ANALYSIS OF BASIC RADICALS (CATIONS) BY WET TESTS

11.16. Preparation of Original Solution of Salt

To identify the basic radicals clear solution of the salt is prepared using following
solvents:
Mote
1. Ifsome gas is evolved.lduring the
The solution may be heated if required. Strictly try the solvents in the order given
below : preparation of original solution.
heat to remove gases, add
() Distilled water (cold or hot), (i) Dilute HCI (cold or hot), (ü) Conc. HCl (cold or
ho), (iv) Dil HNO,, () Conc. HNO,. solvent to get clear solution.more
2. If the original
Dissolve 2g of salt in 10mL of selected solvent, heat if required and label it as
prepared in dil HC,
solution i
original solution or O.S.
Group I is absent and withthen thic
solution proceed for Group II
11.17. Analysis of Group Zero Cation (NH) analysis.

Procedure
In a test tube, heat a smallamount of salt with concentrated solution of sodium
hydroxide.
Gas with ammoniacal smell is evolved indicating the presence of NH, radical.
Confirmatory Tests of Ammonium Ion NH
Experiment
Observations Inference
1, Sodium hydroxide test
() Heat the salt with few drops of conc.
NaOH solution in a test tube. Colourless gas with
(i) White fumes test typical NH presen:.
ammoniacal smell evolved.
Bring a glass rod dipped in dil. HCI near the mouth of test tube.
Dense white fumes are formned.
2. Nessler's reagent test NH confirmed.
Pas the gas in step () through Nessler's reagent taken in a gas
detector. A brown ppt. is NH confirmed.
formed.
 11.18. Analysis of Group I Gation (Ph+)
Group I includes lb, Ag* and Hg,*. But in the present discussion, we shall
study the analysis of only ro
Group reagent : Dilute bydrochloric acid ; Group reaction: Ph2+ is
precipitated as lead chloride.
Procedure
To about 2 mL of the original solution of the salt, add 1-2 mL of dil. HCI, Formation of white precpite
presence ofGroup I((P). Filter and wash the ppt. with water and boil it with 5-10 mL of water till it dissolves. Divide the
solution in three parts.
Group I
W.E. + dil. HCI

White ppt. Pb2+

Confirmatory tests of Pb2+
Inference
Observations
Experiment
1. Di. H,SO, Test Pb2* confirmed.
White ppt. separates out
To one part of above solution, add few drops of dil. H,SO
Potassium iodide Test Pb2+ confirmed.
2.
potassium iodide (KI) Yellow ppt. is formed
To second part of above soluion, add few drops of
solution.
Potassium Chromate Test PL2* confirmed.
3.
solution, add few drops of potassium chromate (K,CO) Yellow ppt. is formed
To third part of above
solution.

Cations (Pb+, Cu?+, Ag3+)

11.19. Analysis of Group II
reagent : Hydrogen sulphide in thepresence of dil. HC.Ifgroup I is absent, then the salt is tested for group l radicals.
Group precipitatedas their suphides.
Group reaction : Radicals are
through this
HCI, and pass H,S gas
Procedure
of the salt in a test
tube, add 1-2 mL dil.
II radicals. Pass more ofH,S
original solution presence of Group
Take abour 2 mL of the Formation of precipitateindicates precipitates or centrifuge the contents using a
as shown in Fig. 10. the radical sulphide. Filter the
using Kipps' apparatus
complete precipitation of
gas so as to ensure explained in flow sheet diagram.
Proceed as
centrifugal machine.

Dil. H,SO4 aH,S Gas-

Iron
sulphide
pleces

Wash bottie
Kipps' apparatus

of H,S gas
Kipps' apparatus for supply
Figure 10.
 proceed as given i
Dissolve the yellow PPt. in conc. HNO, and divide the solutioninto two parts and the flow
Group-II (Pb2+, Cu2+, As3+)
she r
0.S. of salt

add dil. HC, pass H,S gas

Black
(Pb2+, Cu2+)
Group ILA

Heat the ppt. with minimum

quantity of 50% HNO,

ppt, dissolve
(Pb2*, Cu²)
Add dil H,SO, and ethyl alcohol

No ppt. formed
(Cu2+)
Add NHOH in excess
to above solution
white ppt. formed Blue coloured solution Yellow ppt.
(Pb2+ present) (As3+)
(Cu2t present) Group IIB
Box-1 Box-2 Box-3
Confirmatory test of Pb2+ Confirmatory tests of Cu2+ Confirmatory test of As3+
White ppt. (Pb2+) Deep Blue solution (Cu2+) Yellow ppt. (A_+)
Dissolve the white ppt in hot ammonium Dissove the yellow ppt. in conc. HN0, to get a clear solution.
acetate solution.

