CHEMISTRY PRACTICAL

Important Points
Chemical analysis : Analytical chemistry deals with qualitative and quantitative analysis of substances.
Qualitative analysis : A salt consists of two parts known as radicals. The positively charged part of a salt
(cation) Which has been derived from a base is termed as basic radical and the negatively charged part of salt
(anion) which has been derived from an acid is termed as acidic radical. In qualitative inorganic analysis, the given
compound is analysed for the basic and acid radicals (i.e., the cations and the anions), that it contains. For
example zinc blende is analysed for the Zn2+ and S2+ ions that it contains
Systematic Procedure for Qualitative Analysis of Inorganic Salts
It involves the following steps : (1) Preliminary tests (2) Wet tests for acid radicals and (3) Wet tests for basic
radicals
(1) Peliminary Test
(i) Physical examination : It involves the study of colour, smell, density etc.
Colour Salt
Black Oxides: MnO2 , FeO, CuO, Co3O4 , Ni2O3
Sulphides : Ag2S, CuS, Cu2S, FeS, CoS, NiS, PbS, Bi2S2
(blackish brown)
Blue Hydrated CuSO4 , anhydrous CoSO4
Orange KO2 , some dichromate (K2Cr2O7 ) , Sb2S3,
ferricyanides
Green Nickel salts hydrated ferrous salt potassium
permanganate (KMnO4 ), some copper (II) salts
Brownish yellow SnS
Dark brown PbO2 , Ag2O, CdO, Fe2O3, CuCrO4 , FeCl2 (but yellow in
aq. Solution)
Pale brown MnCO3
Light pink Hydrated manganese salts
Reddish pink Hydrated cobalt (II) salts
Red Hgl2 , Pb3O4
Yellow CdS, PbI2, AgBr, AgI, chromates

(ii) Flame test :

Characteristic flame colour : Certain metals and their salts impart specific colours to Bunsen burner flame.
(a) Pb imparts pale greenish colour to the flame.
(b) Cu and Cu salts impart blue or green colour to the flame.
(c) Ba and its salts impart apple green colour to the flame.
(d) Ca imparts brick red colour to the flame.
(iii) Borax bead test :
The transparent glassy bead (NaBO2 + B2O3) when heated with inorganic salt and the colour produced gives
some idea of cation present in it.
Colour of bead in oxidising Colour of bead in reducing flame Basic radical
flame present
Greenish when hot, blud in cold Red and opaque Cu
Yellow when hot Green Fe
Brown in cold Grey or black or opaque Ni
(iv) Charcoal cavity test

(a) Compound fused in cavity directly

 Nature and colour of bead Pb 2 
Yellow, soft bead which marks on paper ZnO
White yellow when hot ZnO
White yellow when hot ZnO
Grey metallic particles attracted by Fe, Ni, CO
magnet
(2) Wet tests for acid radicals:
Salt or mixture is treated with dil. H 2SO 4 and also with conc. separately and by observing the types of gases
evolved. Confirmatory tests of anions are performed.
Observations with Dilute H 2SO 4
Observations Acid Radical Confirmatory test
Brisk 2
CO3 (carbonate) Gas turns lime water milky but milkyness disappears on passing gas
effervescence inexcess, Na 2CO3  H 2SO4   Ne 2SO 4  H 3O  CO3
Brown fumes NO2 (Nitrite) Add KI and starch solution blue colour
2MnNO3  H 2SO 4   Na 2SO 4  2HNO2 : HNO 2   NO
(colourles): 2NO + O2 (akl 
 2NO2 (brown)
2KI  H 2SO 4  2NHO 2   K 2SO 4  2H 2O  2NO  l1  l 2 
starch blue colour
Smell of rotten 8th (sulphide) Gas turn lead acetate paper black Sodium carbonate extract (SE) +
eggs ( Sodium nitroprusside – purple colour.
H 2S smell) Na 2S  H 2SO4   H 2S  Na 2SO 4
on heating
H 2S  (CH 3COO)3 Pb 
 PbS  2CH 3COOH
Na 2S  Na 2 (Fe(CN) 2 NO]   NO4 [Fe(CN)3 NOS]
Sodium nitroprusside (purple)

