Scheme for the Analysis of Inorganic Mixtures

A) Preliminary Examinations
1) Noted the color a) Green Solid Cu2+ or Ni2+ may be present

b) Pale green solid Fe2+ may be present

c) Blue solid Cu2+ may be present
d) Bluish yellow solid Fe3+ may be present
e) Light pink or Brown Mn2+ may be present
solid Co2+ may be present
f) Pink solid Absence of Cu2+, Ni2+, Fe3+,
g) colorless Co2+ etc.
2) Noted the Solubility
a) In water Soluble partly or completely Presence of ammonium
and the solution part does not
yield any precipitate when
treated with sodium carbonate
solution.

b) In dil. HCl Soluble Absence of group I cation

c) In dil.HNO3 ( Need Soluble and a precipitate is Presence of group I cation

be tested only if formed on adding dil. HCl to
the mixture is this solution
insoluble in
dil.HCl)
3) The mixture is made a a) Blue/ Bluish green Copper may be present
paste with conc. HCl color
on a watch glass. A b) Pale green color Barium may be present
little of this paste is c) Brick red color Calcium may be present
taken at the end of a d) Crimson red color Strontium may be present
glass rod and shown e) Lilac color Potassium may be present
very near a f) Golden yellow color Sodium may be present
nonluminous Bunsen g) Caramine red color Lithium may be present
flame. The color
imparted to the flame
is noted.

B) Preliminary test for Anions

1) A little of the Brisk effervescence in the cold with Carbonate may be
mixture is placed on the liberation of a colorless odorless present
a tile and add 2 gas
drops of dil. HCl
CO32-+ 2 HCl→ Cl-+
H2O+ CO2
2) The above gas is Lime water turns milky
collected in a micro Presence of carbonate
test tube and add 2 confirmed
drops of limewater
Ca(OH)2 +CO2→
CaCO3+ H2O

3) A little of the
mixture is rubbed
with dil.H2SO4 on a Vinegar smell
watch glass and the Presence of acetate
smell issuing from
the paste is noted.
2CH3COO-+ H2SO4→
2 CH3COOH +SO4 2-
4) A little of the
mixture is boiled
with dil. H2SO4 in a
micro test tube until
evolution of gases. Brisk effervescence of a colorless
A pinch of MnO2 is odorless gas turning lime water
added. milky Presence of Oxalate
C2O42- +H2SO4→
H2C2O4+ SO42-
H2C2O4+ MnO2+
H2SO4→ MnSO4+
2 CO2+2H2O a) A colorless fuming gas which
5) A little of the gives a white deposit on a
mixture is warmed moist glass rod and the test Presence of fluoride
with 2 drops of tube appears oily
conc. H2SO4 in a 2F-+ H2SO4→ SO42- +
micro test tube 2 HF
SiO32-+ 6HF→ 2F-+3H2O+SiF4
3SiF4+4 H2O→ 2
H2SiF6+H4SiO4
b) A colorless gas with a
pungent smell which fumes Presence of chloride
in moist air and gives dense
white fumes when a glass
rod dipped in NH4OH is
shown in it
Cl- +H2SO4→ HSO4- +HCl
NH3+HCl→NH4Cl
c) A reddish brown gas and the
solution turns red Presence of bromide
Br- ++H2SO4→HSO4- +HCl
2HBr+H2SO4→2H2O+SO2+Br2
 d) A violet gas which
condenses to a black solid Presence of Iodide
on the cooler sides of the
micro test tube

I-+H2SO4→HSO4- +HI
2HI+H2SO4→2H2O+SO2+I2
e) Reddish brown gas on a
strong heating Presence of nitrate
NO3-+H2SO4→HSO4-+HNO3
4HNO3→2H2O+4NO2+O2

6) A little of the
mixture is heated
with few drops of Evolution of reddish brown gas in
Conc. H2SO4 and plenty Presence of nitrate
then a small paper NO3-+H2SO4→HSO4-+HNO3
ball is added to the C+4HNO3→2H2O+4NO2+CO2
system

7) A little of the
mixture is mixed
with calcium
fluoride and made a Green color Presence of Borate
paste with conc. B4O72-+6CaF2+7H2SO4→
H2SO4 on a watch 4BF3+6CaSO4+SO42-+7H2O
glass. A little of the
paste is taken at the
end of a glass rod
and shown very
near a non-
luminous Bunsen
flame.

