PRINCIPLES RELATED TO PRACTICAL CHEMISTRY

Preface

In this chapter you will learn about various methods of detection of extra elements &
functional groups in organic compounds, methods of preparation of inorganic & organic
compounds according to the syllabus. It also possesses the chemical principles involved in
the titration and salt analysis, experiment for the enthalpy of solution, enthalpy of
neutralization, preparation of solutions, chemical kinetics.
After successful completion of the topic, you will be able to know about -
(i) How to detect of a particular extra element or a functional group in the given organic
compounds
(ii) How to prepare the required organic & inorganic compounds.
(iii) Titrimetric and qualitative salt analysis.
(iv) How to calculate the enthalpy of solution, enthalpy of neutralization.
(v) How to prepare lyophilic & lyophobic solutions.
(vi) Kinetic study of a reaction.

“Remember that without Chemistry

Nothing would exist !”
[Link] of extra elements (N, S, Halogens) 1.2 Detection for S :
in organic compounds/(Qualitative Analysis):: (A) Sodium nitroprusside Test :
Sodium Extract + Few drops of sodium
1.1 Detection of N
nitroprusside  A deep violet colour confirms ‘S’.
(A) Soda Lime Test :
Na2S + Na2[Fe(CN)5NO]  Na4[Fe(CN)5NOS]
O.C. + (NaOH + CaO)  NH3
Sodium thionitro prusside
Evolution of NH3 gas indicates the presence of N (violet colour)
in organic compounds.
(B) Lead Acetate Test :
e.g. CH3CONH2 + NaOH CaO  CH3COONa Sod. Extract is first acidified with CH3COOH
followed by Lead Acetate solution, a black ppt.
Acetamide Sod. Acetate
is obtained.
+ NH3
Note : - This test is not reliable, many org. comp. 2Na + S fusion
  Na2S (Sod. Extract)
containing N such as nitro (–NO 2 ), azo Na2S + Pb(CH3COO)2  PbS + 2CH3COONa
(–N = N–) groups etc. do not give this test. black ppt.
Detection for N and S both
(B) Lassaigne’s Test : Sod. Ext. + FeCl3 (aq)  Red colour; N & S
Ignition tube + O.C. + Na-piece + heat gently confirmed
fusion NaCNS + FeCl 3  FeCl 2 (CNS) + NaCl
  NaCN containing mixture.
ferric chloride thio-
This mixture is then dissolved in water, heated
cyanate (red colour)
and filtered. The filtrate contains solution of NaCN
is known as Sodium Extract or Lassaigne Extract. 1.3 Detection of Halogens : -
O.C. + Na  NaCN (A) Lassaigne Test :
Na + C + N  NaCN
Sod. Extract + few drops of conc. HNO3 Boil 
Detection of N :- Now add AgNO3 (aq)  White ppt. of AgCl if Cl
light yellow ppt. of AgBr if Br
2 ml. Sod. Ext. + freshly prepared FeSO 4 (aq) +
Dark yellow ppt. of AgI if I.
few drops of alkali  Green ppt. of Fe (OH)2
NaX + AgNO3  AgX + NaNO3
Note : If N and S are also present, the formation
of NaCN & Na2S will hinder in identification of
colour of precipitate because both NaCN & Na2S
give white & black precipitate of AgCN & Ag2S
Green or prussion blue colour confirms ‘N’.
respectively. It is therefore necessary to remove
2NaCN + FeSO4  Fe(CN)2 + Na2SO4
NaCN & Na2S from extract. This is done by
Fe(CN)2 + 4NaCN  Na4Fe(CN)6 boiling extract with conc. HNO3.
Fe2+ OH
– 3+ NaCN + HNO3  NaNO3 + HCN
 Fe
Na2S + HNO3  NaNO3 + H2S
4Fe3+ + 3Na4Fe(CN)6  12Na+ + Fe4[Fe(CN)6]3
(B) Layer Test for Br and I
Ferriferrocyanide,
(Prussion Blue.) Sod. Extract + Dil. HNO3 + CHCl3 or CCl4 +
Note : (i) This test fails in case of diazo shake
Cl2 water  Brown layer if Br
compounds, since these lose N2 on heating before
Na has a chance to form NaCN. Violet layer if I
(ii) Also compounds such as NH2.NH2, NH2OH 2NaBr + Cl2  2NaCl + Br2
i.e. those not having carbon in addition to N, do Br2 + CHCl3  Brown layer
not give this test.
2NaI + Cl2  2NaCl + I2
(iii) A freshly prepared Aq. solution of FeSO4 is
used in this test for N, because FeSO4 (aq) on I2 + CHCl3  violet layer
keeping for sometime is oxidized to Fe2(SO4)3.
 (C) Beilstein test for halogens : Note :- Enolizable ketones give a positive
Xanthate test and hence should not be confused
Halogens containing organic compounds on with free alcoholic group.
heating over a Cu wire loop impart green or blue (iii) Sodium metal test : A small piece of sodium
colour to flame. The green or blue colour is metal is added to the given compound or its
produced due to the interaction of halogens with solution. Evolution of hydrogen gas indicates the
copper wire to form volatile copper halide. presence of –OH group in the organic compound.
ROH + Na  RONa + 1/2 H2
Note : (i) The test although very sensitive, is not
(iv) Phosphorus pentachloride test : Phosphorus
reliable because some other substances such
pentachloride is added to the given compound or
as urea, thiourea, pyridine, organic acid etc. its solution, if it becomes warm with evolution of
Which do not contain halogens also respond this hydrogen chloride, the organic compound contains
test. a hydroxyl group.
(ii) This test is also not for fluorides because of ROH + PCl5  RCl + POCl3 + HCl
their volatile nature. HCl + NH3  NH4Cl
(white fumes)
*Distinction between 1º, 2º and 3º Alcohols.
Examples
based on Qualitative Analysis (i) N-bromo Succinimide :- Dissolve 0.2 gm. of
O.C. in about 10 mL. of 0.01% solution of Br2 in
Ex.1 In Lassaigne’s test when both N and S are CCl4. Add about 0.2 gm of N-bromo- succinimide
present, blood red colour obtained is due to and place the test tube in a water bath at 80ºC.
the formation of- Note the colour.
(A) Ferric ferrocyanide Permanent orange colour  1º Alcohol
(B) Ferric sulphacyanide Transitory orange colour  2º Alcohol
(C) Ferric cyanide No colour change  3º Alcohol
(D) None of these (ii) Lucas Test :-
Sol.(B) 3 NaCNS + FeCl3  Fe (CNS)3 + 3NaCl Take 1 mL. of the compound in a test tube and
add 5 mL. of Lucas reagent (Zn + HCl) with
Ex.2 Lassaigne’s test for the detection of nitrogen shaking at 30ºC. Note the following observations-
will fail in case of - Separation of insoluble chloride layer at once 
(A) NH2CONH2 3º Alcohol
(B) H2NCONHNH2, HCl Appearance of cloudiness
(C) H2NNH2, 2HCl within 5 minutes  2º Alcohol
(D) C6H5NHNH2, 2HCl Solution remains clear
with some darkening  1º Alcohol
Sol. (C) For Lassaigne’s test of N, compound must
contain N in addition to carbon, so that NaCN (iii) Victor Meyer’s test :
can be formed in sodium extract.
Primary Secondary Tertiary
2. Detection of Functional Groups :: RCH2OH R2CHOH R3C OH
(A)Detection of alcoholic –OH group : P/I2or HI P/I2or HI P/I2or HI
(i) Ceric Ammonium Nitrate Test :- 5 drops of
O.C. + 0.5 ml. of Ceric ammonium nitrate solution
RCH2I R2CHI R3C I
diluted with 3 ml. of distilled water  Red colour
indicates the presence of alcoholic –OH group. AgNO2 AgNO2 AgNO2
2ROH + (NH4)2. Ce (NO3)6 Ce(NO3)4(ROH)2
(Red colour)
RCH2NO2 R2CHNO2 R3C NO2
+ 2NH4NO3
(ii) Xanthate Test :- DryT.T. + 0.5 ml of O.C + HONO HONO HONO
one-pellet of KOH + heat the T.T. till KOH
dissolves + Cool + 1ml. of Ether + 0.5 ml. of R C NO2 R2C NO2 No reaction
CS 2 dropwise  Yellow ppt. indicates the
presence of alcoholic –OH group. NOH NO NaOH
ROH + KOH  ROK + H2O Nitrolic acid Pseudo nitrol

