicals)and anions(acidic radicals) in a salt or in a mixture is known as
Qualitative Analysis.

Some Important Observations during Qualitative Analysis

1. List of different coloured salts

S.No Salts Colour

i) Copper salts Bluish green
ii) Nickel salts Greenish blue
iii) Chromium salts Dark green
iv) Cobalt salts Pinkish or purple
v) Manganese salts Light pink
vi) Ferrous salts Light green

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24 | Salt Analysis

SOLVED EXAMPLE

Example-1
An aqueous solution of gas (X) shows the following reactions :-
(i) It turns red litmus blue.
(ii) When added in excess to a copper sulphate solution, a deep blue colour is obtained.
(iii) On addition of FeCl3 solution a brown ppt. soluble in dilute nitric acid is obtained.
Identify (X) and give equations for the reactions at step (ii) & (iii)
Solution: X - NH3
Reactions : (i) CuSO4 + 4NH4OH  Cu(NH3)4 SO4 + 4H2O
deep blue
(ii) FeCl3 + 3NH4OH  Fe(OH)3  + 3NH4Cl
brown ppt.
Fe(OH)3 + 3HNO3  Fe(NO3)3 + 3H2O
Soluble
Example-2
An aqueous solution of a gas (X) gives the following reactions:
(i) It decolourizes an acidified K2Cr2O7 solution.
(ii) On boiling with H2O2 , cooling it and then adding an aqueous solution of BaCl2, a white ppt.
insoluble in dilute HCl is obtained.
(iii) On passing H2S into the solution, turbidity is obtained.
Identify (X) and give equations for the steps (i), (ii), (iii) .
Solution: X - SO2
Reactions :
(i) K2Cr2O7 + H2SO4 + 3SO2  K2SO4 + Cr2(SO3 )3 +H2O
(ii) SO2 + H2O2  H2SO4
H2SO4 + BaCl2  BaSO4  + 2HCl
white ppt.
(iii) SO2 + 2H2S  3S + 2H2O
white turbidity
Example-3
A white amorphous powder (A) on strongly heating gives a colourless non-combustible gas (B) and solid
(C). The gas (B) turns lime water milky and turbidity disappears with the passage of excess of gas.The
solution of (C) in dilute HCl gives a white ppt. with an aqueous solution of K 4[Fe(CN)6]. The solution of
(A) in dilute HCl gives a white ppt. (D) on passing H2S in presence of excess of NH4OH. Identify (A) to
(D) by giving chemical equations.
Solution :
(A) ZnCO3 (B) CO2 (C) ZnO (D) ZnS

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25 | Salt Analysis
Reactions : (i) ZnCO3  ZnO + CO2
(A) (C) (B)
(ii) CO2 + Ca(OH)2  CaCO3 + H2O
(B) White
CaCO3 + H2O + CO2  Ca(HCO3)2
Excess Soluble
(iii) ZnO + 2HCl  ZnCl2 + H2O
2ZnCl2 + K4Fe(CN)6  Zn2[Fe(CN)6] + 4KCl
White ppt.
(iv) ZnCl2 + H2S  ZnS + 2HCl
(D)

Example-4
A certain compound (X) is used in laboratory for analysis. Its aq. solution gave the following reactions.
(i) On addition to copper sulphate solution, a brown ppt. is obtained which turns white on addition of
excess of Na2S2O3 solution.
(ii) On addition to Ag+ ion solution, a yellow ppt. is obtained which is insoluble in NH4OH. Identify
(X), giving reactions
Solution: X - KI
Reactions : (i) 2CuSO4 + 4KI  2CuI2 + 2K2SO4
2CuI2  Cu2I2 + I2
white
I2 + 2Na2S2O3  Na2S4O6 + 2NaI
(ii) Ag+ + KI  AgI + K+
Yellow ppt.
The white ppt. of Cu2I2 is coloured brown due to the presence of I2. On adding sodium thiosulphate, I2 is
consumed. Therefore the ppt. appears white.

Example-5
An aqueous solution of inorganic compound (X) gives the following reactions:
(i) With an aq. solution of barium chloride a ppt. insoluble in dil. HCl is obtained.
(ii) Addition of excess of KI gives a brown ppt. which turns white on addition of excess of hypo.
(iii) With an aqueous solution of K4[Fe(CN)6] a chocolate coloured ppt. is obtained.
Identify (X) and give equations for the reactions for (i), (ii) and (iii) observations.
Solution: X - CuSO4
Reactions : (i) CuSO4 + BaCl2  BaSO4 + CuCl2
White ppt. (insoluble in HCl)
(ii) 2CuSO4 + 4KI  2CuI2 + 2K2SO4

I2+ Cu2I2
I2 + 2Na2S2O3  Na2S4O6 + 2NaI
(iii) CuSO4 + K4[Fe(CN)6]  Cu2 [Fe(CN)6] + 2K2SO4
Chocolate Coloured ppt.

