SYSTEMATIC SCHEME FOR ANALYSIS OF SALT FOR THE PRESENCE OF ACID AND BASIC

RADICALS

1. Physical Examination:
Experiment Observations Inference
(a) Colour Blue or bluish green Cu2+ or Ni2+
Greenish Ni2+
Light green Fe2+
Dark green Cr3+
Dark brown Fe3+
Pink Co2+
Light pink, flesh colour or earthy colour Mn2+
White
Shows the absence of Cu2+, Ni2+,
Fe2+,Fe3+, Cr3+, Mn2+, Co2+
(b) Smell
Take a pinch of the salt Ammonical smell NH4+
between your fingers and Vinegar like smell CH3COO-
rub with a drop of water Smell like that of rotten eggs S2-

(c) Density (i) Heavy Salt of Hg2+, Pb2+, Ba2+

(ii) Light fluffy powder Carbonates

2. Flame Test: Certain metal salts, notably chlorides are volatile in nature. They are thermally ionizable and their
vapours impart characteristic colour to flame.
Flame Test for Cations
Flame colour with naked eye Flame colour through blue glass Inference
1. Dark-green Bluish-green Cu2+
2. Pink-violet Pink K+
3. Brick red Light-green Ca2+
4. Grassy-green Bluish-green Ba2+
5. Crimson (deep-red) Purple Sr2+

Procedure for Flame Test

(i) Take a platinum wire and make a small circular loop at its end. (by winding it around a pencil)
(ii) Dip the loop of platinum wire in conc. HCl taken in a watch glass, for cleaning the platinum wire.
(iii) Introduce the loop of platinum wire in the non-luminous flame. It should not impart any colour to flame.
When the loop is clean.
Repeat cleaning with conc. HCl till the wire imparts no colour to flame.
(iv) Make a paste of 0.5g of salt with 2-3 drops of conc. HCl on a clean watch glass.
(v) Take a small amount of the paste on the loop of the platinum wire and introduce it into the flame. Observe
the colour of the flame directly, and then observe through a blue glass.

Principle of flame test:

When metal salts (chlorides) are heated strongly in a flame, they are thermally ionized. The cation so formed absorbs
heat energy and the valence electrons get provided to higher energy level. When the electrons drop back to the ground
state, they release energy in the form of light which corresponds to a characteristic colour. Since different metal ions
emit light energy of different wave lengths therefore the colour imparted by various salts is different.

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 SYSTEMATIC IDENTIFICATION OF BASIC RADICALS (CATIONS) BY WET TESTS

General Notes:

1. Treatment of the salt with dil. or conc. HCl converts the basic radicals into chlorides. Treatment with conc. Nitric

acid converts them into their nitrates. Wait till effervescence ceases, while preparing original solution.

2. The solution should be clear, i.e. , it should not contain any suspension or precipitate.

3. The solution may have a colour, e.g., copper sulphate solution is blue in colour.

4. Use distilled water for preparing ‘original solution’.

5. When a salt is soluble in hot HCl but precipitates down on cooling, led radical is present.

6. The solution should be transparent (i.e. you should be able to see through the solution).

7. If there is any turbidity in aqueous solution adds a drop or two of conc. HCl to it. It may clear up.

8. In case the solution is prepared in cold dil HCl, that means group I cations are absent. Proceed directly with

group II analysis.

9. In case the salt is soluble in hot water but on cooling a white ppt appears which cascades down (heavy ppt) it may

be due to lead chloride precipitate.

10. Never pass H2S gas through whole of the solution in the beginning. Take only a small portion of it and first ensure

the presence of group II.

11. Pass H2S gas at least for five minutes to ensure complete precipitation of sulphides.

12. For the precipitation of group II radicals as insoluble sulphides, the acidity of the solution should be between 0.3 and

0.5M.

13. (a) If the solution is slightly acidic, H2S cannot precipitate arsenic.

14. (b) If acidity of the solution is too high, cadmium is incompletely precipitated or not precipitated at all. Therefore,

H2S should also be passed after diluting the solution.