Observations with concentrated H 2SO 4

Observation Acid Radical Confirmatory Test
Colourless prongent gas giving Cl  (Chloride) (i) Add MnO 2 in the same test tube
white flames with aq. and heatpale green Cl 2 gas
NH 4OH
(ii) S.E. + HNO3  AgNO3 solution
– white ppt soluble in aq NH 4
(iii) Chromyl chloride east
Reddish brown fumes Br  (bromide) (iv) Add Mn 2O and heat –
yellowish brown Br2 gas
(v) S.E. + MNO 2  AgNO3
solution –pale yellow ppt
partially soluble aq NH 2
(vi) Layer test
Violent prongent vapours turning I  (iodide) (vii) S. E + HNO2  AgNO 2 
starch paper blue yellow ppt. insoluble in aq
NH 2
(viii) Layer test
Brown prongent furn as intensified NO3 (nitrate) (ix) Ring test
by the addition of Cu-
turnings
Reactions
Chloride :
(i) KCl  conc.H 2SO4 
 KHSO4  HCl
HCl  NH 2 
 NH 4Cl

4HCl  MnO2   MnCl 2  Cl 2  2H 2O
(ii) KCl  AgNO3 
 AgCl   KNO3
AgCl  aq.2NH 3  [Ag(NH 3 ) 2 ]Cl
(iii) Chromyle chloride test :
heat
Chloride + K 2Cr2O7 (solid)  conc.H 2SO 4   reddish brown vapours of chromyl-chloride (CrO3Cl 2 ). Pass
these vapours into NaOH, when yellow Na 2CrO 4 solution is formed. On adding CH 3COOH and (CH 3COO) 2 Pb.
yellow ppt. of lead chromate (PbCrO 4 ) is formed.
Bromide :
 
(iv) KBr  conc.H 2SO4   KHSO 4  H;4HBr  MnO 2   Br2  2H 2O  MnBr2
(v) NaBr  AgNO 2 
 AgBr   NaNO 2
AgBr  aq.2NH 2 
 [Ag(NH 2 )2 ]Br
partially solub le
shake
(vi) Layer Test : S. E. + Cl 2 water + CHCl3   yellowish orange colour in layer or can be taken instead of
CHCl 2 );
2NaBr  Cl 2 
 2NaCl  Br2
In case of I  , violet colour of l 2 in CHCl3 layer, 2Nal  Cl 2   2NaCl  l 2 (violet)
Iodide :

(vii) Kl  conc.H 2SO 4   KHSO 4  Hl; 2Hl  H 2SO4   I 2  2H 2O  SO2
Nitrate :
NaNO 2  H 2SO4   NaHSO4  HNO 2
4HNO3 
 4NO 2  O 2 2H 2O
Cu  4HNO2 
 Cu(NO3 )2  2NO 2  2H 2O
(viii) Ring test : To water extract (all NO 2 are water soluble) add freshly prepared FeSO 4 solution and then conc.
H 2SO 4 carefully by the side of the test-tube A dark brown ring of [Fe(H 2O)3 NO]2  SO 42  at the interface between
the two liquids is formed
2NaNO3  H 2SO 4   2NaHSO 4  2HNO 2 ;
 3Fe 2 SO 4  3  2NO  4H 2O
2HNO3  6FeSO 4  3H 2SO 4 
[Fe(H 2O)6 ]SO 4  NO  [Fe(H 2O)4 NO]2  SO 24   H 2O
Specific test in solution
(i) Sulphate : S. E. add dil (to decompose CO 22  until reaction ceases) Add BaCl 2 solution. White ppt insoluble in
conc. HNO3 , BeCl2  NaSO4 
 BaSO 4  2NaCl
white ppt

(ii) Borate: Ignite the mixture containing borate, conc. H 2SO 4 . And ethanol in a china-dish with a burning splinter-
green edged flame of ethyl borate.
2Na 2 BO3  3H 2SO 4  2H 3BO3  3Na 2SO 4 ;
 
H 2 BO3  3C2 H 5OH  (C2 H 5O)3 B  3H 2O
In presence of Cu 2  , perform this test in a test tube since salts are not volatile
(iii) S.E  HNO2  ammonium molybdate solution. Heat, yellow crystalline ppt. confirms

Na 2 PO 4  12(NH 4 ) 2 MoO 4  24HNO3   (NH 4 )2 PO4 .12MoO6  21NH 4 NO3  3NaNO3  12H 2O
yellow ppt.
Arsenic also gives this test. Hence presence of phosphate should also be checked after group II.
(iv) Fluoride : Sand + salt (F )  conc. H 2SO 4 ; heat and bring a water wetted rod in contact with vapours at the mouth
of the test tube. A white deposit on the rod shows the presence to F .