ROK + CS2  ROCSSK Colourless

NaOH NaOH
(yellow ppt.)
Blood red colour Blue colour
(B) Detection of phenolic –OH group OH OH
(i) Ferric chloride Test :-
Take a dilute aqueous or alcoholic solution of the
O.C. in a test tube and add two drops of dilute H + H Conc.H SO
   2 4 
neutral FeCl3 solution. A sharp colour change to O
violet, blue or green indicates the presence of C
O
phenolic – OH group. C
O

+ FeCl3 

Note :-
(i) Enols, hydroxamic acids, hydroxy acids, some
oximes and enolisable compounds also give sharp
colour changes with FeCl3.
(ii) Most nitrophenols, hydroquinones, m-and
p-hydroxybenzoic acids and their esters,
tribromophenol etc. give a negative test.
(iii) -Naphthyl amine, aniline salts and benzoic NaOH
acid with FeCl3, produce blue, black and buff
colours respectively.
(ii) Nitrous Acid Test :
O ONa
T.T. + O.C. + 1mL. of conc. H2SO4
+ NaNO2 + Shake + warm 
Green, purple or blue colour
Pour the test mixture in a little of water, the C
colour will change to red or blue-red. Add a little
of 20% NaOH, the colour of the test mixture will
COONa
become blue or green.
Sodium salt of Phenol-
Note :- phthalein (Pink)
(i) p-substituted phenols and nitro phenols do
not give this test. (iv) Test for nitrophenols
(ii) Catechol & hydroquinone also do not give O.C. + 3ml. of Dil. NaOH solutions
this test. A sharp yellow colour  p-nitro phenol
Orange colour o-nitrophenol
(iii) Phenolic compounds containing –CHO,
(v) Liebermann’s Test :-
–COOH, –COCH3 groups gives negative test.
O.C.+ few crystals of NaNO2 + few drops of
(iii) Phthalein Test : conc. H2SO4  Green or blue colour which
Dry T.T. + O.C. + equal qty. of phthalic anhydride changes to red on dilution and again turns blue
+ 2 – 3 drops of conc. H2SO4 + gently fuse for or green on making the solution alkaline with
2 minutes + cool & pour the contents to a dilute NaOH
solution of NaOH. Appearance of pink, red or Note :- (i) Nitrophenols and p-substituted phenols
green fluorescent colour confirms the presence do not give this test.
of phenolic – OH group. (ii) This test is also shown by o-cresol.
 (C) Detection of Carbonyl Group :- Note :- Aromatic aldehydes, however, do not
(Aldehydes & ketones) reduce fehling’s solution.
Dry T.T. + O.C. + 3-4 ml. of 2, 4-Dinitro phenyl- (iii) Benedict’s Solution Test :-
hydrazine + 1 drop of conc. H2SO4  Yellow or Benedict solution is alkaline copper sulphate
orange ppt. confirms the presence of C=O containing citrate ions as complexing agent.
group. Aldehydes on warming with this solution, give
brick red precipitates.
C = O + [Link] NO2 RCHO + Cu2+  Cu2O + Oxidation products
Carbonyl 2,4- Dinitro- (Complex) Red ppt.
Compound Phenyl NO2
Note : Aromatic aldehydes, however, do not
hydrozine
reduce fehling’s solution.
NO2 (b) Test for ketones:
(i) Nitroprusside Test :-
C = [Link] NO2 + H2O
To a little quantity of the compound add 1 ml. of
Yellow coloured Hydrazone freshly prepared solution of sodium nitroprusside
and an excess of dilute NaOH solution formation
Specific Tests for Aldehydes & Ketones
of red colouration is a positive test for ketones
(a) Test for Aldehydes :-
(i) Tollen’s Reagent Test :- ( Silver Mirror
Test):- T.T. + O.C. + 4 ml . freshly prepared containing group.
Tollen’s reagent. Shake & keep the T.T. in warm (ii) m-Dinitro benzene Test :-
water ( about 40oC) formation of a silver mirror or T.T. + 1mL. of O.C. + 0.1 gm of finely powdered
grey or black ppt. confirms the presence of an m-dinitrobenzene + excess of dil. NaOH solution
aldehyde.  Violet colouration confirms the presence of
RCHO + 2 [Ag(NH3)2]OH RCOONH4
Tollen’s Reagent + 3NH3 + H2O
ketones containing group.
+2AgSilver Mirror
Preparation of Tollen’s Reagent :- To 2ml. of Note :- The above tests are only for
5% aqueous AgNO3 solution add 4 drops of a methyl ketones.
5% NaOH solution. (c) Detection of Carboxylic Group :-
Shake and dissolve the grey ppt. by dropwise (i) Litmus Test :-
addition of minimum quantities of dil. NH4OH Aq. solution of O.C. + Blue litmus paper  Blue
solution. colour changes to red. There may be carboxylic
AgNO3 + NaOH  AgOH + NaNO3 group.
AgOH + 2NH4OH  [Ag(NH3)2]OH + 2H2O (ii) Sodium Bicarbonate Test :-
Tollen’s Reagent T.T. + O.C. + Conc. NaHCO3  Evolution of
Note :- Both aliphatic & aromatic aldehydes effervescence (due to the formation of CO2)
reduce Tollen’s Reagent. indicates the presence of a carboxylic group.
(ii) Fehling’s solution Test :- RCOOH + NaHCO3  RCOONa + H2O + CO2
Fehling solution contains complex cupric ions Note :- This test is not reliable, because a few
and is prepared by adding fehling A solution which phenolic compounds like 2 , 4 , 6- tribromophenol,
contains CuSO4 (aq), to fehling B solution which picric acid etc. also give effervescence with
contains NaOH & Rochelle salt (sodium NaHCO 3 and should not be confused with
potassium tartarate) in 1 : 1. Its colour is deep carboxylic group.
blue.
(iii) Iodate-Iodide Test :-
2 ml. of fehling solution + 0.1 gm or 2-3 drops of
O.C. + boil for 5 min.  brown or brown-red T.T. + O.C. + 5 – 6 drops of 2% KI solution
colour confirms the presence of aliphatic + 5 – 6 drops of 4% KIO3 solution. Cork the test
aldehyde. tube and place it in boiling water for 1 - 2 minutes.
 Cool and add about 5 - 10 drops of starch solution.
CH3CHO + 2Cu(OH)2  CH3COOH + 2H2O
Appearance of a blue colour indicates the
Acetaldehyde Fehling’s + Cu2O
presence of a carboxylic group.
Solution Blue Red ppt.
 5 KI + 3KIO 3 + 6RCOOH  3I 2 + 3H 2 O Note :- Some electronegatively substituted
+ 6RCOOK amines such as 2,4-dinitroaniline do not diazotise
(iv) Ester Test :- by this method.
T.T. + O.C. + 5-drops of C2H5OH + 2-drops of (c) Hinsberg Test :-
conc. H2SO4. Warm the tube on water bath. A T.T. + 4-5 drops of O.C. + 4 ml. of pyridine + 1.5
fruity smell of ester indicates the presence of ml. of freshly prepared 2% aqueous NaOH
– COOR group. solution + Shake the contents thoroughly and
Conc.H SO add 2-drops of benzene sulphonyl chloride. Shake
CH3COOH+C2H5OH  2
4
 CH3COOC2H5
+ H2O it again. Development of a yellow colour indicates
the presence of a primary amine.
(D) Detection of Amines
Note : The test is reliable for alkylamines and for
Amines are basic compounds and have been
classified as aryl amines that have only one ring.
(i) Primary amines (– NH2) Secondary Amines
(ii) Secondary amines (= NH) (a) Libermann’s Nitroso Test :-
(iii) Tertiary amines ( N) T.T. + O.C. + 4-5 ml. [Link] + shake to dissolve
+ Aqueous NaNO 2 solution dropwise with
Primary Amines
shaking, till a yellow oil separates out at the
(a) Isocyanide Test :- bottom of the solution. Transfer the contents to
T.T. + O.C. + chloro form (fewdrops) + 2-3 ml. of small separating funnel . Add about 15-20 ml. of
alcoholic KOH or NaOH solution. Shake the ether and shake thoroughly. Separate the etherial
contents and warm gently. A nauseating odour of layer and wash it with H2O, dilute NaOH & again
carbylamine (Isocyanide) shows the presence of with H2O. Evaporate the ether carefully and
aliphatic or aromatic primary amino group. transfer the residual oil in a test tube. Add 0.5 –
R – NH2 + CHCl3 + 3 KOH  R – NC + 3KCl 0.6 gm. of phenol & warm gently. Cool & add
+ 3H2O about 1 ml. of concentrated H2SO4. Formation of
(b) Dye Test :- greenish blue colouration which turns red on
T.T. + O.C. + 1 ml. of conc. HCl + shake & dilute dilution with H 2 O, shows the presence of
with 3 – 4 ml. of H2O + cool + NaNO2 solution secondary amine group.
+ alkaline solution of -naphthol  Red or orange R R
dye shows the presence of aromatic primary
amino group. NH + HNO2  N – NO + H2O
R R
2º amine Nitroso amine
NH2 N = [Link] R
N – NO H
2SO4
 HONO
+ HNO2 + HCl  + 2H2O R
(NaNO2 + HCl)
Diazonium + OH
Chloride