15. Formation of white or yellow milky solution is due to the formation of colloidal sulphur, take group-II as absent in

such a case.

16. Test for group-0 ammonium ion NH4+ before you proceed with the scheme of salt analysis.

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 FLOW CHART FOR GROUP I TO V
Original Solution

Dil. HCl

(White ppt) (No ppt) I group absent

Warm and pass H2S gas in one part.

Group I present ppt

(Pb2+ may be) (No ppt) II group absent

(Black ppt) (Yellow ppt) Add 1-2 drops conc.

Group II present Group II present HNO3 + NH4Cl (2gm)

(Pb2+, Cu2+, Hg2+ may be present) (Cd2+, As3+ may be present) + NH4OH excess

(No ppt) group III absent (ppt) group III present

Pass H2S gas in a portion of above solution. Gelatinous white-Al3+

Reddish Brown- Fe3+

(Ppt) group IV present (No ppt) group IV absent

Black ppt- Co2+, Ni2+ Add (NH4)2CO3 in remaining solution.

Dirty White ppt- Zn2+

Light-pink/ buff ppt- Mn2+

(No ppt) group V absent (White ppt) group V present

Ba2+, Sr2+, Ca2+

Proceed for group VI

Mg2+
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 SYSTEMATIC IDENTIFICATION OF BASIC RADICALS (CATIONS) BY WET TESTS

Experiment Observation Inference

0-group
a) To 0.5 g of the dry salt in a clean dry test tube. Smell of ammonia gas NH4+ may be present
Add concentrated solution of NaOH to it. Warm
gently
b) Take a rod dipped in HCl near the mouth of the Evolution of dense NH4+ may be present
test tube white fumes
Confirmatory Test-
Heat the test tube containing original salt and conc. Reddish-brown NH4+ confirmed
NaOH solution after adding more salt to it and pass the precipitate.
evolved gas through Nessler’s Reagent taken in
another test tube
Preparation of original solution (O.S.) Clear solution was Labelled it as
Shook a pinch of the salt with water. obtained Original
Solution(O.S.)
White precipitate which
I-group cascades down (falls I-group present
To 1 ml of the original solution (O.S.) add dil HCl down fast) Pb2+ may be present
Confirmatory Test- The ppt dissolves in hot
Filter and wash the above ppt and dissolve it in 5 ml of water.
hot water (or boil it with water). Divide the hot solution
into three parts. White crystalline ppt
(a) Cool the first part under tap water Pb2+ confirmed
(b) Potassium Chromate Test (K2CrO4)- Bright yellow ppt
Add 1ml K2CrO4 solution to the second part Pb2+ confirmed
(c) Potassium Iodide Test (KI)- Yellow ppt
Add 1 ml KI to the third part Pb2+ confirmed
II-group
Take 1 ml O.S. add dil HCl to it and pass H2S gas. Black or yellow
precipitate II-group present

Black ppt-Pb2+,Cu2+,
Hg2+ may be present
Black ppt- Add 1-2 ml of 50% HNO3( distilled water Clear transparent Yellow ppt-Cd2+, As3+
and HNO3 in equal volume) to the black ppt and heat solution Pb2+ may be present
the content and observe the solution.
Clear blue solution
Cu2+ may be present
Yellow ppt- Boil the ppt with 4-5ml of yellow Yellow ppt dissolves
ammonium sulphide or 3M KOH for 5 minutes. Cool As3+ may be present
and filter Yellow ppt does not
Wash the ppt with water and reject the washing. dissolve Cd2+ may be present
Dissolve the yellow ppt in minimum quantity of dil.
HCl. Divide the solution into two parts.