NaF  H 2SO 4   NaHSO 4  HF

SiO 2  4HF   SiF4  2H 2O
3SiF4 4H 2O   2H 2SiF6  H 4SiO4
(3) Wet tests for basic radicals :
Analysis of Basic Radicals
Grou Basic radicals Group reagent Ppt as Explanation
p
I Ag  , Hg 22  (I), Pb 2  dil HCl Chloride Ksp values of
(AgCl, Hg 2Cl 2 , PbCl 2 ) chlorides are
low, hence
precipitated
Others have
higher Ksp
values hence
not
precipitated
II Cu 2  ,Cd 2  .Pb2  H 2S gas in Sulphides Ksp values of
(CuS, As2S2 etc.)
Hg 2  (II), Bi 2  , As3 ,Sb3 ,Sn 2  presence of sulphides are
dil HCl low hence
precipitated
by low
(S2  ) ion.
HCl (with
common H 
ion)
decreases
ionization of
H 2S which
gives low
[S2  ] .
Hence II
group is
precipitated
Others with
higher Ksp
values not
precipitated
III Al3 ,Cr 2  , Fe2  NH 4OH in Hydroxide, Al(OH)2 Ksp values of
presence of etc. Al(OH)3
NH 4Cl etc. are low.
NH 4Cl
(with
common
NH 4 ion)
decreases
ionization of
NH 4OH
giving low
[OH  ] .
Hence group
III is
precipitated.
IV Zn 2  , Ni 2  , Mn 2  ,CO3 H 2S in Sulphides (ZnS) etc) Ksp values of
ammonical sulphides of
medium group IV are
high hence
precipitation
takes place
in higher
[S2  ]. Basic
medium
increases
ionization of
H 2S
increasing
[S2  ] hence
precipitation
of group IV.
V Ca 2  , Be 2  ,Sr 2  (NH 4 ) 2 CO3  NH 4ClCarbonates Ksp values of
(CoCO3etc) carbonate are
less than that
of group VI
(Mg 2  )
Hence
precipitation
before
Mg 2 
VI Mg 2  ,(Na  , K  also NH 4OH + White ppt. –
included) Na 2 HPO 4 (MgHPO 4 )

(only for Mg2  )

0 NH 4 – – Tested
(Zero independentl
) y from
original
solution
 Chemical reactions involved in the tests of basic radicals
Group I : When dil HCl is added to original solution, insoluble chlorides of lead, silver mercurous mercury are
precipitated.
Pb(NH 2 )2  2HCl   PbCl 2  2HNO 2 ;
AgNO 2  HCl 
 AgCl  HNO3
Hg(NO3 ) 2  2HCl 
 HgCl 2  2HNO 2
Pb2  (lead)
(i) PbCl 2 is soluble in hot water and on cooling white crystals are again formed.
(ii) The solution of PbCl 2 gives a yellow precipitated with potassium chromate solution which is insoluble in acetic
acid but soluble in sodium hydroxide.
PbCl 2  K 2CrO 4   PbCrO 4  2KCl;
PbCrO 4  4NaOH 
 Na 2 PbO 2  Na 2CrO 4  2H 2O
(iii) The solution of PbCl 2 forms a yellow precipitate with potassium iodide solution.
PbCl 2  2KI 
 PbI 2  2KCl
Yellow ppt
(iv) White precipitate of lead sulphate is formed with dilute H 2SO 4 .
The precipitate is soluble in ammonium acetate. PbCl 2  H 2SO 4 
 PbSO 4  2HCl :
PbSO 4  2CH 3COONH 4   Pb(CH 3COO) 2  (NH 4 )2 SO 4
Group II: When hydrogen sulphide is passed in acidified solution, the radicals of second group are precipitated as
sulphides. The precipitate is treated with yellow ammonium sulphide. The sulphides of IIB are first oxidised to
higher sulphides which then dissolve to form thio-compounds.
Ag 2S2  2(NH 4 ) 2 S2 
 2(NH 4 ) 2 S  As2S3
Sb 2S2  2(NH 4 ) 2 S2 
 2(NH 4 )2 S  Sb 2S2
SnS  (NH 4 )2 S2 
(NH 4 ) 2 S  SnS2
As2S3  3(NH 4 )S 
 2(NH 4 )2 AsS4
Sb 2S4  3(NH 4 )2 S 
 2(NH 4 )2 SbS4
SnS2  (NH 4 )2 S  (NH 4 )2 SnS3
All the three are soluble.
In case the precipitate does not dissolve in yellow ammonium sulphide, it may be either HgS or PbS of Bs 2S3 or CuS
or CdS. The precipitate is heated with dilute HNO2 Except, all other sulphides of are soluble.
3PbS  8HNO3  3Pb(NO3 )2  2NO  3S  4H 2O
B2S8  8HNO3 
 2Bi(NO3 )2  2NO  3S  4H 2O
3CuS  8HNO3  3Cu(NO3 )2  2NO  3S  4H 2O 3CdS  8HNO3  3Cd(NO3 ) 2  2NO  3S  4H 2O
Pb2  (lead)
In case the sulphide dissolves in dilute HNO 3. a small part of the solution is taken. Dilute H 2SO 4 is added. If lead is
present, a white precipitate of lead sulphate appears. Pb(NO 2 )2  H 2SO4  PbSO4  2HNO3
(white ppt)
In absence of lead, the remaining solution is made alkaline by the addition of excess of NH 4OH. Bismuth forms a white
precipitate of Bi(OH)3 . Copper forms a deep blue coloured solution while cadmium forms a colourless soluble
complex.
Bi(NO2 )2  3NH 4OH   Bi(OH) 2  3NH 4 .NO2
White ppt
Cu(NO 2 ) 2  4NH 4OH 
 [Cu(NH 3 ) 4 ][NO2 ) 2  4H 2O
Tetram min e cupirc nitrate
(deep blue solution)

