Qualitative Analysis for Inorganic Mixtures

Acid Radicals: Cl-, Br-, I-, NO2-, S2-, SO42-, PO43-, BO33-, H3BO3
Basic Radicals: Na+, K+, Ca2+, Sr2+, Cr3+, Mn2+, Fe3+, Ni3+, Cu2+, NH4+
Colour of Some Common Inorganic Compounds:
Colour Inorganic Compounds
Black Ag2S, CuO, CuBr2, CuS, HgS, PbS, FeS, MnO2, CoO, CoS,
NiS, NiI2, NiO
Green All Cr (III) compounds (except Cr(OH)3 greyish green
and Cr2(CO3)3 grey), all Fe(II) compounds (except black
FeS), all Ni(II) compounds (expect black NiO, NiS),
CuCO3, CuCl2∙6H2O, Cu(OH)2
Red Cu2O, HgS, HgI2, As2S2, Fe2O3
Orange red Sb2S3, CdS
Brown Fe2O3, Fe(OH)3, Bi2S3, SnS
Yellow AgI, CdS, As2S3, SnS2

Colour of Aqueous and HCl Solution of Cation:

Compounds Colour in Aqueous Colour in HCl solution
Solution
Dichromates Orange Orange
Chromate Yellow Orange
Permanganates Purple -
Cobalt (II) Pink Blue
Nickel (II), Chromium Green Green
(II)
Copper (II) Blue Bluish Green
Manganese (II) Pale pink Green
Iron (III) Yellow Yellowish brown
Iron (II) Light green Green
Aqueous solution of all alkali and alkaline earth salts are colourless unless the anion is
coloured.
Preliminary Examination for Basic Radicals:
Test Tube Heating Test:
Take a little of the substance in a clean dry test tube, in such a way that no particles
adhere to the side of the test tube. Heat the test tube at first gently and then strongly,
observe and note the change carefully.
Observations Inferences
Residue turns black Cu, Ni, Co, Mn-salt
Brown to blackening when hot, brown when cold Fe-salt
 Green Cr-salt
Droplets of water deposited at the cooler part of the Compounds with water of
test tube crystallisation
Greenish yellow gas with pungent smell, turns Chloride
starch iodide paper blue
Violet vapours condensing to black crystals Heavy metal Iodide, i.e.
PbI2
Brown gas Nitrite, Nitrate or Bromide
of heavy metals
SO2 gas with smell of burnt sulphur turning acidified Sulphite
K2Cr2O7 paper green
H2S gas with smell of rotten egg turning lead acetate Sulphite
paper black
NH3 gas with characteristic pungent odour turning NH4-salt
mercurous nitrate paper black
White sublimate with pungent smell of NH3, no NH4-salt
change of colour with H2S

Flame Test:
Clean a platinum wire by moistening it with conc. HCl, kept in a watch glass, on
holding it at the base of the non-luminous flame until the flame became colourless.
Hold the clean Pt-wire near the base of the non-luminous flame again moistened
with conc. HCl and a little of the powdered sample at the tip of the wire. Observe and
note the changes carefully.
Observations
With double blue Inferences
Without blue glass
glass
Bluish violet Crimson red K+
Crimson red Purple Sr2-
Brick red Light green Ca2+
Bluish green - Cu
Transient deep red Crimson red CaF2
Persistent apple green Bluish green Ba
Golden yellow Colourless Na+

Borax Bead Test:

Borax bead test is performed in case of coloured salts only. (MnSO 4 is very light
pink).
Prepare a transparent borax bead in a loop of a clean platinum wire by heating the
Pt-with borax. Take a tiny particle by just touching the salt with the hot bead and heat
first in the oxidising flame and then in the reducing flame. Observe and note the
changes carefully.
Observations
Colour in oxidising Colouring reducing Inferences
flame flame
Amethyst (violet) Colourless Mn2+
Green when hot, blue Opaque red when cold Cu2+
when cold
Reddish brown Grey opaque Ni2+
Reddish yellow when Bottle green in both hot Fe2+
hot, yellow when cold and cold
Green in both hot and Green in both hot and Cr3+
cold cold