C) Confirmation test for Anions

1) A little of the The vapors burn with a micro green edged Presence of borate
mixture is flame confirmed
mixed with 2 B4O72-+H2SO4+5H2O→SO42-+4H3BO3
drops conc. H3BO3+3C2H5OH→(C2H5)3BO3+3H2O
H2SO4 and 4
drops of
ethanol in a
dry micro test
tube and
boiled. The
 issuing vapors
are ignited.
2) A little of the
mixture is
mixed with
two drops of Presence of acetate
conc.H2SO4 confirmed
and about four A pleasant fruity smell
drops of
ethanol. This
mixture is 2CH3COO-+H2SO4→2CH3COOH+SO42-
warmed and CH3COOH+C2H5OH→CH3COOC2H5+H2O
poured in to
water taken in
a small
beaker.
Tests using sodium carbonate extract
Preparation of sodium carbonate extract:-
1 g of the mixture is mixed with about 3g of anhydrous sodium carbonate and 20ml
deionized water in a small beaker and then boiled for about 15 minutes with frequent stirring. It
is then cooled and filtered. The following tests are done using the extract. The residue is used
for anion analysis.
1) A little of the a) White curdy precipitate soluble in Presence of chloride
sodium NH4OH confirmed
carbonate Cl-+AgNO3→AgCl+NO3-
extract is AgCl+2NH4OH→Ag(NH3)2Cl+2H2O Presence of
acidified with b) A pale yellow precipitate partially bromide confirmed
dil. HNO3, soluble in NH4OH
boiled to expel Br-+AgNO3→AgBr+KNO3
CO2 and c) A yellow precipitate insoluble in NH4OH Presence of iodide
cooled. The AgNO3+KI→AgI+KNO3 confirmed
clear solution
is treated with
two drops of
silver nitrate
solution.
2) i) A little of the
sodium
carbonate
extract is A white precipitate Presence of
acidified with SO4 +BaCl2→BaSO4+2Cl
2- - sulphate
dil. HCl, boiled
to expel CO2
and cooled.
The clear
solution is
treated with
barium
 chloride
solution.
ii) The above
precipitate is The precipitate remain as such, without Presence of
collected and dissolving sulphate confirmed
is shaken with
conc.HCl
3) a) ) A little of
the sodium
carbonate
extract is A white precipitate
acidified with 2F-+CaCl2→CaF2+Cl- Presence of
acetic acid, Or fluoride/oxalate
boiled and C2O42-+CaCl2→CaC2O4+2Cl-
treated with
calcium
chloride
solution.
b) The
precipitate is
collected,
centrifuged a)The first few drops of KMnO4 are decolorized. Presence of oxalate
and dissolve in 2KMnO4+3H2SO4→K2SO4+2MnSO4+3H2O+5[O] confirmed
hot dil.H2SO4.
To this hot a) KMnO4 is not decolorized Presence of fluoride
solution dil. is confirmed
KMnO4 is
added in
drops.
4) A little of the
sodium carbonate
extract is acidified
with dil. H2SO4, boiled
to expel CO2 and A brown ring at the junction of two layers
cooled well. The NO3-+H2SO4→HSO4-+HNO3
solution is mixed with 6FeSO4+3H2SO4+2HNO3→3Fe2(SO4)3+4H2O+2NO
freshly prepared FeSO4+NO→FeSO4.NO(brown nitroso ferrous Presence of nitrate
ferrous sulphate sulphate) confirmed.
solutions.
Concentrated H2SO4 is
then added to it
carefully along the
sides of the micro
Test tube without
shaking.
D) Test for Cation
Test for Ammonium
 1) A little of the A gas with the smell of ammonia which gives Presence of
original dense white fumes when a glass rod dipped in Ammonium
mixture is conc. HCl is shown in it
boiled with NH4++NaOH→Na++H2O+NH3
sodium NH3+HCl→NH4Cl
hydroxide
solution.