N = [Link]
C H OH
OH 6 
5

+

-Naphthol HO NaOH
N O
OH

N=N O N O

 Indophenol anion (Blue)

(b) Dithio Carbamate Test :-
Orange dye T.T. + O.C. + 5 ml. of H2O + shake to dissolve.
 If clear solution is not obtained, add a drop of Ex.3 Which test is applicable for the detection of
conc. HCl and shake to dissolve. In another T.T. only aldehyde -
take about 5 ml. of Nickel chloride-Carbon (A) Tollen’s test (B) Lucas test
disulphide reagent and about 1 ml. of conc. (C) Ohkuma test (D) None of these
NH4OH solution. To it add 1 ml. of the solution
of the compound from the first T.T. Note the colour Answers :- 1 (A) 2 (C) 3 (A)
of the ppt. obtained.
Green yellow ppt. ...... 2º aliphatic amine [Link] involved in the preparation of
White or tan coloured ppt. – 2º Aromatic amine Inorganic compounds & organic compounds ::
Preparation of the Ni-chloride-Carbon disulphide Inorganic Compounds :
reagent -
(a) Mohr’s salt : [FeSO4. (NH4)2 SO4. 6H2O]
0.5 gm of NiCl2 .6H2O + 100 ml. H2O + CS2 till
Mohr’s salt is prepared by dissolving an equimolar
saturation
mixture of hydrated ferrous sulphate and
S ammonium sulphate in minimum amount of water
NH3 R containing a little sulphuric acid. Evaporate the
  
aqueous N – C – SNH4
R resulting solution to crystallization point and then
keep it aside for cooling undisturbed when light
S green crystals of ferrous ammonium sulphate
NiCl2 R
 N – C – S – Ni separate out.
R
2 FeSO4. 7H2O + (NH4)2SO4 
White or tan ppt.
1 mol = 278 g 1 mol = 132 g
(c) Hinsberg Test :- proceed as in test for primary FeSO4. (NH4)2SO4.6H2O + H2O
amines. Development of an orange colour shows
the presence of a 2º amine. 1 mol = 392 g
Tertiary Amines Chemicals required :
(a) Ohkuma Test 1. Ferrous sulphate crystals = 10 g
T.T. + O.C. + 5-6 drops of citric acid 2. Ammonium sulphate = 4.7 g
+ Acetic anhydride reagent + shake + heat gently 3. dil. sulphuric acid = 2 - 3 mL
in a boiling water bath. Development of a red or Result :
purple colour within 2 - 3 minutes is a positive
test for 3º amines. 1. Yield of cystals is about 12-13 g
[Preparation of citric acid – acetic anhydride 2. Colour : Light green
reagent :– 2g citric acid + 100 ml. of 3. Shape of crystals : Monoclinic
Acetic anhydride + shake and heat to get a clear Precautions :
solution]
(i) Small amount of dil. sulphuric acid is added
(b) Hinsberg’s Test :-
to prevents hydrolysis of ferrous sulphate.
Proceed as in test for 1º amines, development of
a deep red or purple colour is indicative of a 3º (ii) Do not concentrate the solution too much.
amine. This may result is a solid mass instead of
crystals.
Examples
based on Detection of functional Groups (iii) Cooling the concentrated solution slowly to
Ex.1 In Xanthate test for alcohols, the yellow ppt. get larger crystals. Rapid cooling results in
is of - many smaller crystals.
(A) ROCSSK (B) ROK (iv) Concentrated solutions should be cooled
(C) RCSSK (D) None of these undisturbed. A slight disturbance of solution
Ex.2 Which test is applicable for the distinction may change the shape, size and quantity of
between 1º, 2º and 3º alcohols - the crystals.
(A) Ester test (b) Potash Alum (Phitkari) :
(B) Litmus test W hen a solution containing an equimolar
(C) Lucas test quantities of potassium sulphate and aluminium
(D) Liebermann’s test
sulphate is heated to crystallization point and Procedure:- In a 150 ml. conical flask containing
then cooled slowly undisturbed, colourles 10 ml. of aniline add 10 ml. glacial acetic acid
octahedral of potash alum (a double salt) separate and 10 ml. acetic anhydride. Fit a reflux
out. condenser and boil the mixture gently for 10
K2SO4 + Al2(SO4)3. 18H2O + 6H2O  minutes. Pour the hot mixture in 200 ml. of ice
1 mol = 174 g 1 mol = 666 g cold H2O with stirring. The acetanilide crystallises
K2SO4.Al2(SO4)3. 24H2O rapidly. Filter and wash with H2O. Recrystallise
1 mol = 948 g from water or dilute alcohol.
Chemical required : Yield : : 10 gm
1. Potassium sulphate = 3 g M.P. : 114oC
2. Aluminium sulphate = 12 g Appearance : White shining flakes
3. dil. sulphuric acid = 4-5 drops.
Result : (b) p-Nitroacetanilide:-
1. Yield of crystals : 13 - 14 g Theory:-
2. Colour : Colourless Acetanilide on treatment with a mixture of conc.
3. Shape of crystals : Octahedral nitric acid and conc. H 2 SO 4 given
Precautions : p-nitroacetanilide.
Nitric acid in presence of sulphuric acid produces
(i) A few drops of dil. sulphuric acid should be
a large number of nitronium ions (NO2+). These
added while preparing a saturated solution of
ions then attack acetanilide molecules to form
aluminium sulphate to prevent its hydrolysis. p-nitroacetanilide via the intermediate formation
(ii) Dry the crystals by placing them between of cyclopentadienyl cation.
filter pads or by spreading them over porous plate. HNO3 + 2H2SO4 NO2+ + 2HSO4–+H3O +
Organic compounds :
(A) Acetanilide:
H NO2
Theory :
+NO+2 slow  Fast
Primary amines react with acid chlorides or
anhydrides to form the mono-acetyl derivative. NHCOCH3
NHCOCH3
The mechanism may be written as follows :-
Acetanilide Cyclopentadienyl
O O Cation
CH3 – C – O – C – CH3+ : NH2– C6H5
Aniline NO2
+
O O + H
O O
+
CH3 – C – O – C – CH3 H CH3 – C – O – C – CH3 NHCOCH3
+ p-nitroacetanilide
NH2 C6H5 NH C6H5