Oxidative Fusion Test for Cr and Mn:

If there is sufficient indication for the presence of Cr and Mn in the given salt, mix 1
part of the substance with - 2 parts of anhydrous Na2CO3, 1 bead of NaOH and 1 part of
KNO3. Heat the mixture strongly on a mica foil or on a broken porcelain basin or on a
Pt-loop. Observe and note the changes carefully.
If the sample is white do not perform this test.
Observations Inferences
Yellow melt:
The melt is dissolved in boiling water and
Cr - salt
acidified with acetic acid then a few drops of Pb-
acetate solution are added – yellow ppt.
Green melt:
The met is dissolved in boiling water and acidified
Mn - salt
with dill. HNO3 or dill. CH3COOH until acidic – a
pink colour develops.

Special Test with HCl and HNO3 Extracts:

Heat the sample with conc. HCl and the divide the solution into 2 parts. Then
following test was performed. Observe and note the change carefully.
Experiments Observations Inferences
Dilute one part of the Deep blue ppt. or
solution, and then add solution of Prussian Fe2+
solution of K4Fe(CN)6 blue
To another part of the
extract, add diluted White ppt. Ba2+ and Sr2+
H2SO4
 Heat the sample with (1:1) HNO3 and divided the solution into 3 parts. The following
test was performed. Observe and note the changes carefully.
Experiment Observations Inferences
Add to one part of the Solution turns pink Mn 2+

HNO3 solution, a pinch

of NaBiO3
Alkaline the second part Rose red ppt. Ni2+
with NH4OH and then
add dimethylglyoxime
solution
Alkaline the third part Chocolate brown ppt. Cu2+
with NH4OH, then
acidify with acetic acid.
Add K4Fe(CN)6 solution

Reaction of Preliminary Dry Tests for Basic Radicals:

1. Action of heat
a) Decomposition of the substance:
ZnCO3 → ZnO + CO2
2Pb(NO3)2 → 2PbO + 4NO2 + O2
4BiONO3 → 2Bi2O3 + 4NO2 + O2
b) Elimination of water from water of crystallisation:
CuSO4, 5H2O (Blue) → CuSO4 (White) + 5H2O
Ni(OH)2, 5H2O (Green) → NiO (Black) + 5H2O
c) A gas is evolved:
(NH4)2CO3 → 2NH3 + CO2 + H2O
2Pb(NO3)2 → 2PbO + 4NO2 + O2
2. Flame test:
Conc. HCI used in flame tests converts the different compounds into their
volatile chlorides that impart characteristic flame colouration.
Conc. HCI converts metallic salts into the volatile chlorides when heated in the
Bunsen flame with the help of a Pt-wire. The heat excites one of the valence
electrons of metal ion to a higher energy level. When the excited electron drops
back to its original energy level it gives out the extra energy gained. The energy
emitted will correspond to a particular wavelength in the visible region and this
imparts characteristic flame colouration.
Alternatively, the colour may arise from electronic transitions in short-lived
species, which are formed momentarily in the flame. The flame is rich in
electrons and thus in case of sodium, Na+ ions are temporarily reduced to the
atoms. The golden yellow colour of sodium (sodium D-line) arise from the
electron transition 3s' - 3p' in sodium atoms formed in the flame.
 3. Borax Bead Test:
Na2B4O7, 10H2O →2NaBO2 + B2O3 + 10H2O
CoCO3 →CoO + CO2
CoO + B2O3 →Co(BO2)2 (Blue in both oxidising and reducing flame)
In Oxidising Flame:
CuCO3 →CuO + CO2
CuO + B2O3 →Cu(BO2)2
The following reaction may also take place:
CuO + NaBO2 →NaCuBO3
In Reducing Flame:
2Cu(BO2)2 + C →Cu2(BO2)2 + CO + B2O3
Cu2(BO2)2 + C →2Cu + B2O3 + CO
4. Oxidative fusion test for Mn and Cr:
Mn salt are converted to green sodium manganate which on acidification turns to
pink permanganate:
MnO2 + KNO3 + 2NaOH → Na2MnO4 + KNO2 + H2O
3NaMnO4 + 4HNO3 → 2NaMnO4 + MnO2 + 2NaNO3 + 2H2O
Cr salt are converted to yellow chromate:
Cr2O3 + 2Na2CO3 + 3KNO3 → 2Kn2CrO4 + 2CO2 + 3KNO2
Na2CrO4 + Pb(CH3COO)2 → PbCrO4 + 2CH3COONa
5. Special Test for Mn, Ni, Fe and Cu:
Potassium Ferrocyanide test for Fe:
FeCl3 + KI[De(CN)6] = KFe[Fe(CN)6] (Prussian blue) + 3KCl
Dimethyl glyoximet test for Ni:

Potassium Ferrocyanide test for Cu(II):

In acetic acid medium, Cu-salts react with K4Fe(CN)6 solution to produce the
chocolate precipitate of cupric ferrocyanide, Cu2[Fe(CN)6].
2Cu2+ + K4[Fe(CN)6] = Cu2[Fe(CN)6] (Chocolate ppt.) + 4K+
Sodium Bismuthate test for Mn:
2MnSO4 + 5NaBiO3 + 16HNO3 = 2HMnO4 (Pink) + 5Bi(NO3)3 + NaNO3 + 2Na2SO4 +
7H2O

Dry Test for Acid Radicals:

Preliminary Test for Acid Radical:
Treatment with dil. H2SO4:
Add dilute H2SO4 to a little of the dry substance in a test tube and warm if required.
Observe and note the changes carefully.
Observations Inferences
Effervescence of colourless and odourless gas CO32-
turning lime water milky
Evolution of brown fumes NO2-
Evolution of colourless gas having a smell S2-
rotten egg turning Pb-acetate paper black

Treatment with conc. H2SO4:

Add concert. H2SO4 is to a little of the substance in a test tube and warmed. Observe
and note the changes carefully.
Observations Inferences
Evolution of brown fumes NO 2-

Evolution of reddish brown gas Br-

Evolution of violet vapour I-
Evolution of colourless gas with pungent Cl-
smell – dense white fumes when a glass rod
moistened with NH4OH is held at the mouth
of the test tube

Chromyl Chloride Test for Chloride:

Take a little solid sample in a clean dry hard glass test tube and mix thoroughly with
equal quantity of K2Cr2O7 and 1mL of conc. H2SO4. The mouth of the test tube is fitted
with a delivery tube bent twice at right angles. The other end of the bent tube is led into
dilute NaOH solution kept in a test tube. Now heat the mixture.
Note: HgCl2 and Hg2Cl2 do not respond to this test. Partial conversation to CrO2Cl2
occurs with SnCl2, PbCl2, AgCl2 and SbCl2. Bromides and iodieds evolved ref and violet
vapours. Nitrites and nitrates interfere as NOCl is formed.
Observation Inference
Pass the issuing deep brownish red vapour of Cl-
chromyl chloride into NaOH solution acidify
the solution with acetic acid and then add
lead acetate solution.

Yellow ppt. of PbCrO4

Treatment with MnO2 and conc. H2SO4:

 Warm a little of the substance with a small quantity of MnO 2 and 1mL of conc. H2SO4.
Observations Inferences
Greenish yellow gas of Cl2 comes out and Cl-
turned starch iodied paper blue.
Reddish brown gash that turns CS2 layer Br-
yellow when passed in a test tube containing
CS2 and water (distinction from nitrate).
Violet vapour comes out which turns CS2 I-
layer violet when passed in a test tube
containing CS2 and water.