2) A little of the
original A brown stain appears on the paper Presence of
mixture is NH3+2K2[HgI4]+3NaOH→HgO.Hg(NH2)I+7NaI+2H2O ammonium
boiled with This is due to the formation of brown basic confirmed
sodium mercuric amino iodide
hydroxide
solution and
a piece of
filter paper
moistened
with
Nessler’s
reagent is
shown in the
issuing gas

Intergroup Separation
To the residue of sodium carbonate extract add dil. HCl and filtered
Residue Centrifugate: H2S is passed through it and centrifuged.
A white Residue Centrifugate: H2S is boiled off. Add one drop of conc. HNO3 and
residue (Black(Cu, boiled again. Cooled, add excess of solid ammonium chloride and 1:1
Presenc Bi)/ ammonia until the solution strongly smells of ammonia.
e of yellow(Cd))
group I Presence of
cation Residue Centrifugate:Through the ammoniacal solution, H2S
group II (White is passed and centrifuged
cation. gelatinous(Al)/
Reddish Residue Centrifugate: H2S is boiled off.
brown(Fe)) (Black(Co, Add 1:1 ammonia until the
Presence of Ni/flesh solution strongly smells of
group III cation coloured ammonia and add ammonium
(Mn)/Dirty carbonate solution.
white(Zn))
Presence of
 group IV cation Residue Centrifuga
(White(Ba,Ca,Sr) te: The
Presence of group filtrate is
V cation tested for
group VI
cations
and are
found to
be
present/a
bsent
ANALYSIS OF THE GROUP RESIDUES
1) Analysis of group I residue
The group I residue is boiled with water and centrifuged
No residue Centrifugate: The hot solution is divided in to two portion
Absence of silver (Ag+) and a) One portion is acidified with acetic acid and
mercurous mercury(Hg22+) potassium chromate solution is added to it. A yellow
precipitate. Presence of lead (Pb2+)
Pb2++2CH3COOH→(CH3COO)2Pb
(CH3COO)2Pb+K2CrO4→PbCrO4+2CH3COOK

b) The second portion is treated with potassium iodide

solution. A yellow precipitate which dissolves in hot
water and reappears as golden spangles on cooling.
Presence of lead (Pb2+) confirmed.
(CH3COO)2Pb+2KI→PbI2+2CH3COOK
2) Analysis of group II residue- Separation of IIA$&II B
The group II residue is boiled with sodium hydroxide solution and two drops of ammonium
polysulphide solution. Centrifuged
Residue: Presence of II A Centrifugate: The filtrate acidified with dil.HCl and
(Black/yellow residue) warmed. No residue- Absence of II B
a) Analysis of group IIA residue
The group II A residue is boiled with dil. HNO3 and and centrifuged
Residue Centrifugate: It is treated with excess of H2SO4 and centrifuged.
No No Centrifugate: It is concentrated. Add 1:1 NH3 in drop until the solution
residue. residue strongly smells of ammonia.
Absence .
of Residue Centrifugate:
Absenc A white residue- a) Blue solution- Presence of
mercuric e of
presence of bismuth copper(Cu2+)
mercury( lead 3+
(Bi ). The residue is [Cu(NO3)2+2NH4OH→
Hg2+) (Pb2+) dissolved in minimum Cu(OH) +2NH NO
2 4 3
quantity of dil.HCl and Cupric hydroxide dissolves in excess of
divided in to two NH4OH forming the deep blue complex
portions. tetra ammine Cu(II)hydroxide
a) One portion is Cu(OH)2+4NH4OH→
added to large [Cu(NH3)4](OH)2+4H2O]
 excess of b) Colorless solution- Absence of
water taken in copper(Cu2+)
a boiling tube. It is divided in to two portions.
A white a) One portion is acidified with acetic
turbidity. acid and potassium Ferro cyanide
Presence of solution is added to it. A brown
Bi3+. precipitate. Presence of copper
Bi(OH)3+3HCl (Cu2+) confirmed.
→BiCl3+3H2O [Cu(NH3)4](OH)2+6CH3COOH→(CH3COO)2Cu+
BiCl3+H2O→ 4CH3COONH4+2H2O
BiOCl+2HCl 2(CH3COO)2Cu+K4[Fe(CN)6]→
b) The second Cu2[Fe(CN)6]+4CH3COOK
portion is
treated with b) H2S is passed through the second
sodium portion. A yellow precipitate.
stannite Presence of cd2+ confirmed.
solution. A CdS+2HNO3→Cd(NO3)2+H2S
black Cd(NO3)2+2NH4OH→Cd(OH)2+2NH4NO3
precipitate. Cd(OH)2+2NH4NO3+2NH4OH→
Presence of [Cd(NH3)4](NO3)2+4H2O
Bi3+ Tetra ammine Cd(II) complex is formed
confirmed. [Cd(NH3)4](NO3)2+2H2S→
2BiCl3+6NaOH CdS+(NH4)2S+2NH4NO3
+3Na2SnO2→
2Bi+3Na2SnO3
+6NaCl+3H2O
(BiCl3 is
reduced to
black metallic
Bi which gets
precipitated)