O H+ + HSO4–  H2SO4
– O – C – CH3 Reagents :-
Acetanilide : 8 gm.
O
Glacial acetic acid : 8 ml.
C  CH3 Fuming nitric acid: 3.2 ml.
NH. C6H5 Conc. H2SO4 : 16 ml.
Acetanilide Ice
Reagents :- Procedure :- Take 8 gm of acetanilide and 8 ml.
Aniline : 10 ml. of glacial acetic acid in a 100 ml of beaker. Stir
Acetic Anhydride : 10 ml. or warm the contents to get a clear solution.
Glacial Acetic Acid : 10 ml.
 Now add 16 ml. of conc. H2SO4 gradually with Aniline (s) 8 gm
stirring. (the solution will become hot). Cool the 2.5N HCl 50 ml
contents in an ice bath to 0-5oC and add with Ice
stirring drops by drop 3.2 ml. fuming NHO3 . Procedure :-
Allow the mixture to stand at room temperature Dissolve 5ml Aniline (l) in a mixture of 16ml Conc.
for half an hour and then pour the contens in 100 HCl and 20ml H2O. Cool the solution in ice to
gm of ice. Filter the crude product obtained & 0 – 5°C and then add to it a solution of 4gm.
wash with cold water. Recrystallise the pale NaNO2 in 15ml. H2O dropwise with continuous
yellow mass with methylated spirit. Yellow shaking and controlling the temperature below
o-nitroacetanilide will remain in the solution while 5°C. In other flask dissolve 8 gm of solid aniline
colourless crystals of p-nitroacetanilide will be in 50 ml of 2.5 N HCl. Cool it in the ice bath to
obtained. 0° – 5°C. Now add either of the cold solutions to
Yield : 6.5 gm other cold solution drop by drop with continuous
M.P. : 214oC stirring. Continue stirring at least for half an hour
Appearance : Colourless crystalline compound without allowing the temperature rise above 10°C.
Note :- Reaction mixture should be poured in ice Filter the product, wash with cold water, dry and
very carefully, at the dilution of Conc. H2SO4 is recrystallise from ethyl alcohol or glacial
an exothermic process.
CH3COOH.
Appearance :- Deep shining yellow crystals.
(c) Aniline Yellow
Yield : 13gm
Theory :-
M.P. : 131°C
Primary Aromatic amines when treated with HNO2
in presence of HCl at temperatrue 0 – 5°C are
(d) Iodoform:-
converted into diazonium salts (chlorides); the Theory:-
reaction being known as diazotisation. When methyl ketones are treated with hypo-
C6H5NH2 + HCl + HONO  C6H5N = NCl + H2O halides, they produce trihalogenmethane. This
Diazonium salts are soluble & reactive reaction is known as Haloform reaction. Thus
when acetone is treated with sodium-hypoiodide
compounds. On condensation with phenols in
(KI + NaOCI), Iodoform is obtained.
alkaline medium and on condensation with NaOCl + KI  NaOI + KCl
aromatic amines in acidic medium, they produce CH3 CH3
NaOI NaOH CH COONa +CHI
highly coloured compounds known as azo dyes, C=O C= O 3 3
I3C (aq)
the reaction being known as coupling reaction. Iodoform
CH3
Acetone
+ Reagents :-
+ – H(pH4 – 5)
N  NCl + H2N Potassium iodide : 6 gm
273 – 278 K Acetone : 2 ml.
(–HCl) Sodium hypochloride Solution (5%)

+ Procedure:- In a small flask take 6 gm. KI, 100

H, ml. water and 2ml. acetone. To it add slowly with
N = N – NH
(Rearranges) shaking a 5% solution of sodium hypochloride till
Diazoaminobenzene
the preparation of iodoform is complete ( about
60-70 ml.). Allow the mixture to stand for 15
minutes and filter. Wash the product with water
N=N NH2 and crystallise from alcohol.
Yield : 3.5 gms
p-aminoazobenzene (yellow)
M.P. : 119oC
Reagents :- Appearance : Yellow crystals
Note:- Acetone used in this preparation should be
Aniline (l) 5 ml
very pure otherwise a very low yield would
Conc. HCl 16 ml result.
Sod. Nitrite 4 gm
Examples Prepartion of inorganic and organic compounds 4. Chemistry involved in the titrimetric exercise ::
based on

Ex.1 Aniline Yellow is -

(i) Acids bases and the use of indicators
(A) p-nitroaniline (ii) Oxalic-acid vs KMnO4
(B) m-nitroaniline (iii) Mohr’s salt vs KMnO4

(C) p- aminoazobenzene (i) Acids bases and the use of indicators :

Introduction :- Acidimetry-alkalimetry is that
(D) p-hydroxyazobenzene
branch of analytical chemistry in which one acid
Ex.2 Aniline Yellow is formed by the reaction of is titrated against an alkali or vice versa. The
(A) Benzene diazonium chloride and aniline strength of one of them being known, that of the
other is calculated. When an acid is dissolved in
(B) Benzene diazonium chloride and phenol.
water, it ionises as in (i) and a base ionises as
(C) Aniline and Nitric acid in (ii).
–
(D) Aniline and Alcohol HA H ++ A (i)
–
Ex.3 The reactants for the formation of required BOH B ++ OH (ii)
Mohr’s salt are- On the addition of one to the other, the only
reaction occurring is the neutralisation of
(A) FeSO4 & (NH4)2. SO4. 6H2O
hydrogen ions with hydroxyl ions to form
(B) FeSO4. 6H2O & (NH4)2. SO4. H2O unionised water as is shown by the following
(C) Fe2 (SO4)3. 7H2O & (NH4)2. SO4 equations:-
– – –
H++A + B+ + OH B++A +H2O
(D) FeSO4. 7H2O &(NH4)2. SO4 –
or H++OH H 2O
Ex.4 The crystals of potash alum are- At the point of equivalence, the pH of the solution
(A) Tehrahedral (B) Octahedral will be = > or < 7 depending upon the strength
of the acid and alkali.
(C) Cubic (D) None of the above
Indicators :-
Ex.5 The formation of acetanilide is due to the Broadly defined, as indicator is substance which
reaction between - is used for the visual detection and determination
of a specific constituent present in any sample.
(A) Acetone & Aniline
The visual observation used is primarily that of
(B) Aceticanhydride & Aniline
colour, but observations of fluorescence and
(C) Aceticanhydride & benzylamine
turbidity are also [Link] under this
(D) Acetone & benzylamine
general definition include all reagents which can
Ex.6 The composition of Mohr’s salt is- be used in colorimetry flurimetry and turbidimetry.
(A) Fe(SO4)3. (NH4)2 SO4. 24H2O It is convenient, therefore, to define on indicator
(B) FeSO4. (NH4)2 SO4. 24H2O in a more limited way, as substance which is
(C) FeSO4. (NH4)2 SO4. 7H2O used for the visual detection of the completion of
(D) FeSO4. (NH4)2 SO4. 6H2O a particular reaction that is for the end point of
a titration.
Ex.7 The composition of Potash Alum is-
(A) K2SO4.Al2(SO4)3. 24H2O Acid-Base Indicators :- Acid- base indicator are
(B) K2SO4.Al2(SO4)3. 6H2O organic substances which have one colour in acid
(C) K2SO4.Al2(SO4)3. 7H2O solution while an altogether different colour in
(D) K2SO4.Al2(SO4)3. 12H2O alkaline solution.
Answers : 1 (C) 2 (A) 3.(D) 4.(B)

5.(B) 6.(D) 7.(A)

