READY REFERENCE CHART FOR QUALITATIVE ANALYSIS OF BASIC RADICALS
Make the solution of the given mixture in distilled water, in dil. HCl or conc. HCl cold or hot. Label it original solution (O.S.). To the O.S., add dil. HCl.
White ppt.
(Pb²⁺)
Con irmation of Pb²⁺
Boil white ppt. with distilled
water and divide the solution
into two parts :
(i) Add KI solution to one white ppt. is formed Pb²⁺ is indicated. If no Dissolve the brown ppt. in dil. HCl and
part of above solution. white ppt. is formed, add excess NH₄OH to divide the solution into two parts.
Yellow ppt. con irms Pb²⁺. the second part of solution - Blue coloured
(ii) Add K₂CrO₄ solution to
the second part of the
above solution. Yellow
ppt. con irms Pb²⁺
If group I is absent, pass H₂S gas through O.S. for suf icient time after acidi ication with dil. HCl & Filter.
Ppt. -Group II
Black ppt. - (Pb²⁺, Cu²⁺)
Yellow ppt. - (As³⁺)
Dissolve, the black ppt. in minimum quan- White ppt. - (Al³⁺)
tity of 50% HNO₃₊To one part of the above
solution add dil. H₂SO₄ and alcohol. If a
solution indicates Cu²⁺
Con irmation of Cu²⁺
(i) Add excess of NH₄OH solution to
original solution. Deep blue solution. (iii) To second part of solution add
(ii) Acidify the above deep blue solution
with dil. acetic acid. Add Pot.
ferrocyanide solution. Chocolate
brown ppt. con irms Cu²⁺
Con irmation of Pb²⁺
(i) Pot. iodide test. To the O.S. add KI
solution Yellow ppt.
(ii) Pot. chromate test. To the O.S. add
K₂CrO₄ Yellow ppt.
If the ppt. obtained is yellow in colour - As³⁺
is indicated.
Con irmation of As³⁺
(i) Amm. molybdate test. Yellow ppt.
+ conc. HNO₃ + Amm. molybdate
solution - Yellow ppt.
(ii) Magnesia mixture test. To the O.S.
add magnesia mixture - White ppt.
If group II is absent, add solid NH₄Cl, O.5 ml conc. HNO₃ to the O.S. Boil and cool & add NH₄OH till it smells of ammonia. If a ppt. is formed, group III is present.
Reddish brown ppt. - (Fe³⁺)
Con irmation of (Fe³⁺)
(i) To one part of solution add pot.
ferrocyanide solution. A prussion
blue colour or ppt.
pot. sulphocyanide solution - A
blood red colouration.
Con irmation of Al³⁺
(i) Perform charcoal cavity - cobalt
nitrate test with white ppt. Blue
mass.
Con irmation of Co²⁺
(ii) Lake test. White ppt. + dil. HCl + a
few drops of blue litmus solution + (i) Take O.S. and neutralise the acid by
NH₄OH Solution in excess. A blue
ppt., suspended in a colourless
medium (called a lake).
(ii) Perform borax bead test with salt
If group III is absent, through a part of the solution obtained in Group III pass H₂S gas. if a ppt. is obtained
group IV is present.
If group IV is absent, to the O.S. add solid NH₄CI, NH₄OH and (NH₄)₂CO₃ Solution.
White ppt - (Zn²⁺)
Black ppt. - (Ni²⁺ and Co²⁺)
Flesh coloured ppt. - (Mn²⁺) White ppt. - (Ba²⁺, Sr²⁺, Ca²⁺) If group V is absent, test for Mg²⁺
Con irmation of Zn²⁺
(i) To the O.S. add a pinch of NH₄Cl, a
Dissolve a part of white ppt. in dil. HCl and Dissolve a part of white ppt. in dil. acetic few drops of NH₄OH and excess of
acid & boil off CO₂. amm. phosphate solution - White
divide the solution in two parts
ppt.- Mg²⁺
(i) To one part of solution add pot.
ferrocyanide solution- Bluish (i) To one part of the above solution add
white ppt. K₂CrO₄ solution. Yellow ppt. Con irms (ii) Perform charcoal cavity cobalt
(ii) To second part of solution add NaOH Ba²⁺ nitrate test with white ppt. - A Pink
solution. White ppt. soluble in excess. mass.
(ii) If Ba²⁺ is absent, then to the second
part of above solution add ammonium
Con irmation of Ni²⁺ and Co²⁺ Test for NH₄⁺
+ sulphate solution. A White ppt. con-
If the ppt. obtained is black Ni²⁺or Co² is
irms Sr²⁺. Heat the salt and sodium hydroxide
indicated. Note the colour of the salt, if the
solution. If ammonia gas evolves, NH₄⁺
salt is greenish - Ni²⁺ is indicated and if
(iii) If Both Ba²⁺and Sr²⁺are absent, then is present.
the salt is purple Co²⁺is indicated
to the third part of the above solution
Pass the gas through Nessler's reagent.
add ammonium oxlate solution. A
A brownish ppt. or colouration is
adding NH₄OH. Add a pinch of potassium
white ppt. con irms Ca²⁺ . obtained.
nitrite and acidify with dil. acetic acid
- Yellow ppt.
Perform the lame test with a part of the Note. NH₄⁺ may be tested in the beginning
salt. of analysis of basic redicals as zero group.
Blue bead.
Con irmation of Ni²⁺ (i) Light green lame-Ba²⁺ con irmed.
(i) Take O.S. and make alkaline by adding
(ii) Crimson red lame- Sr²⁺ con irmed.
NH₄OH and then add a few drops of
dimethyl glyoxime - Bright red ppt.
(iii) Brick red lame - Ca²⁺ con irmed.