3) Analysis of group III residue

The group III residue is mixed with sodium hydroxide solution and hydrogen peroxide solution boiled
until the evolution of oxygen ceases and is centrifuged.
Residue Centrifugate: The filtrate is
A brown residue- Presence of iron. It is dissolved in hot dil. HCl and boiled with solid ammonium
this solution is divided in to two portions. chloride-A white gelatinous
a) One portion is treated with potassium Ferro cyanide precipitate-Presence of
solution-A deep blue precipitate(or color)- Presence of iron aluminum.(Al3+)
4FeCl3+3K4[Fe(CN)6]→Fe4[Fe(CN)6]3+12KCl Al(OH)3+NaOH→
Ferricferrocyanide (Prussian blue )is formed NaAlO2+2H2O(Soluble sodium
b) The second portion is treated with ammonium thiocyanate meta aluminate)
 (ammonium sulphocyanide) solution- A blood red coloration- NaAlO2+H2O+NH4Cl→
Presence of iron. Al(OH)3+NaCl+NH3
FeCl3+3NH4CNS→Fe(CNS)3+3NH4Cl This precipitate is collected and
To test whether ferrous(Fe2+) or ferric(Fe3+) boiled with a little concentrated
1) To a little of the original solution a little of potassium HNO3 and few drops of cobalt
ferricyanide solution is added- A deep blue precipitate (or nitrate solution. A piece of filter
color) - Presence of Fe2+. paper is moistened with this
3FeSO4+2K3[Fe(CN)6]→Fe3[Fe(CN)6]2+3K2SO4 solution and burnt in to ashes-A
2) 1) To a little of the original solution, some dil.H2SO4 is blue tinted ash- Presence of
added. To this dil.KMnO4 is added in drops. The KMnO4 aluminum (Al3+) confirmed.
solution is decolorized- Presence of Fe2+ [This is due to the formation of
Fe2+ reduces permanganate to colorless Mn2+ a double oxide of aluminium
2KMnO4+8H2SO4+10FeSO4→K2SO4+2MnSO4+8H2O+5Fe2(SO4)3

3) 1) To the little of the original solution, a little of

potassium Ferro cyanide solution is added. A deep blue
precipitate (or color)- Presence of Fe3+
4FeCl3+3K4[Fe(CN)6]→Fe4[Fe(CN)6]3+12KCl

4) 1) To the little of the original solution, ammonium

thiocyanate solution is added- A blood red coloration-
Presence of Fe3+.
FeCl3+3NH4CNS→Fe(CNS)3+3NH4Cl
4) Analysis of group IV residue