Cd(NO2 )2  4NH 4OH 

 [Cd(NH 3 ) 4 ](NO3 )2  4H 2O
Tetram min e cadmium nitrate
(colourless solution)

Cu 2  (copper) :
Blue coloured solution is acidified with acetic acid. When potassium ferrocyanide is added a chocolate coloured
precipitate is formed.
Cu(NH 2 ) 4  (NO3 )2  4CH 3COOH   Cu(NO 2 ) 2  4CH 2COONH 4
2Cu(NO3 )2  K 4 [Fe(CN)4 ] 
 Cu 2 [Fe(CN) 4  4KNO3
Chocolate ppt.
Group III : Hydroxides are precipitated on addition of excess of ammonium hydroxide in presence of ammonium
chloride.
AlCl 3  3NH 4OH   Al(OH)3  3NH 4Cl
CrCl 2  3NH 4OH 
 Cr(OH)2  3NH 4Cl
FeCl 2  3NH 4OH 
 Fe(OH)3  3NH 4Cl
Fe3 (iron) : The brownish red precipitate dissolves in dilute HCl. The solution is divided into two parts.
Part I:
K 4 [Fe(CN)6 ] solution is added which forms deep blue solution or precipitate
Fe(OH)3  3HCl 
 FeCl 2  3H 2O
4FeCl 3  3K 4 [Fe(CN)6 ] 
 Fe4 [Fe(CN)6 ]3  12KCl
Part II :
Addition of potassium thiocyanate solution gives a blood red colouration
FeCl3  3KCNS   Fe(CNS) 2  3KCl
Al3 (alu min ium) :
The gelatinous precipitate dissolves in NaOH, Al(OH)3  NaOH 
 NoAlO 2  2H 2O
The solution is boiled with ammonium chloride when Al(OH)2 is again formed.
NoAlO 2  NH 4Cl  H 2O 
 Al(OH)3  NaCl  NH 3
Group IV : On passing H 2S through the filtrate of the third group, sulphides of fourth group are precipitated. Nis and
CoS are black and insoluble in concentrated HCl while MnS (buff coloured). ZnS (colourless) are soluble in conc.
HCl.
2
Zn (Zinc) : The sulphide dissolves in HCl. ZnS  2HCl   ZnCl 2  H 2S
When the solution is treated with NaOH, first a white precipitate appears which dissolves in excess of NaOH
ZnCl 2  2NaOH   Zn(OH) 2  2NaCl Zn(OH)2  2NaOH   Na 2 ZnO 2  2H 2O
White ppt