 Theories of Acid-Base Indicators :- represented as MeOH. Its undissociated molecule
Two important theories have been put forwarded
to explain their behaviour: is yellow while gives red coloured Me+ ions on
dissociation,
(I) Ostwald’s theory (1891) : According to this + –
theory: MeOH Me + OH
(i) Acid- base indicators are weak organic acids or (Yellow) (Red) (Colourless)
bases. If a base (i.e., OH– ions) is added to the indicator,
(ii) They have different colours in ionised and non- the OH– ions will suppress the ionisation of the
ionised states i.e. indicator. Hence, the indicator will remain yellow
HIn in an alkali. However, if a small excess of acid
(one colour) (different colour) (say, HCl) is added, the latter will force the
(iii) The colour of the indicator depends on the equilibrium to the right by removing OH– ions
relative proportions of the unionised indicator to form H2O. This will result in the formation of
red coloured Me+ ions in the solution.
molecules and its ions.
+ –
MeOH Me + OH
On the basis of above postulates. Ostwald
(Yellow) (Red) (Colourless)
explained the action of phenophthalein, methyl
– +
orange, methyl red and other acid-base indicators. HCl Cl + H
(a) Action of Phenolphthalein:- Phenolphthalein is
MeCl H2O
a weak acid (HPh) and is almost unionised. Its
(Highly ionised) (Unionised)
unionised molecules are colourless whilst on
(II) Modern Quinoid Theory :- Main postulates of
ionisation give colourless H + ions and pink this theory are:
coloured Ph– ions. (i) The indicators used in acid-alkali titrations are
aromatic organic compounds which are
HPh
equilibrium mixtures of at least two tautomeric
(colourless) (colourless) (pink) forms, ordinarily one form is benzenoid while the
In the presence of acid due to increase in the other is quinoid.
(ii) The two forms have different colours. The quinoid
concentration of common H+ ions, the dissociation
form is usually deeper in colour than the
of HPh is suppressed and thus the solution benzenoid form. Out of these one form exists in
becomes colourless. acidic solution while other in alkaline solution.
CH–CH CH–CH
On the other hand, the addition of strong bases
–C C– C=
(like NaOH, KOH), however, the OH – ions CH=CH CH=CH
produced from them combine with the H+ ions Benzenoid form Quinoid form
from the phenonphthalein to form feebly ionised (lighter colour) (deeper colour)

water. The equilbrium (i) is thus disturbed and (iii) Change in pH causes the transition of benzenoid
form to quinoid form and vice versa and
more of the phenolphthalein ionises to produce consequently a change in colour.
Ph– ions. The latter combine with Na+ ions to This theory explains the action of phenolphthalein,
form the strongly ionised sodium salt NaPh and methyl orange and other acid-base indicators.
hence remains in the ionic state giving pink (a) Action of Phenolphthalein:- Phenolphthalein is
coloured Ph– ions. an acidic indicator undergoing the following
transformation:
HPh H+ + Ph– ....(i)
OH OH
– +
NaOH OH + Na ...... (ii) C C
OH O
H2O NaPh O=C O COOH
(feebly ionised) (strongly ionised) colourless