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 1. Potassium ferrocyanide test [K4Fe(CN)6]-
To 1ml of O.S. directly or the above solution in dil HCl Greenish / bluish
add HNO3 and then add potassium ferrocyanide white ppt Cd2+ confirmed
solution.
2. Sodium hydroxide test-
To 1ml of O.S. directly or the above solution in White ppt
dil HCl add NaOH solution in excess. Cd2+ confirmed

Dissolve the yellow ppt in yellow ammonium sulphide Any yellow ppt
[(NH4)2S] add conc. HNO3 and divide it into two parts. As3+ confirmed
1. Ammonium Molybdate Test[(NH4)2MoO4]-
To 1ml of O.S. directly or the solution in conc.
HNO3 acidify with conc. HNO3, then White ppt
ammonium molybdate solution powder and heat As3+ confirmed
strongly.
2. Magnesium Mixture Test-
To 1ml of O.S. directly or the solution in
conc.HNO3 acidify with conc.HNO3, then add
magnesia mixture (MgSO4, NH4Cl and NH4OH
solutions mixed in equal volumes) and heat.
Cool the contents and observe.
III-group
Take 1-2 ml of O.S. or boil off H2S from the previous III-group present
solution. Add 4-5 drops of conc.HNO3. Boil for some Reddish brown ppt
time. Add about 1-2 g of solid NH4Cl (add distilled Fe3+ may be present
water around test tube if salt stick in side of the test Gelatinous white ppt
tube) and boil again. Cool under tap water. Add excess Al3+ may be present
of NH4OH till the solution give smell of ammonia.
Filter the precipitate.
Reddish brown ppt Ppt dissolve in dil HCl
Dissolve the reddish brown ppt in dil HCl and divide
the solution into two parts. Prussian blue
1. Potassium ferrocyanide test [K4Fe(CN)6]- coloration Fe3+ confirmed
To 1ml of O.S. directly or the above solution in
dil HCl add potassium ferrocyanide solution

2. Potassium Sulphocyanide Test [KCNS]- Blood red coloration

To 1ml of O.S. directly or the above solution in Fe3+ confirmed
dil HCl, add potassium Sulphocyanide solution.

Gelatinous white ppt-

Dissolve the white ppt in dil HCl and divide it into two
parts. Blue ppt floating in a
1. To 1ml of O.S. directly or the above solution in colourless solution Al3+ confirmed
dil HCl add 2-3 drops of blue litmus solution. To
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 this add NH4OH solution dropwise the blue
colour develops. Leave the test tube undisturbed
for some time. White ppt
2. To 1ml of O.S. directly or the above solution in Al3+ confirmed
dil HCl add NH4OH in excess.
IV-group present
IV- group Dirty white ppt
Zn2+ may be present
Pass H2S gas in the group –III solution, if group-III Buff coloured ppt
is absent. Note the colour of the precipitate. Mn2+ may be present
Black ppt
Ni2+, Co2+ may be
The white ppt dissolves
White ppt- in HCl.
Dissolve the white ppt in dil HCl. Boil of H2S.Cool
the contents and divide it into two parts. White ppt which
1. Sodium Hydroxide Test: redissolves in excess Zn2+ confirmed
To 1 ml O.S. directly or the above solution in NaOH.
HCl add NaOH slowly.
Bluish white ppt
2. Potassium Ferrocyanide Test: Zn2+ confirmed
To 1 ml O.S. directly or the solution in dil HCl
add potassium ferrocyanide solution. The ppt dissolves in
HCl.
Buff coloured ppt-
Dissolve the buff coloured ppt in dil HCl. Boil of H2S
completely. Cool and divide the solution into two parts. White ppt that slowly
1. Sodium hydroxide test- turns brown and Mn2+ confirmed
To 1 ml O.S. directly or the above solution in finally to a black
HCl add NH4OH in excess and wait for 2-3 colour.
minutes.
Appearance of green Mn2+ may be
2. Fusion Test mass
(a) To the original salt (0.5g) or the buff ppt add
PbO2 along with 3-4 pellets of solid KOH.
Fuse the contents carefully by heating
steadily on a direct flame and note the A green solution Mn2+ confirmed
change in colour of the solid mass
(b) Cool the test tube by keeping it aside for 10 Pink colouration Mn2+ confirmed
minutes, and then add water to the fused
mass.
(c) Add excess H2SO4 to a little amount of this
green solution in a separate test tube Blue residue Co2+ may be
Black ppt
Dissolve the black ppt in minimum quantity of aqua Yellow residue Ni2+ may be
regia (Aqua regia is a mixture of 3parts of conc. HCl
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and 1 part of conc. HNO3). Evaporate the solution to
dryness in a china dish. Scrap the solid and dissolve it in
distilled water.
The blue residue dissolves in water to give a pink
solution. Divide the solution into two parts: Yellow ppt Co2+ confirmed
1. Potassium Nitrate test-
To 1 ml O.S. directly or the above solution add
excess NH4OH to neutralize the acid. Add acetic
acid and a crystal of potassium nitrate. Warm the Bright blue Co2+ confirmed
contents. colouration
2. Ammonium Thiocyanate Solution-
To 1 ml O.S. directly or the above solution add
ammonium thiocyanate solution. Mix the
contents then slowly add 1 ml of acetone by
tilting the test tube. Do not shake/ mix the
solution Rosy red ppt Ni2+ confirmed