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26 | Salt Analysis
Example-6
An aq. solution of an inorganic compound (X) shows the following reactions.
(i) It decolorizes an acidified KMnO4 solution accompanied with evolution of O2.
(ii) It liberates I2 from acidified KI solution.
(iii) It gives brown ppt. with alkaline KMnO4 solution with evolution of O2.
(iv) It is used to restore old oil paintings. Identify (X) and give chemical reactions for the steps (i) to
Solution: X - H2O2
Reactions: (i) 5H2O2+2KMnO4+3H2SO4 K2SO4+2MnSO4+8H2O +5O2
(ii) H2O2 + 2KI + H2SO4  I2 + K2SO4 + 2H2O
(iii) 3H2O2 + 2KMnO4  2MnO2  + 2KOH + 3O2 + 2H2O
(iv) 4H2O2 + PbS PbSO4 + 4H2O
white

Example-7
An inorganic Lewis acid (X) shows the following reactions :
(i) It fumes in moist air.
(ii) The intensity of fumes increases when a rod dipped in NH4OH is brought near it.
(iii) An acidic solution of (X) on addition of NH4Cl and NH4OH gives a precipitate which dissolves in
NaOH solution.
(iv) An acidic solution of (X) does not give a precipitate with H2S. Identify (X) and give chemical
equation for steps (i) to (iii) .
Solution: X - AlCl3
Reactions : (i) AlCl3 + 3H2O  Al(OH)3 + 3HCl 
fumes
(ii) HCl + NH4OH  NH4Cl + H2O
White fumes
(iii) AlCl3 + 3NH4OH  Al(OH)3 + 3NH4Cl
White ppt.
Al(OH)3 + NaOH  NaAlO2 + 2H2O
Soluble

Example-8
A solid laboratory reagent (A) gives the following reactions.
(i) It imparts green colour to flame.
(ii) Its solution does not give ppt. on passing H2S.
(iii) When it is heated with K2Cr2O7 and conc. H2SO4 a red gas is evolved. The gas when passed in aq.
NaOH solution turns it yellow. Identify (A) giving chemical reactions.
Solution: A - BaCl2
Reactions : (i) 2BaCl2 + K2Cr2O7 + 3H2SO4 K2SO4 + 2CrO2Cl2 + 2BaSO4 + 3H2O
red gas
(ii) CrO2Cl2 + 4NaOH  Na2CrO4 + 2NaCl + 2H2O
yellow solution
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27 | Salt Analysis
Example-9
Ag2S is soluble in NaCN due to formation of :
(A) Na[Ag(CN)2] (B) Ag(CN)2 (C) Na2Ag(CN)3 (D) Na2[Ag(CN)2]
Solution: (A)
Ag2S is soluble in NaCN due to formation of coordinate complex of sodium dicyanoargentate (I)
Ag2S + 4NaCN  2Na[Ag(CN)2] + Na2S

Example-10
There is foul smell in presence of moisture with :
(A) AlCl3 (B) Al2(SO4)3 (C) FeS (D) FeSO4
Solution: (C)
FeS in presence of moisture gives a foul smell due to the formation of H2S gas.
FeS + 3H2O  Fe(OH)3 + 3H2S

Example-11
AgNO3 on treatment with hypo gives white ppt. changing to black after some time. Black ppt. is :
(A) Ag2S2O3 (B) Ag2SO4 (C) Ag2S4O6 (D) Ag2S
Solution: (D)
Silver Nitrate on reaction with hypo (Sodium thiosulphate) gives the white precipitate of silver
thiosulphate. The white precipitate formed is gradually changes its colour to blcak due to formation of
Ag2S.
Na2S2O3+2AgNO3 Ag2S2O3 + 2NaNO3
Ag2S2O3 + H2O  Ag2S + H2SO4

Example-12
Yellow coloured solution of FeCl3 changes to light green when :
(A) SnCl2 is added (B) Zn is added
(C) H2S gas is passed (D) Any one of the above is added.
Solution: (D)
When yellow colour solution of FeCl3 is reduced to FeCl2 it gives green colour solution.
2FeCl3 + SnCl2 2FeCl2 + SnCl4
2FeCl3 + H2S  2FeCl2 + 2HCl + S
2FeCl3 + 3H2O  Zn
 Fe(OH)3 + 3HCl
green

Example-13
Evolution of deep red vapours when an inorganic salt is mixed with powdered K2Cr2O7 and heated
with conc. H2SO4 confirms the presence of a :
(A) chloride (B) fluoride (C) borate (D) phosphate
Solution: (A)
When inorganic salt contains chloride reacts with potassium dichromate and sulphuric acid, it
produce red vapours of chromyl chloride.
K2Cr2O7 + 4KCl + 3H2SO4 2CrO2Cl2 + 3K2SO4 + 3H2O
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28 | Salt Analysis
Example-14
Which of the following would enable you to remove SO42– ions from a mixture of SO42- and Cl–
ions?
(A) NaOH (B) KOH (C) Ba(OH)2 (D) BaSO4
Solution: (C)
Ba(OH)2 is used to remove sulphate ion from the given mixture of ions

Example-15
Which of the following sulphates is insoluble in water?
(A) CuSO4 (B) CdSO4 (C) PbSO4 (D) Bi(SO4)3
Solution: (C)
Lead sulphate is insoluble in water whereas other given sulphates are soluble in water

Example-16
A fire work gave bright crimson light. It probably contained a salt of :
(A) Ca (B) Sr (C) Ba (D) Mg
Solution: (B)
Stronium salts gives bright crimson red light to fire works.

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