Group 4 Anions

Franchezca Marie Unknown Sample

C. Alcomendras
BSMLS 1G

Remaining Unknown Sample 3 drops unknown sample

Silver acetate precipitates the
ions of this group into a solution, Transfer, test tube
acid with acetic acid: Add 5 drops AgAc
Add saturated AgAc slowly (Max. 15 drops)
Add 3M HNO3 till acid
Stir till complete precipitation
Cl-+ Ag+ = AgCl Acidify with Acetic Acid
Stir
CNS- + Ag+ = AgCNS Centrifuge

(+) Yellow, orange, (–)

The solubilities are so reduced Precipitate Centrifugate THIOSULFATE brown and black THIOSULFATE
that only AgCl significantly ION percipitate? ION
Wash twice with H2O + (3-5
dissolves, thus allowing the
drops) 3M HNO3 Discard
chloride ion to be separated
from other Group IV anions: Discard washings
10 drops Ammoniacal
AgCl + 2NH3 AgNO3 
END
Stir
= Ag(NH3)2+ + Cl-
Centrifuge
A white precipitate with the thiosulfate
ion is produced by the group
Centrifugate Precipitate precipitating agent, the silver ion in acid
solution: 
Add HNO3 till 1 drop of 3M HCl
2Ag++ S2O3- = Ag2S2O3
decidely acid 1 drop of 1M FeCl3

Silver thiosulfate is unstable and at room

temperature, it breaks down into silver
(+) (–) sulfide:
Fromation of red
THIOCYANATE THIOCYANATE  Ag S O +2H O= Ag S + H O+ + HSO -
(+) Formation of (–) coloration? 2 2 3 2 2 3 4
ION ION
CHLORIDE white CHLORIDE
ION precipitate ION
END

 A portion of Group IV anion, containing AgCNS, is

END treated with hydrochloric acid and ferric chloride
solution precipitates, a red coloring is produced.

Using ammonia silver complex, white precipitate AgCNS + Cl-= AgCl + CNS-
is formed. This in turn gives us the presence of
chloride ion: The thiocyanate ion mixed with ferric ion
produces a colored complex. This, in turn, gives
Ag(NH3)2++ Cl- + 2H3O+ = AgCl + 2NH4++ 2H2O us the presence of thiocyanate ion:

Fe3+6CNS = Fe(CNS)63-
 Group 5 Anions
Unknown Sample

1st Portion 2nd Portion 3rd Portion 4th Portion

Add 5 drops Place in evaporating Equal

concentrated HNO3  dish volume of
2 drops of 0.5M 5 drops of concentrated urea in Test 1 Test 2
H2SO4  HCl
AgNO3 
 Cool solution 1 drop unknown
Stand, 2 minutes Small crystal of
3 drops of carminic acid sample, spot plate
Centrifuge ferrous sulfate,
Warm 2 drops H2SO4 
Discard precipitate (+) Vigorous (-) spot plate
Add NaNO2 crystals 1 drop  1 drop unknown
NITRITE evolution of NITRITE
α-naphthylamine sample
Stir ION gas ION
Stand, 3 minutes 1 drop
(+) Change (-)
concentrated
BORATE of red to BORATE
(+) (-) H2SO4 
ION bluish-violet ION END
NITRATE Purple ring NITRATE
Formation ION ION
(+) (-)
of
CHLORATE CHLORATE END
white (+) Brown (-)
ION ION
precipitate END NITRATE ring around NITRATE
ION  crystal ION

Nitrite ion in diluted solution of hydrochloric acid reacts

as redox products with urea to develop nitrogen and
END carbon dioxide. Thus, there is a presence of nitrite ions. END
CO(NH2)2 + 7H2O = CO2 + N2 + 6H2O+ + 6e
6e + 2NO2- + 8H3O+ = N2 + 12H2O
The chlorate ion is reduced to the chloride ion by _____________________________________
nitrous acid, which is then precipitated as AgCl:
CO(NH2)2 + 2NO2- + 2H3O+ = CO2 + 2N2 + 5H2O
ClO3- + 3HNO2 + 3H2O = Cl- + 3NO3- + 3H3O+

Cl- + Ag+ = AgCl

Thus, formed a white precipitate, which results to

the presence of Chlorate ion  In the brown ring test, in the presence of the nitrite ion, the
nitrate ion can not be identified, as two ions give the same test:
NO2- + NH4+ = N2 + 2H2O

The presence of the nitrate ion is confirmed by the reduction of

nitric acid by ferrous ions at a high concentration of sulfuric acid
in the absence of the nitrite ion.
A ceartain hydroxyanthraquinones (alizarin
dyes), dissolved in concentrated sulfuric acid, give boric acid characteristic 3Fe(H2O)5++ + NO3- + 4H3O+ = 3Fe(H2O)63++ NO + 6H3O
changes in colour. The specific dye used in this scheme is a carminic acid
solution of sulfuric acid. This changes from red to a bluish-violet color with the presence of
boric acid The test of chemistry transcends the scope of qualitative analysis. This test Fe(H2O)6++ + NO = Fe(H2O)5 NO++ + H2O
interferes with oxidizing agents. Thus, the other group IV anions has to be destroyed or
removed.
First, the Chlorate ions converted into perchloric acid which volatilizes at this temperature.

3HClO3 = HClO4 + 2ClO2 + H2O

Second will be the nitrate ion. When heated with concentrated sulfuric acid, the nitrate
ion is in the form of nitric acid, which boils off at 86oC with some decomposition into NO2,
H2O, and O2
4HNO3 = 2H2O + 4NO2 + O2

The third one to be eliminated will be the nitrite ion. When heated in the presence of
concentrated sulfuric acid, the nitrite ion, in form of nitrous acid, is decomposed into H2O,
NO2, and NO, all of which are volatile

2HNO2 = H2O + NO2 + NO

Thus, this gives us the presence of borate ion