(ii) Perform borax bead test with salt-
Brown bead in oxidising lame
and grey bead in reducing lame.
Con irmation of Mn²⁺
(i) Dissolve lesh coloured ppt. in dil. HCI,
boil off H₂S , add NaOH and Br₂ water
- White ppt. turning grey.
(ii) Perform borex bead test with group
ppt - Pink bead in oxidising lame and
colourless in reducing lame.
 READY REFERENCE CHART FOR QUALITATIVE ANALYSIS OF ACID RADICALS
Dil. H₂SO₄ Test
Treat the salt with dil. H₂SO₄
(i) CO₂ gas, turns lime water milky - CO₃²
(ii) H₂S gas (smells like rotten eggs), turns lead acetate paper black - S
2 (ii) Br₂ gas turns starch paper yellow or orange - Br.-.
2 (iii) I₂ vapours turns starch paper blue - I-.
(iii) SO₂ gas, turns acidi ied potassium dichromate paper green - SO₃
(iv) NO₂ gas (reddish brown), turns FeSO₄ solution black - NO₂
CONFIRMATORY TESTS
Con irmation of CO₃²
-
Try to dissolve the salt in water. If the salt dissolves soluble CO₃² is indicated.
(i) To the solution add dil. HCl - CO₂ gas evolves with brisk effervescence.
(ii) To the solution add MgSO₄ solution - White ppt. con irms soluble carbonate.
If the salt does not dissolve in water - insoluble carbonate is indicated.
To the solid salt add dil. HCl - CO₂ gas evolves with brisk effervescence - con irms
insoluble carbonate.
Con irmation of S²-
(i) W.E. or S.E. + acetic acid + lead acetate solution - Black ppt.
(ii) W.E. or S.E. + Sod. nitroprusside solution - A purple or violet colouration.
(ii) W.E. or S.E. + suspension of CdCO₃ - A yellow ppt.
-
Con irmation of SO₃²
(i) W.E. or S.E. + BaCl₂ solution - White ppt. which dissolves with evolution of
SO₂ on adding dil. HCl.
(ii) Salt + a few drops of acidi ied KMnO₄ - Pink colour of KMnO₄ disappears.
Con irmation of NO₂-
(i) W.E. + acetic acid + FeSO₄ - Dark brown or black colour.
(ii) W.E. + 2-3 drops of H₂SO₄ + KI solution + 2-3 drops of starch solution - Blue
colouration.
(iii) W.E. + a few drops of acidi ied KMnO₄ solution - Pink colour disappears.
If no gas is evolved when the salt is treated with dilute sulphuric acid.
- Absence of CO₃²- , S ²-, SO₃²-and NO₂-
Conc. H₂SO₄ Test If no gas is evolved when mixture is heated with conc. H₂SO₄₊
Heat a pinch of the salt with conc. H₂SO₄
-
(i) HCl gas gives white ppt. (soluble in NH₄OH) with AgNO₃ - Cl - - - - - -
Absence of Cl , Br , I , NO₃ , CH₃COO and C₂O₄²
If the salt does not react with dil. H₂SO₄ as well as conc. H₂SO₄ test for
SO₄²- and PO₄ ³-
(iv) NO₂ gas (on adding a paper pellet) turns FeSO₄ solution black - NO₃-
(v) A colourless, odourless gas (CO₂) - C₂O₄2-
(vi) Colourless vapours with vinegar smell - CH₃COO- Con irmation of SO₄²-
(i) Barium chloride test. W.E. or S.E. + dil. HCl + BaCl₂ Solution - White ppt.
CONFIRMATORY TESTS
insoluble in dil HCl
Con irmation of Cl-
(i) To the salt solution add conc. HNO₃ and AgNO₃ solution -A white ppt. soluble (ii) Match stick test. Mix the salt with Na₂CO₃. Make its paste. Fuse a little
in NH₄OH solution. paste on the end of match stick. Dip the fused mass in sod. nitroprusside
(ii) To the salt add MnO₂ and conc. H₂SO₄ and heat - Cl₂ gas evolves.
solution - Purple steaks.
(iii) Salt + K₂Cr₂O₇ solid + conc. H₂SO₄, heat - Red vapours. Pass the vapours
through NaOH solution. To the yellow solution obtained add acetic acid and Con irmation of PO₄³-
lead acetate solution - yellow ppt. con irms Cl- (i) Ammonium molybdate test. S.E. + conc. HNO₃ and boil. Now add amm.
Con irmation of Br- molybdate sol. and heat - Yellow ppt.
(i) Salt solution + conc. HNO₃ + AgNO₃ solution - Pale yellow ppt. partially (ii) Magnesia mixture test. W.E. or neutral S.E.+ Magnesia mixture - White
soluble in NH₄OH. ppt.
(ii) Chlorine water test. Salt solution + dil. HCl + 1-2 ml of carbon disulphide +
chlorine water, shake - Orange colour in CS₂ layer.
Con irmation of I-
(i) Salt solution + conc. HNO₃+ AgNO₃ solution - Yellow ppt. insoluble in NH₄OH.
(ii) Chlorine water test. Salt solution + dil. HCl + 1-2 ml of CS₂+ Chlorine
water, shake - violet colour in CS₂ layer.
Con irmation of CH₃COO-
(i) Oxalic acid test. Solid salt + oxalic acid + 2-3 drops of water, rub - Vinegar
smell.
(ii) Ester test. Salt + conc. H₂SO₄ + Ethyl alcohol, heat - Fruity smell.
Con irmation of C₂O₄2-
(i) Salt solution + acetic acid + CaCl₂ solution - White ppt.
(ii) Salt + dil. H₂SO₄, warm and add 2-3 drops of KMnO₄ solution - Pink colour is
discharged.
Con irmation of NO₃-
(i) Mixture + conc. H₂SO₄+ Cu chips. Heat - Reddish brown gas.
(ii) W.E. + FeSO₄ solution + conc. H₂SO₄ by the sides of the tube- Dark brown
ring.
 Table : Physical Examination