On passing H 2S, White precipitate of zinc sulphide is formed Na 2 ZnO2  H 2S 

 ZnS  2NaOH
White ppt
2
Mn (manganese) : Manganese sulphide dissolves in HCl MnS  2HCl   MnCl 2  H 2S
On heating the solution with NaOH and Br2 -water, manganese dissolve gets precipitated.
MnCl 2  2NaOH 
 Mn(OH) 2  2NaCl Mn(OH)2  O 
 MnO 2 H 2O
The precipitate is treated with excess of nitric acid and PbO2 or Pb3O4 (red lead). The contents are heated. The
formation of permanganic acid imparts pink colour to the supernatant liquid.
2MnO 2  4HNO3   2Mn(NO3 ) 2  2H 2O  O 2
2Mn(NO3 ) 2  5Pb2O 4  26HNO3   2HMnO 4  15Pb(NO 3 ) 2  12H 2O
The above test fails in presence of HCl
Ni 2  (nickel) and Co2  (cobalt)
The black precipitate is dissolved in aqua-regia.
3NiS  6HCl  2HNO3   2NiCl 2  2NO  3S  2H 2O
3CoS  6HCl  2HNO3   3CoCl 2  2NO  3S  4H 2O
The solution is evaporated to dryness and residue extracted with dilute HCl. It is divided into three parts.
Part I: Add NH 4OH (excess) and dimethyl glyoxime A rosy red precipitate appears, if nickel is present.
Part II : Add CH 3COOH in excess and KNO2 . The appearance of yellow precipitate confirms the presence of cobalt.
KNO2  CH 3COOH 
 CH 3COOK  HNO 2
CoCl 2  2KNO2 
 Co(NO 2 ) 2  2KCl
Co(NO 2 )2  2HNO2 
 Co(NO 2 ) 2  NO  H 2O
Co(NO 2 )3  3KNO 2 
 K 3[Co(NO 2 )6 ]
Part III : Solution containing either nickel or cobalt is treated with NaHCO3 and bromine water. Appearance of apple
green colour is observed, the solution is heated when black precipitated is formed, which shows the presence of
nickel. CoCl 2  2NaHCO2   Co(HCO3 ) 2  2NaCl
Co(HCO 3 ) 2  4NaHCO3 
 No 4Co(CO 3 ) 2  3H 2O  3CO 2
Br2  H 2O 
 2HBr  O 2Na 2Co(CO3 )3  H 2O  O 
 2Na 2Co(CO3 ) 2  2NaOH
NaCl 2  2NaHCO3 
 NiCO3  2NaCl  H 2O  CO 2
2NiCO3  [O] 
 Ni 2O3  2CO 2
Group V : Ammonium carbonate precipitates V group radicals in the form of carbonates are soluble in acetic acid.
BaCO3  2CH 3COOH   CH 3COCl 2 Ba  CO2  H 2O
SrCO3  2CH 3COOH 
(CH 3COO)2 Sr  CO2  H 2O
CaCO3  2CH 3COOH 
(CH 3COCl 2Co  CO 2  H 2O
Ba 2  (barium) : Barium chromate is insoluble and precipitated by the addition of potassium chromate solution.
Ba(CH 3COO)2  K 2CrO4 
 BaCrO 4  2CH 3COOK
Ca 2  (calcium) : Calcium oxalate is insoluble and precipitated by the addition of ammonium oxalate.
Ca(CH 3COO) 2  (NH 4 ) 2 C2O4 
 CoC2O4  2CH 3COONH 4
White ppt
Group VI : In the filtrate of V group, some quantity of ammonium oxalate is added as to remove Be, Ce and Sr
completely from the solution. The clear solution is concentrated and made alkaline with NH 4OH. Disodium
hydrogen phosphate is now added, a white precipitate is formed.
MgCl 2  No2 HPO 4  NH 4OH   Mg(NH 4 )PO 4  2NaCl  H 2O
Zero group NH 4 (ammonium) : The substance (salt or mixture) when heated with NaOH solution evolves
ammonia.
NH 4Cl  NaOH   NaCl  NH 3  H 2O
When a red dipped in HCl is brought on the mouth of the test tube, white fumes of ammonium chloride are formed,
NH 3  HCl   NH 4Cl
To the aqueous solution of ammonium salt when Nessler’s reagents is added, brown coloured precipitate is formed.