The group IV residue is shaken with very dil. HCl and is centrifuged.
Residue Centrifugate: H2S is boiled off. Excess of NaOH solution is
A black residue- Presence of added, boiled and centrifuged
Nickel (Ni2+) or cobalt (Co2+). Residue Centrifugate: It is divided in to
The residue is dissolved in A white residue turn in two portions
aquaregia and evaporated brown in air ZnS+2HCl→ZnCl2+H2S
to dryness in a china dish Presence of ZnCl2+2NaOH→Zn(OH)2+2NaCl
a) A yellow residue- manganese(Mn2+) Zn(OH)2+2NaOH→
Presence of Ni2+ A very small part of the Na2ZnO2+2H2O
b) A blue residue- residue is mixed with a) One portion is acidified
Presence of Co2+ conc.HNO3 and lead with acetic acid and
The residue is dissolved dioxide. The mixture is treated with potassium
in water and the boiled, diluted with water Ferro cyanide solution- a
solution is divided in to and allowed to stand for white precipitate-
three portions. a while- A pink Presence of Zn2+
1) To one portion supernatant liquid- Na2ZnO2+4CH3COOH→
NH4Cl, excess Presence of Mn 2+ (CH3COO)2Zn+2CH3COONa+2
NH4OH and confirmed. H2O
potassium MnO(OH)2+2HNO3→ 2(CH3COO)2Zn+K4[Fe(CN)6→
ferricyanide Mn(NO3)2+2H2O Zn2[Fe(CN)6]+4CH3COOK
solutions are added. 2Mn(NO3)2+5PbO2+6HNO b) H2S is passed through
A reddish brown 3→ the second portion- A
precipitate- 5Pb(NO3)2+2HMnO4+2H2 white precipitate-
Presence of Co2+ O Presence of Zn2+
3CoCl2+2K3[Fe(CN) (This is due to the confirmed.
6]→ formation of pink This precipitate is collected
6KCl+Co3[Fe(CN)6]2 permanganic acid) and heated with conc. HNO3
2) To the second and few drops of cobalt
portion , solid nitrate solution. A piece of
ammonium filter paper is moistened
thiocyanate is with this solution and then
added and then burnt to ashes- A green
shaken well with a tinted ash- Presence of Zn2+
mixture of amyl further confirmed.
alcohol and ether- A (This is due to the
blue organic layer- formation of a double
Presence of Co2+ oxide of Zinc and cobalt,
confirmed ZnO.CoO)
CoCl2+2NH4CNS→
Co(CNS)2+2NH4Cl
Co(CNS)2+2NH4CNS→
(NH4)2[Co(CNS)4]
(Blue ammonium
cobaltothiocyanate complex
is formed which is soluble
and more stable in the
amylalcohol- ether layer)
3) To the third portion
NH4Cl, excess
NH4OH and
dimethyl glyoxime
reagent are added-
A rose red
precipitate.
Presence of Ni2+
confirmed.
5) Analysis of group V residue

The group V residue is dissolved in minimum quantity of hot acetic acid and warmed. To this solution, a
slight excess of potassium chromate solution is added.
Residue Centrifugate: It is concentrated by evaporation and
An yellow residue-Presence of barium divided in to two portions.
(Ba2+) 1) To one portion calcium sulphate solution is added
BaCl2+(NH4)2CO3→BaCO3+2HCl and boiled(The inner side of the micro test tube is
BaCO3+2CH3COOH→(CH3COO)2Ba+H2O+CO2 scratched using a glass rod- A scandy white
(CH3COO)2Ba+K2CrO4→BaCrO4+2CH3COOK precipitate- Presence of strontium(Sr2+). The
The residue is dissolved Conc. HCl and the precipitate is made in to a paste with conc.HCl
solution is divided in to two portions. and
1) To one portion dil. H2SO4 is added- A small portion of this paste is taken in a glass rod
A white precipitate- Presence of and shown very near to a nonluminous Bunsen
Ba2+ confirmed flame- a crimson red flame- Presence of Sr 2+
BaCrO4+2HCl→BaCl2+H2CrO4 confirmed.
BaCl2+H2SO4→BaSO4+2HCl 2) To the second portion of the centrifugate , excess
2) The second portion is evaporated in of NH4OH is added followed by ammonium
a china dish to a paste. A small oxalate solution- A white precipitate- Presence of
portion of this paste is taken in a Ca2+. Flame test is conducted with the above
glass rod and shown very near to a precipitate- A brick red flame- Presence of Ca2+
nonluminous Bunsen flame- a pale confirmed.
green flame- Presence of Ba 2+ Ca2++(NH4)2C2O4→CaC2O4→2CH3COONH4
further confirmed.

6) Analysis of group VI residue

The filtrate is evaporated nearly to dryness in a china dish. A few drops of conc.HNO 3 is added to the
paste and then evaporated to dryness. Heating is continued until the evolution of white fumes.

The residue is dissolved in minimum amount of water

a) To the solution saturated NH4Cl solution and excess of NH4OH are added followed by an excess of
disodium hydrogen phosphate solution and shaken well. The inner side of the test tube are
scratched with a glass rod- A white crystalline precipitate- Presence of Mg2+
Mg2++NH4OH+Na2HPO4→Mg(NH4)PO4+H2O+2Na+
b) To a little of the original solution a few drops of magneson reagent followed by excess of NaOH
solution is added- A blue precipitate- Presence of Mg2+ further confirmed.
(Magneson reagent is para-nitrobenzene-azoresorcinol. Mg(OH)2 formed adsorbs the dye to yield
a blue precipitate.)