Experiment Observations Inference

1. Colour Blue or bluish green Cu ²⁺ or Ni ²⁺

Greenish Ni ²⁺
Light green Fe ²⁺
Dark brown Fe ³⁺
Pink Co ²⁺
Light pink, lesh colour or earthy colour Mn ²⁺

White Shows the absence of

Cu ²⁺, Ni ²⁺, Fe ²⁺, Fe ³⁺,
Mn ²⁺, Co ²⁺

2. Smell
Take a pinch of the Ammonical smell NH₄⁺
-
salt between your Vinegar like smell CH₃COO
-
ingers and rub with Smell like that of rotten eggs S²
a drop of water

(i) Heavy Salt of Pb ²⁺ or Ba ²⁺

3. Density

(ii) Light luffy powder Carbonate

4. Deliquescence Salt absorbs moisture and (i) If coloured, may be

becomes paste like Cu(NO₃)₂ , FeCl₃

(ii) If colourless, may be

Zn(NO₃)₂ , chlorides of
Zn²⁺, Mg²⁺ etc.
 DILUTE SULPHURIC ACID TEST

Take a small quantity of the salt in a test-tube and add 1-2 ml of dilute sulphuric acid.
Identify the gas and draw inferences from Table

Table : Dilute Sulphuric Acid Test

Inference
Observations
Gas Radical
-
1. Colourless, odourless gas with brisk effervescence, CO₂ CO₃²

turns lime water milky.