Reactions of the Dry Tests for Acid Radicals:

1. Reaction with dil. H2SO4:
MS + H2SO4 = MSO4 + H2S
2. Hearing with conc. H2SO4:
MX2 + H2SO4 = 2HX + MSO4 (X = halide ion)
The halogen acids fume on air but on strong heating HBr and HI liberate Br 2
(Reddish brown) and I2 (Violet) respectively.
2HX + H2SO4 = X2 + SO2 + 2H2O
3. Chromyl chloride test:
2MCl2 + K2Cr2O7 + 6H2SO4 = 2M(HSO4)2 + 2KHSO4 + 3H2O + 2CrO2Cl2
This vapour is then passed into a test tube containing NaOH solution, acidified
with acetic acid and then add Pb(OAc)2 solution
CrO2Cl2 + 4NaOH = Na2CrO4 + 2NaCl + 2H2O
Na2CrO4 + Pb(OAc)2 = PbCrO4 (Yellow ppt.) + 2Na(OAc)
4. Heating with MnO2 and conc. H2SO4:
2MX + 3H2SO4 + MnO2 = 2MHSO4 + MnSO4 + 2H2O + X2
Cl2 is yellowish green, New is reddish brown, I2 is violet

Test for Interfering Acid Radicals:

Test for Phosphate:
Dissolve the substance in (1:1) dillite HNO3 then to it add 2mL of ammonium
molybdate solution and warmed.
Observation Inference
 A canary yellow precipitate PO42-

Test for Borate and Boric Acid:

(a) Take a little of the substance in a test tube fitted with a bent delivery tube. Add
2-3 mL of conc. H2SO4 and a little methyl alcohol, heat and ignite the issuing
gas coming out of the delivery tube.
(b) If borate is defected, the above experiment is repeated without adding conc.
H2SO4.
Observations Inferences
A green-edged flame Borate
A green-edged flame Boric acid

Reaction of the Test for Interfering Acid Radicals:

1. Test for Phosphate:
Na2HPO4 + 12(NH4)2MoO4 + 23HNO3 = (NH4)3[PMo12O40] (Yellow) + 21NH4NO3 +
2NaNO3 + 12H2O
2. Test for Borate and Boric Acid:
Na2B4O7 + H2SO4 + 5H2O = 4H3BO3 + Na2SO4
H3BO3 + 3CH3OH = B(OCH3)3 + 3H2O

Wet Test for Acid Radicals

Test with Sodium nitroprusside solution:
A small amount of sample was dissolved in distilled water and to it Sodium
nitroprusside added.
Observations Inferences
A purple colouration S 2-

Test for Cl-, Br- and I-:

A small amount of sample was dissolved in distilled water, acidity with dil. HCl and
then add AgNO3.
Observations Inferences
The white ppt. dissolves readily in dil. Cl -

HN4OH
The pale yellow ppt. partially dissolves in Br-
dil. NH4OH, but dissolves readily in strong
NH3
The light yellow ppt. does not dissolve even I-
 in conc. HN3

Test for Sulphate:

Take a few amount of Na2CO3 extract in a test tube, acidify with dil. HCl, boil off CO 2
and then add BaCl2 solution.
Observations Inferences
A heavy white ppt. insoluble in HCl SO4 2-

Preparation of Solution:
1. If the sample is soluble in water, dissolve about 500 mg of the sample in about 20
mL of distilled water and perform wet test for acid radicals with this aqueous
Solution.
2. When the sample is insoluble in water, mix about 500 mg of the sample with 2 g
of Na2CO3 in a 100 mL conical flask, fitted with a funnel, boil with about 20 mL of
distilled water for about 10-15 minutes. Filter the solution and use the filtrate
called “Na2CO3extract” to perform wet test for acid radicals.

Reactions of the Wet Test for Acid Radicals:

1. The salts on boiling with Na2CO3solution are converted into soluble Na-salts.
MX2 + Na2CO3= MCO3 + 2NaX
MY + Na2CO3= MCO3 + 2Na2Y
[M = Divalent metals, X = Univalent acid radicals, Y = Divalent acid radicals]
2. Reaction of Sulphide with Na-nitroprusside.
Na2S + Na[Fe(CN)5NO)] = Na4[Fe(CN)5NOS] (violet)
3. Reaction of Halides with AgNO3.
NaX + AgNO3 = AgX + NaNO3 [X = Cl, Br, I]
AgCl – white ppt, AgBr – Pale yellow ppt, AgI – Light Yellow ppt.
AgCl + 2NH4OH = [Ag(NH3)2]Cl + 2H2O
4. Reaction of Sulphate with BaCl2.
Na2SO4 + BaCl2 = BaSO4 + 2NaCl