1. Potassium iodide test 1. Potassium ferrocyanide test

To one part of the above solution, add few 1. Ammonium molybdate test
To one part of blue solution, add few drops of acetic To one part of above solution, add few drops of ammonium movbdate
drops of potassium iodide solution.
’yellow ppt. acid and potassium ferrocyanide solution. solution
2. Potassium chromate test chocolate brown ppt ’ yellow ppt
another part of solution, add few drops 2. Potassium iodide test 2. Magnesia mixture test
of potassium chromate solution To another part of blue solution, add few drops of To other part of the above solution, add NH,OH in exaeSs and maqnesia
potassium iodide solution. mixture.
yellow ppt. soluble in NaOH ’ white ppt.
+ white ppt. in brown solution.

11.20. Analysis of Group III Cations (Feß+, A8+)

Group reagent : NH OH in the presence of NH,C;Group reaction : Radicals are precipitated as their hydroxides.
Procedure
Ifgroup I and group ll are absent then the salt is tested for group IIl radicals.
() Take about 5 mlL of the original solution of the salt and add 4-5
drops of conc. nitric acid. Boil the solution.
(i) Add about 2 g of solid ammonium chloride and boil again. Do not add excess of
ammonium chloride because it will ga
crystallised on cooling.
(ii) Cool the solution under tap water, add ammonium hydroxide solution
hydroxide till there is typical ammoniacal smell. slowly with shaking, add excess of ammon
(iv) Abrownish precipitate indicates Fe"and a gelatinous uwhite
indicates Al³*, centrifuge and wash the ppt. with watet.
The group Ill cations are precipitated as hydroxides on the addition of
excess of ammonium hydroxide.
 Group-III (Fe, AP)
0.S. of the sale
Add NH,CI G), boil, cool, add
Mote
NH,OH in excess 1. The function of concentrated
is to
Reddish brown ppt. (Fe) HNO, acid in Group IIl ions.
Gelainous white ppt. (AP*) oxidise Fe2t to F t
Confirmatory tests of Fe3+ Concentrated HNO, should be
Dissolvethe reddish brown ppt. in dil. HCI.
Confirmatory tests of AI'* added only if Fet is present in
test Dissolve gelatinous white ppt. in dil. HCI. the salt. The presence of Fet
1. Potassium ferrocyanide 1. Disodium hydrogen 0n the salt can be tested by adding
To one part of the above solution, add
potassium ferrocyanide solution, To one part of above phosphate solution test
solution, add few drops of Na,HPO4 few drops of potassium
solution ferricyanide solution to the
Prussian bue colouration.
’white ppt. origínal solution of the salt. A
2. Potassium sulphocyanide test
To the second part of above solution
2. Sodium acetate
test deep blue colouration indicates
To
few drops of potassium sulphocyanide acetatesecond part of above solution, add few drops of sodium Fe2+. If this test is not positive,
solution then HNO, should not be added.
solution. ’
Blood red colouration. No. ppt. in cold but whie ppt. on boiling.
3. Lake test 2. Use excess of NH CI to avoid
precipitation of cations of higher
To a portion of above solution add 2 drops of blue litmus
solution a pink colour is obtained. To this, add NH,OH groups alongwith the radicals of
dropwise till blue colour develops. Group II.
Blue ppr. floating in the colourless solution. 3. Add NH OH until ammoniacal
smell is given off from the
11.21. Analysis of Group IV Cations (Ni?+, Mn?+, Zn2+) solution.

Group reagent :H,S gas in the presenceofNH,C and NH, OH;Group racion :Radicas are precipitated as their suphrdes.
Procedure : Ifgroup IIl is absent then the solution for radical of GroupIV.Pass H,S directly into it ablack, buff or white
precipitace ppt. indicates the presence of group IV radicals. Pass H,S gas 2-3 times to ensure the complete precipitation. Flter
the precipitates, wash with water and proced as given in flow shet.
Group IV : (N², Mn, Znz)
Group II solution
Pass H,S
Black ppt. (Ni) Buff coloured ppt. (Mn) Dirty white ppt. (Zn+)
To black ppt. add 10 drops of conc. HCI
and few drops of conc. HNO,, heat to dryness.
Yellow residue (Ni2)
Confirmatory tests of Zn2+
Confirmatory tests of NiZ Confirmatory tests of Mn2+
Dissolved the yellow residue in distilled Dissolve buff coloured ppt. in dil. HCI, boil Dissolve dirty white ppt. in dil. HCI, boil
off H,S and divide the solution in two
water to get green coloured solution. off H,S and divide the solution in two parts.
parts.