(b) Methyl orange :- It is a weak base and can be

 (a) Strong acid and strong base:- ([Link], and
OH
NaOH). The neutralisation curve at different pH,
C obtained by adding N/10 NaOH to 20 ml of N/10
O HCl is shown by the curve AB.
pink
Strong base B
In alkaline medium, OH– ions combine with H+
ions produced by the indicator, the equilibrium 14 Weak base
D
shifts to the right producing pink colour. In acid
12
medium the dissociation of the organic acid is
suppressed, the equilibrium shifts to the left and 10
the solution becomes colourless.
8
(b) Action of Methyl Orange Weak acid
Methyl orange is a basic indicator. More correctly 6
C
it is an amphoteric compound containing both 4 Strong acid
acidic group -SO3H and basic group -N(CH3)2. A
The quinoid form (red) combines with the OH– 2 Equivalence Point
ions in alkaline medium favouring the formation
of yellow. 0
5 10 15 20 25 30 35
H3C  • • •• 
N N–NH SO3 + OH Vol. of 0.1 N alkali added to 20 ml of 0.2N acid.
H3C
From the curve it is evident that the pH remains
Red
almost constant at 3.3 when 19.9 ml of NaOH
H3C • • • • •• has been added on further addition of 0.1 ml of
N N=NH SO3+H2O
H3C NaOH, the pH suddenly rises to 10.5 as indicated
Yellow by nearly straight portion. From this it is evident
that any indicator with pH range from 3.3-10 can
(c) Action of Methyl Red
be used an indicator in finding out the end- point
Methyl red is a basic indicator and the colour
in such types of titration, i.e. methyl orange
change takes place according to the following phenolphthalein, litmus etc.
scheme: (b) Weak acid and strong base :- (Acetic acid and
H3C  • • ••  NaOH or oxalic acid and NaOH). The
N N–NH +OH
H3C neutralisation curve at different pH, obtained by
Red – adding N/10 NaOH to 20 ml of N/10 acetic acid
COO
is shown by the curve CB. At the end point, the
H3C • • • • •• pH varies from 6.5–10.5 and so end point lies on
N N=N +H2O
H3C alkaline side. Hence phenolphthlein having pH
Yellow COO
– range 8.3–10.5 is a suitable indicator for such
titration but methyl orange having pH range 3.2–
Choice of Acid-Base Indicators in Titrations 4.5 is not at all suitable indicator in such titrations
As we know that indicators are substances and hence cannot be employed.
which change-coloure at different pH, it means (c) Strong acid and weak base :- (HCl and NH4OH
that the choice of a suitable indicator for a or HCl and lime water). Curve AD is the
particular titration depends upon the nature of neutralisation curve of 20 ml of N/10 strong acid
acid and base used in that titration. A suitable (HCl) against N/10 weak base (NH4OH or lime
indicator is that which exhibits a distinct colour water). At the null point the pH varies from
at a pH close to that obtaining at the equivalence 3.5–7.0 so that the null point lies on the acid
point. side. Hence, any indicator with pH range 3.0–7.5
The stability of an indicator can be studied may be employed e.g. methyl orange and methyl
red, but phenolphthalein (pH) range 8.3–10.5 is
with the help of neutralisation curves obtained by
not at all suitable indicator for such titrations
plotting pH against the ml of standard alkali
and cannot be employed.
(say, N/10 added to a definite volume say, 20 ml
(d) Weak acid and weak base:- (CH3COOH and
of N/10 of acid) as shown in fig.
NH4OH).
 Take 20 ml of N/10 acetic acid in a beaker and dissolved in a mixture
add NH 4OH of the same strength from the of 50 ml ethanol and
burette. The pH changes that take place are 50 ml water.
represented by the curve CD. The pH range near
7 Thymol blue ............. 0.1 g of solid is dissolved
the equivalence point is not sharp and it is quite
gradual during the whole titration. Hence, no (available as Na salt) in 100 ml water.
indicator can be employed for such tiration. The 8 Thymolphthalein ........ 0.1 g of solid is dissolved
pH varies in a very narrow range of 6.0–7.5 in in a mixture of 90 ml
which no suitable indicator is available. Hence, ethanol and 10 ml
such titrations should be avoided. water.
Acid-Base Indicators with pH range of colour Choice of Indicators:-
change
At the equivalence point of acid- base titration
Colour pH range there occurs a sudden jump in pH of the solution.
Colour in
Indicator in of colour An indicator, the pH range of colour change of
acid
alkali change which falls within this limit, is suitable and is
Methyl orange Red Yellow 3.2 - 4.4 used in that titration. No sudden pH jump of the
Bromo-cresol solution in the titration of weak acid with weak
Yellow Blue 3.8 - 5.4
green
base occurs and so not indicator is suitable for
Methyl red Yellow Red 4.8 - 6.0
this titration.
Bromothymol
Yellow Blue 6 - 7.5
blue Nature of pH Jump at Suitable Indicator
Phenol red Yellow Red 6.3 - 8.4 Titration the
Phenolphthalein Colourless Pink 8.2 - 10 Equivalence
Thymol blue Yellow Blue 8 - 9.6 point
1. Strong acid 4-10 Any Indicator
Thymolphthalein Colourless Blue 9. 4 - 10.6
and strong (Methyl orange,
base Methyl red
Preparation of Indicator Solution
Phenolphthalein,
Name of the Indicator Process Bromo thymol
blue etc.)
1 Methyl orange ........... 0.05 g of solid is
(available as free acid or dissolved in 100 ml 2. Weak acid 6.5 - 10 Phenolphthalein,
and strong Thymol blue,
Na–salt) water.
base Thymolphthalein
2 Bromocresol green........ 0.1 g of solid is
dissolved in 100 ml 3. Strong acid 4 - 7.5 Methyl orange,
water. and weak Methyl red
3 Methyl red .............. 0.1 g of solid is base Bromocresol
(available as free acid) dissolved in a mixture green
of 60 ml ethanol and 4. Weak acid 6.5 - 7.5 No indicator is
40 ml water. and weak suitable
base
4 Bromothymol blue ........ 0.5 g of solid is
dissolved in a mixture Mixed and Universal Indicators
of 20 ml ethanol and Sometimes a mixture of two indicatore is used
80 ml water. to have a sharp colour change over a narrow and
5 Phenol red ............ 0.1 g of solid is selected pH range; it is not possible with any
dissolved in a mixture single acid-base indicator. Two indicators of very
of 20 ml ethanol and close pKln values are used so that their
80 ml water.
overlapping colour are complementary at an
6 Phenolphthalein ........ 0.5 gof solid is intermediate pH value.
A Common example is a mixture of equal parts
of 0.1% alcoholic solution of methylene blue & (iii) Pure calcium carbonate.
0.1% alcoholic solution of neutral red; it shows (b) For standardisation of alkalimetry:
a sharp colour change from violet-blue to green (i) Oxalic acid
at pH=7.0 in going from acidic to alkaline (ii) Succinic acid
Summary of Titration Characteristics
medium. This indicator may be used for titrating
Titration Indicator Solution
acetic acid with ammonia solution where a single
indicator is unsuitable for the extensive hydrolysis added
of the salt and flat nature of the titration curve. form the
burette
Mixtures of certain indicators obtained by mixing
in definite proportion to extend the colour change Stong acid- (i) Phenolphthalein (i) alkali
over wide portion of the pH range are called strong base
(ii) Methyl orange (ii) Acid
Universal Indicators or Multiple Range Indicators.
They are not at all suitable for tirations of
Strong acid- Methyl orange Acid
quantitative estimation, but they are useful for weak base
determining the approximate pH of a solution by Weak acid- Phenolphthalein Alkali
colorimetric method. Following is an example of strong base
this indicator.
(ii) Titration of oxalic acid v/s KMnO4
Preparation Colour at different pH value Standardisation of KMnO4 Solution
Experiment
0.05 g of methyl Upto pH = 3, red To estimate the strength of the given sample of
orange, 0.15 g of At pH = 4, orange red KMnO4 solution in g/litre. Prepare a standard
methyl red, 0.30 g At pH = 6, yellow solution of N/10 oxalic acid.
of bromothymol At pH = 7, yellowish-green Theory:- In this method given in 1912 by Mebride,
blue, and 0.35 g of At pH = 8, greenish-blue a solution of oxalic acid acidified with dilute
phenophthalein are At pH = 9,blue sulphuric acid is titrated slowly with potassium
dissolved in one At pH = 10, violet permaganate at a temperature between 60-70oC
litre of 66% At pH = 11, reddish- violet until a permanent pink colour gets developed in
the solution. The reaction is as follows:
aqueous ethanol.
2KMnO4 + 3H2SO4  K2SO4 + 2MnSO4 +
A number of universal indicators are 3H2O+ 5(O)
commercially available both as solution and as [H2C2O4 + (O)  2CO2 + H2O] × 5
test papers.
Litmus
It is an indicator. Commercial litmus contains 2KMnO4 + 3H2SO4 5H2C2O4  K2SO4 +
azolitimin as colouring component together with 2MnSO4 + 10 CO2 + 8H2O
varying amounts of calcium carbonate, calcium Or 2MnO4– + 5C2O42– + 16H+  2Mn2+ + 10 CO2
sulphate etc. As the solution of litmus may + 8H2O
contain variable amounts of colouring matter, so The oxidation of oxalate ions by permanent takes
it is not used for acid base titrations. It is place quantitatively at temperature of 60-70oC and
normally used for qualitative tests of a solution- once the reaction has started, its rate is
whether acidic or alkaline. For this purpose a
automatically increased due to the formation of
litmus paper (a piece of filter paper soaked with
Mn(II) ions which catalyse the reaction
solution of litmus) is used. Acidic solution turns
blue -litmus red and alkaline solution turns red- (autocatalysis).
litmus blue. Litmus solution is prepared by Procedure
dissolving 1.0 g of the solid in 100 ml of distilled It involves the following steps:
water. (i) Preparation of N/10 oxalic acid : Weight out
Primary standard for Acidimetry and accurately 63×1/40 = 1.575 g of pure oxalic acid
Alkalimetry crystals in weighing bottles or a watch glass.
(a) For standardisation of acids. Transfer it to a 250 ml measuring flask. To this
(i) A.R. anhydrous sodium carbonate. add 50 ml of distilled water and dissolve the
(ii) Pure borax Na2B4O7. 10H2O. crystals of oxalic acid by shaking gently and
 then make up the solution up to the mark on it Procedure
with more of distilled water. Again, shake the It involves the following steps :
flask gently up and down to ensure thorough (i) Preparation of 0.1N Mohr’s salt solution : Weight
mixing. out accurately 392× 1/40 = 9.8 g of pure Mohr’salt
(A.R.). Transfer it to a 250 ml measuring flask
(ii) Titration of KMnO 4 with oxalic acid :- Rinse the which is already having a few drops of
burette with potassium permanganate solution and concentrated sulphuric acid. Then add 50 ml of
fill it up to a convenient mark. One should be distilled water. Dissolve it by shaking the flask
sure that nozzle of the burette should not contain and then make up the volume upto the mark on
air bubbles but filled with the KMnO4 solution it by adding distilled water.
only. Pipette out 20 ml of the given standard (ii) Titration of KMnO 4 with Mohr’s salt solution:
Rinse and fill the burette with the given solution
solution of oxalic acid (N/10) into a titration flask of potassium permanganate solution and read the
and add to it a test tube of dilute sulphuric acid. initial reading of the burette by noting the upper
Heat the flask on a wire gauze to 60–70oC, i.e., meniscus only. Pipette out 20 ml of Mohr’s salt
to a temperature which is just unbearable to touch solution into conical flask. To this add a test
by hand. Note the initial reading of the burette by tube of dilute sulphuric acid. Run in KMnO4 from
noting the upper meniscus. Run the potassium the burette into a conical flask till a permanent
light pink colour is developed in solution. Repeat
permaganate solution slowly in small amounts at such titrations to get three concordant readings.
a time into the hot solution and shake till the end Calculations
points is reached. The end point is a change of Suppose 20 ml of N/20 Mohr’s salt solution
colourless solution to a just permanent pink  V ml of KMnO4 solution.
solution. Note the final reading of the burette by N
noting the upper meniscus only. Therefore, 20   V  NKMnO 4
10
Repeat the titration to get a set of three
N
concordant readings. Or NKMnO4 
V
Calculations
N 31.6
Suppose 20 ml of N/10 oxalic acid  V ml of and Strength =  g/litre
KMnO4 solution V N
N Examples Chemistry involved in the titrimetric exercise
or 20   V  NKMnO 4 based on
10
2N Ex.1 pH range of colour change for methyl orange
or NKMnO 4 
V indicator is-
2N 31.6 (A) 6.2 - 7.6 (B) 4.0 - 5.6
or Strength =  g/litre
V N (C) 3.2 - 4.4 (D) 9.4 - 10.6
2
Hence strength of KMnO4 = ×31.6 g/litre Ex.2 The colour of phenolphthalein in acid is-
V
Experiment (A) Red (B) Yellow
To estimate the strength of the given sample of (C) Colourless (D) Green
KMnO4 solution in g/litre. Prepare a standard
Ex.3 Methyl Red is-
solution of N/10 Mohr’s salt.
Theory:-In this method a solution of Mohr’s salt (A) Acidic indicator (B) Basic Indicator
acidified with dilute sulphuric acid is titrated (C) Neutral (D) None of the above
slowly with potassium permaganate at room
temperature until a permanent pink colour gets Ex.4 Phenolphthalein is-
developed in the solution. The reaction is as (A) Acidic Indicator (B) Basic Indicator
follows: (C) Neutral (D) None of the above
2 KMnO4 + 3H2SO4  K2SO4 + 2MnSO4
+ 3H2O+ 5 [O] Ex.5 According to Modern quinoid theory the
indicator used in acid-alkali titrations are-
[2 FeSO4+H2SO4 +[O]  Fe2(SO4)3 + H2O] ×5
(A) Aliphatic organic compounds
2KMnO 4 + 10FeSO 4 +8H 2 SO 4 K 2 SO 4 (B) Aromatic organic compounds
+2MnSO4
+ 5Fe2 (SO4)3 + 8H2O (C) Inorganic acids
–
Or MnO4 + 5 Fe2+ + 8H+ Mn2+ + 5Fe3+ + 4H2O (D) Inorganic bases
Ex.6 Phenolphthalein shows colour change in a borate and (iv) fluoride.
definite pH range, which is-
Group I
(A) 5.5 - 7.4 (B) 4.5 - 6.5
Take 0.2 g of the substance in a test tube and
(C) 8.3 - 6.5 (D) 8.3 - 10.5 add 2ml of dilute HCl or dilute H2SO4. Observe
Answers : 1 (C) 2 (C) 3 (B) 4 (A) the reaction in cold, warm gently the contents
5 (B) 6 (D) and infer as follows:

5. Qualitative Inorganic Analysis ::

S .N. O b se rva tio n I n fe re n c e C o n fi rm a to ry
Introduction :- T e sts
Qualitative inorganic analysis deals with the
1. B ris k P as s t he g a s
identification of radicals (cations and anions) in CO 23 –
e fferve s c e n c e in ( C a rb o n a te ) in a t es t t u b e
an inorganic salt or in a mixture of salts. A salt c o n ta in in g
consists of two parts known as radicals. The c old w it h e volu t ion s m all q u an tity
positively charged part of a salt (cation) which o f c olo u rle s s an d of lim e w a t e r.
has been derived from a base is termed basic o do u rle s s g as .
It t u rns m ilk y .
radical and the negatively charged part of the 2. A c o lo u rle s s ga s M o is t en a
SO 32 –
salt (anion) which has been derived from an acid w it h s u ffoc a tin g (s u lp h ite ) pie c e o f filte r
is termed acidic radical. For example, the salt o do u r ha vin g pa p er w it h
copper sulphate is obtained by the action of a s m e ll o f b urning ac idifie d
base (copper hydroxide) and an acid (sulphuric s ulp hu r. po t as s iu m
dic hro m a t e
acid). Thus, it has copper ion (Cu2+) as a basic
an d p ut it o n
radical and sulphate ion (SO 42–) as the acidic th e m o ut h o f
radical. th e t e s t t ub e .
Cu(OH)2 + H2SO4  CuSO4 + H2O It t u rns g re e n.
Base Acid Salt 3. A c o lo u rle s s ga s M o is t en a
w it h s m e ll o f (s u lp hid e ) pie c e o f filte r
rott en e ggs . pa p er w it h
2+ 2–
Cu SO4 le a d a c e ta te
Basic radical Acidic radical s o lutio n an d
pla c e it o n th e
A mixture may have two or more salt; thus
m o ut h of t h e
qualitative inorganic analysis consists in te s t t u be . It
identifying the presence of various cations and tu rn s b la c k .
anions in it.
Identification Of Acidic Radicals
Most of these salts are acted upon by dilute H2SO4
or dilute HCl and concentrated H2SO4. In each
case, a gas is liberated which is characteristic of
the particular acidic radical. There are some acidic
radicals which are not decomposed either by dilute
H2SO4 or concentrated H2SO4. Hence, for the
identification of the acidic radicals, the following
scheme is followed.
Group I: This group consists of radicals which are
detected by dilute H2SO4 or dilute HCl. These are
(i) carbonate, (ii) sulphite (iii) sulphide (iv) nitrite
and (v) acetate.
Group II : This group consists of radicals which are
detected by concentrated H2SO4. These are
(i) chloride (ii) bromide (iii) iodide (iv) nitrate and
(v) oxalate.
Group III : The radicals which do not give any
characteristic gas with dilute and concentrated
H2SO4. These are (i) sulphate (ii) phosphate, (iii)
4 A light brown (a) Pass the Reactions with Explanations :-
gas NO 2– evolved gas (i) Carbonate : The carbonates are decomposed
through with dilute HCl or dilute H2SO4 with the evolution
ferrous of carbon dioxide gas. When this gas is passed
(Nitrite) sulphate through lime water, the lime water turns milky
solution, it with the formation of calcium carbonate.
turns Na2CO3 + H2SO4  Na2SO4 +H2O+CO2
brown.
Ca(OH)2+ CO2CaCO3 + H2O
(b) Mix the
Lime water (milky colour)
given salt or
mixture with However, if the CO2 gas is passed in excess, the
a little of KI milky solution becomes colourless due to the
and add formation of soluble calcium bicarbonate.
dilute CaCO3 + H2O+ CO2 Ca(HCO3)2
H2SO4. Milky colour soluble
Evolution of Note :
violet (a) Carbonates of bismuth and barium are not
vapours. easily decomposed by dilute H2SO4. Dilute
S2– (c) Place the HCl should be used.
piece of
(b) Sulphur dioxide evolved from sulphites also
filter paper
turns lime water milky. In the test of
on the
carbonates, the evolved gas must be
mouth of
colourless and odourless (SO2 is a pungent
test tube
moistened gas).
with Ca(OH)2 +SO2CaSO3 + H2O
solution of White ppt.
starch, (c) PbCO3 reacts with HCl or H2SO4 to give, in
potassium the initial stage, some effervescence but the
iodide and reaction slows down due to formation of a
acetic acid. protective insoluble layer of PbCl2 or PbSO4
It turns blue on the surface of remaining salt or mixture.

5. Colourless (ii) Sulphite : A sulphite with dilute H2SO4 gives out

CH3COO– (a) To the
vapours with aqueous sulphur dioxide gas which possesses suffocating
(Acetate)
smell of vinegar solution of smell of burning sulphur. When acidified potassium
substance dichromate paper is exposed to the gas it attains
add neutral green colour due to the formation of chromic
FeCl3 sulphate.
solution Na2SO3 + H2SO4Na2SO4 + H2O +SO2
blood red K2Cr2O7 + H2SO4+ 3SO2  K2SO4 + Cr2(SO4)3+ H2O
colour.
(iii) Sulphide : Dilute H2SO4 decomposes a sulphide
(b) Rub the
salt to form H2S gas which smells like rotten
moistened
eggs.
salt or
mixture with Na2S + H2SO4Na2SO4 + H2S
dry oxalic On exposure to this gas, the lead acetate paper
acid turns black due to the formation of lead sulphide.
smell of Pb(CH3COO)2 + H2S PbS + 2CH3COOH
vinegar. Black ppt.