2. Colourless gas, pungent smell, turns acidi ied SO₂ SO₃²-

potassium dichromate paper or solution green.

-
3. Colourless gas, with smell, like that of rotten eggs, H₂S S²

turns lead acetate paper black.

4. Reddish brown gas, punget smell, turns ferrous NO₂ NO₂-

sulphate solution black.

5. No gas is evolved. ------- CO₃² -, SO₃² -, S ² -

NO₂- absent

Note :
1. Do not treat the salt with a large quantity of dilute acid.
2. Do not heat the salt with dilute acid.
 CONCENTRATED SULPHURIC ACID TEST
This test is performed by treating small quantity of salt with conc. sulphuric acid (2-3 ml) in a
test tube. Identify the gas evolved in cold and then on heating. Draw inferences from table.
Table : Conc. Sulphuric Acid Test
Inference
Observations
Gas Radical

1. Colourless, gas with pungent smell, white fumes with aqueous HCl Cl -
ammonia (NH₄OH), white ppt. with AgNO₃ solution.

2. Reddish brown vapours with pungent smell, turns starch paper Br₂ Br -
yellow. It does not turn FeSO₄ solution black.
-
3. Deep violet vapours with pungent smell, turns starch paper blue. I₂ vapours I
A sublimate is formed on the sides of the tube.

4. Reddish brown gas with pungent smell, turns FeSO₄ solution black. NO₂ NO₃-
-
5. Colourless vapours, vinegar smell, turns blue litmus red. CH₃COOH CH₃COO
vapours.
-
6. A colourless gas which turns lime water milky and also a gas which CO₂ + CO C₂ O₄²
burns with pale - bluish lame
- - - -
7. No gas/vapours evolved. -------- Cl , Br I , NO₃ ,
CH₃CHOO - absent

Note:
12.9.
1. Do not boil the salt with conc. sulphuric acid. On boiling the acid may decompose to give SO₂ gas.
2. Nitrates give vapours of nitric acid (colourless) when heated with conc. sulphuric acid. When a paper pellet or
copper chips is added. dense brown fumes evolve. Paper pellet acts as a reducing agent and reduces nitric
acid to NO₂ (Reddish brown gas.)
12.9. QUALITATIVE ANALYSIS
The following table will help the students in the choice of a suitable solvent :

Solvent Salts which dissolve

1. Cold water (a) All NH₄+ , Na+ and K + salts.
(b) All nitrites, nitrates and acetates.
(c) Most of the sulphates except that those of Pb, Ba, Ca, Sr.
(d) All chlorides except that of lead.
2. Hot water Lead chloride, lead nitrate.
3. Dil. HCl All carbonates which do not dissolve in water i.e.,
Carbonates of Ca, Ba, Sr, Mg, Zn, Al, Cu, Ni, Mn, Fe etc.
but not of Pb.

The separation of cations into various groups by making use of suitable reagents (known as a group reagents) is based on the
differences in chemical properties of cations. For example, if hydrochloric acid is added to a solution containing all cations,
only the chlorides of lead, silver and mercury (ous) will precipitate, since all other chlorides are soluble. Thus, these cations
form a group of ions which may be precipitated from solution by addition of group reagent HCl. Similarly, H₂S is a group
reagent for group II. The following Table clearly shows the group reagents for different groups and the form in which cations
of the particular group are precipitated out.

Group Group reagent Cations Form in which cations

are precipitated
Group Zero No NH₄⁺ -----

Group I Dilute HCl Pb ²⁺ Chlorides

Pb ²⁺
Group II H₂S in the presence of dilute HCl Sulphides
Cu ²⁺, As ³⁺

Group III NH₄OH in the presence of NH₄Cl Fe ³⁺, Al ³⁺ Hydroxides

Ni ²⁺, Mn ²⁺, Zn ²⁺
Group IV H₂S in the presence of NH₄OH Sulphides
Co ²⁺

Group V (NH₄)₂CO₃ in the presence of NH₄OH Ca ²⁺, Ba ²⁺, Sr ²⁺ Carbonates

Group VI No Mg ²⁺ -----