1. Sodium hydroxide test - Br, test 1, Sodium hydroxide test

1. Dimethyl glyoxime test To one part of above solution, add sodium
To above solution, add NaOH solution
To a part of green coloured solution, add hydroxide soluion dropwise.
NH,OH illit becomes alkaline. Add few
drops of dimethyl glyoxime reagent ’White ppt. which turns black or browm White ppt. soluble in excess of NaOH
Scarlet red ppt. on adding bromine water.
2. Disodium hydrogen phosphate test 2. Potassium ferrocyanide test
2. Sodium hydroxide test
To another part of above solution, add few
To above solution, add NH,OHtillalkaline, To another part of solution, add few drops
drops of NaOH solution. then add Na,HPO, solution of potassium ferrocyanide solution.
’Pink PPr. White or bluish white ppt.
’ Green pPPt.
3. Borax bead test 3. Charcoal cavity/Cobalt nitrate test
3. Borax bead test
Perform borax bead test with the wich the Perform borax bead test wrih the buff coloured Perform charcoal cavitylcobalt nitrate test
precipitate with the dirty white ppt.
black ppt. ’ Pinkish bead in oxidising anda colourless ’ grenish reidue obrained.
’ Brown bead in oxidising and grey bead in reducing fame is obrained
bead in reducing flame.
 11.22. Analysis of Group VCations (Ba?+, Sr+, Cat)
When the radicals of first four grouns are absent then twe proced for group Vanajysts.
Mote
The radicals of
Group reagent : Ammonium carbonate in the presence of ammonium chloride and am be tested in the Group V
order should
monium ydroxide.
Group reaction : These radical are precipitated as their carbonates.
Ca?t. If Ba2+ is
coBa,irmSedP,
nf
not proceed to test for
s24 o
Procedure : Take the ).S., add 2.3 ems of solid ammonium chloride, boil, cool and Ca2+. Similarly, if S24 and
add ammonium hydroxide in excess,Then add ammonium carbonate solution, formation confirmed, do not test for Ch+
of white ppt. indicate the presence of Group Vradicals, Dissolve the ppt. in 5-10 mL of dil
acetic acid and confirm as follows :
Group-V:(Ba,Sr2*, Cal)
White precipitate (Ba*, Se, Ca)
Add acetic acid, heat

Precipitates dissolve to form cdear solution

To third part of solution

To one part of clear solution To other part of solution add add amonium hydroxide and
add K,CrO, ammonium sulphate solution amonium chromate solution
Yellow ppt. (Ba') White ppt. (S) White ppt. (Cal)

Confirmatory tests of Ba2+ Confirmatory tests of SF2 Confirmatory tests of Ca2+

1.Potassium chromate test 1. Ammonium sulphate test 1. Ammonium oxalate test
To a part of above solution, add few drops of To second part of the
potasium chromate solution. above solution, add few drops To a part of above solution, add NH,COH l
of ammonium sulphate solution. alkaline, then add few drops of (NH),C,0,
yellow ppt. White ppt. White ppt.
2. Flame test 2. Flame test 3. Flame test
Perform the flame test with the paste of group-V Perform the flame test with a paste of white ppt.
ppt. (white ppt.) and conc. HCI. and conc. HCI
Perform the flame test with a paste of white ppt.
(group-V ppt.) and conc. HCL.
Grassy green flame. ’ Grimson red flame visible through blue glas. Brick red flame, seen yellow through blue glar.
Please note that in the sequence of the analsis, first Ba* is tested, then S and last of all Ca radical is
tested.
11.23. Analysis of Group VI Cations (Mg+)
There is no Group reagent for Group VI radicals.
When the radicals of group I to Vare absent then perform the test for Mg as
using the original solution of the salt. given below : The analysis ofM* is done
Table 10. Detection and confirmation of Mg2+
Experiment Observations
1. Ammonium hydrogen phosphate test.
Inference
Take a part of O.S., add about 2 of solid NH,CI, heat
and cool under tap water, then add excess of Awhite ppt. is formed.
ammonium Mgt confrmed.
hydroxide solution and few drops of disodium hydrogen
phosphat. Scratch che sides of test tube with a glass
rod.
2. Charcoal cavity and cobalt nitrate test
() Perfornm the charcoal cavity test with
and sodium carbonate.
mixture of salt White residue is obtained.
(iD Add 2 drops of cobalt nitrate solution on the white
residue and fuse the mas. Apink mass is obrained.
Mg2 confirmed.