The yellow residue dissolves in water to give a green

coloured solution. Divide the solution in two parts.
1. Dimethyle Glyoxime Test-
To 1 ml O.S. directly or the above solution add Black ppt Ni2+ confirmed
excess NH4OH to neutralize the acid. Then add
a few drops of dimethyle glyoxime (DMG)
solution. White ppt V-group present
2. To 1 ml O.S. directly or the above solution add
excess of NaOH solution. Add Br2 water to it Ba2+, Sr2+, Ca2+ may be
and boil the contents carefully. present
V- group
To 1-2 ml of the O.S. or continue with the previous
group solution (after boiling off H2S completely). Add
1-2 g of solid NH4Cl. Boil the contents. Cool and add
excess NH4OH till the solution gives smell of NH3.
Then add saturated solution of (NH4)2CO3 to it. Filter Bright yellow ppt Ba2+ confirmed
the ppt.

Filter and wash the precipitate with water. Dissolve the

ppt in hot dil. acetic acid and divide the solution into Apple green flame Ba2+ confirmed
three parts.
1. Potassium Chromate Test (K2CrO4)-
To 1ml of O.S. directly or the above solution in acetic
acid add a few drops of potassium chromate solution. White ppt Sr2+ confirmed
Flame test-
Do flame test with the help of platinum wire

(only if Ba2+ is absent) Crimson red flame Sr2+ confirmed

1. Ammonium Sulphate Test (NH4)2SO4: (pinkish red)

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 To 1ml of O.S. directly or the above solution in
acetic acid add 1ml of ammonium sulphate solution.
White ppt Ca2+ confirmed
Flame test-
Do flame test with the help of platinum wire
Brick red flame Ca2+ confirmed
2+ 2+
( only if Ba and Sr are absent)
1. Ammonium Oxalate test [(NH4)2C2O4]-
To 1ml of O.S. directly or the original solution in dil
acetic acid add 1ml of ammonium oxalate solution. Add
a little ammonium hydroxide and scratch the sides.
Flame test-
Do flame test with the help of platinum wire

IDENTIFICATION OF GROUP VI CATIONS (Mg2+)

Proceed with the test for Mg2+ only if the test for basic radical of I, II, III, IV and V groups are absent.

Confirmatory Test for Mg2+

Experiment Observation Inference
1. Sodium Dihydrogen Phosphate Test [NaH2PO4]or
Ammonium phosphate
To 1ml of O.S. (which has been concentrated by
evaporation) add NH4Cl and NH4OH in excess, then add White ppt Mg2+confirmed
ammonium phosphate solution and rub the sides of the test-
tube with a glass rod.
2. Magneson test-
To 1ml of original solution add dil HCl and then a few drops Blue colour Mg2+confirmed
of magneson reagent.

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