Note : Sulphides of lead, cadmium, nickel, cobalt,

 antimony and stannic are not decomposed with solution of NH4OH drop by drop with constant
dilute H2SO4. Conc. HCl should be used for their stirring till the precipitate formed does not
test. In such cases, however, brisk evolution of dissolve. At this stage filter the solution. The
H2S takes place even by use of dilute H2SO4, if filtrate is called neutral ferric chloride solution.
a pinch of zine dust is added.
(ii) Before testing acetate in the aqueous solution
Zn + H2SO4  ZnSO4 +2H
of a salt or a mixture, it must be made sure
HgS +2H  Hg + H2S that the solution does not contain the following
(iv) Nitrite : When a nitrite is treated with dilute ions which also combine with Fe3+ ions.
H2SO4, it yields a colourless nitric oxide gas which (i) CO32– (ii) SO32–
in contact with oxygen of the air becomes brown –
(iii) PO34– (iv) I
due to the formation of nitrogen dioxide.
These ions can be removed by addition of
2NaNO2 + H2SO4  Na2SO4 + 2HNO2
AgNO3 solution and only after the removal of
Nitrous acid these ions, the test of acetate should be
3HNO2  H2O + 2NO + HNO3 performed by neutral ferric chloride solution.
2NO + O2  2NO2
(b) Acetates are also decomposed with oxalic
Brown coloured gas acid and give off acetic acid.
(a) On passing the gas in dilute FeSO4 solution, 2CH3COONa + H2C2O4Na2C2O4 + 2CH3COOH
brown coloured complex salt is formed.
FeSO4.7H2O + NO[Fe(H2O)5NO].SO4 +2H2O Group II
Brown colour
Take 0.2g of the substance and add 2 mL of
(b) When a mixture of iodide and nitrite is acted concentrated H2SO4, warm gently, observe the
upon by dilute H 2 SO 4 , the iodide is changes and draw inference as follows :
decomposed giving violet vapours of iodine.
2NaNO2 + H2SO4  Na2SO4 + 2HNO2 Note : W ith concentrated H 2SO 4 , carbonates,
sulphites, sulphides, nitrites and acetates
2KI + H2SO4  K2SO4 +2HI
also behave in the same way as with dilute
2HNO2 +2HI  2H2O + I2 + 2NO
H2SO4.
Violet vapours
(c) Starch-iodide paper is turned blue due to the Reactions with Explanations
liberation of iodine from iodide by nitrous acid (i) Chloride : Colourless pungent fumes of hydrogen
which gives blue colour with starch. chloride are evolved on heating the sodium
2NaNO2 + H2SO4  Na2SO4 + 2HNO2 chloride with conc. H2SO4.
2KI +2CH3COOH + 2HNO2  2CH3 COOK NaCl + H2SO4  NaHSO4 + HCl
+ 2NO + 2H2O + I2 (violet vapours) (a) Yellowish- green gas of chlorine with
I2 + Starch  Blue colour suffocating odour is evolved when the solid
chloride mixed with manganese dioxide is heated
(v) Acetate : Acetates when heated with dilute with conc. H2SO4.
H2SO4 decompose to give acetic acid vapours NaCl + H2SO4  NaHSO4 + HCl
which possess characteristic smell of vinegar.
MnO2+ 4HCl  MnCl2 + 2H2O + Cl2
2 CH3COONa + H2SO4  2CH3COOH +Na2SO4
(b) The gas evolved by heating chloride with
(a) All acetates are soluble in water. On addition sulphuric acid forms white fumes of ammonium
of neutral FeCl3 solution to the solution of an chloride with NH4OH.
acetate, blood red colouration develops due
NH4OH + HCl NH4Cl + H2O
to the formation of ferric acetate.
White fumes
FeCl3 +3CH3COONa  (CH3COO)3 Fe +3NaCl
(c) The gas evolved by heating chloride with
Blood red colour
H2SO4 forms a curdy precipitate of silver chloride
Note : with silver nitrate solution.
(i) The ferric chloride solution supplied in the AgNO3 + HCl AgCl + HNO3
laboratory is always acidic containing HCl. It
ppt.
is made neutral by the addition of dilute
Note: incomplete neutralisation of NaOH solution
The curdy precipitate dissolves in ammonium which reacts with lead acetate to form lead
hydroxide by forming a complex salt. hydroxide.
AgCl + 2NH4OH Ag(NH3)2Cl + 2H2O (v) Bromides and iodides do not give this test.
When the solution having the silver complex is (ii) Bromide :- Reddish-brown fumes of bromine are
acidified with dilute nitric acid, a precipitate of formed when the sodium bromide is heated
silver chloride is again formed. with conc. H2SO4.
Ag(NH3)2Cl + 2HNO3 AgCl + 2NH4NO3 NaBr + H2SO4  2NaHSO4 + HBr
(d) Chromyl chloride test : When solid chloride 2HBr + H2SO4 Br2 + 2H2O +SO2
is heated with conc. H 2SO 4 in presence of More reddish-brown fumes of bromine are evolved
K2Cr2O7, deep red vapours of chromyl chloride when MnO2 is added.
are evolved. 2NaBr + 2H2SO4  2NaHSO4 + 2HBr
NaCl + H2SO4  NaHSO4 + HCl MnO2 + H2SO4  MnSO4 + H2O+ [O]
K2Cr2O7 + 2H2SO4 2KHSO4 +2CrO3 + H2O 2HBr +[O]  H2O +Br2
CrO3 + 2HCl CrO2Cl2 + H2O
Chromyl chloride 2 NaBr + MnO2 + 3H2SO4  2NaHSO4
(deep red vapour) +MnSO4 + 2H2O + Br2
When these vapours are passed through NaOH (a) The aqueous solution of bromide gives pale
solution, the solution becomes yellow due to the yellow precipitate of silver bromide which
formation of sodium chromate. dissolves in excess of NH 4OH forming a
CrO2Cl2 + 4NaOH  Na2CrO4 + 2NaCl + 2H2O soluble complex. [AgBr is sparingly soluble
Yellow colour in NH4OH solution.]
The yellow solution is neutralised with acetic acid NaBr+ AgNO3  AgBr +NaNO3
and on addition of lead acetate gives a yellow Pale yellow ppt
precipitate of lead chromate. AgBr+2NH4OH Ag (NH3)2Br+2H2O
Na2CrO4 + Pb (CH3COO)2 PbCrO4 + 2CH3COONa (b) When the fresh salt or mixture is treated
Yellow ppt. with dilute H2SO4, CHCl3 or CCl4 and chlorine
Note : water, chlorine replaces bromine and the
(i) This test is not given by the chlorides of liberated bromine dissolves in CHCl3 or CCl4
mercury, tin, silver, lead and antimony. In layer giving it brown colour.
such cases this test may be performed by 2KBr + Cl2 2KCl +Br2
taking the residue obtained after evaporation Br2 + Chloroform  Brown layer
of sodium carbonate extract. Note : Excess of chlorine water should not be used.
(ii) The chromyl chloride test is always to be Under this condition the layer attains either
performed in a dry test tube; otherwise the pale yellow colour due to formation of bromine
chromyl chloride vapours will be hydrolysed monochloride or it becomes colourless due
in the test tube. to formation of hypobromous acid.
CrO2Cl2 + 2H2O  H2CrO4 +2HCl Br2 +Cl2 2BrCl (Bromine monochloride)
(iii) The test is said to be positive when all the Br2 +2H2O + Cl2  2HBrO + 2HCl
three observations viz, orange- yellow (red) Hypobromous acid
vapours of chromyl chloride, yellow solution (iii) Iodide : Violet vapours of iodine are evolved on
of sodium chromate, yellow precipitate of lead heating iodide with concentrated H2SO4.
chromate, are correct. 2KI +2H2SO4 2KHSO4 + 2HI
(iv) Sometimes, a white precipitate is obtained 2HI + H2SO4 I2 + SO2 + 2H2O
after the addition of lead acetate solution More violet vapours are evolved when MnO2 is
even in absence of chloride. This may be added.
due to strong heating of the mixture with
2KI +2H2SO4 2KHSO4 + 2HI
conc. H 2 SO 4 when H 2 SO 4 vapours are
MnO2+H 2SO4 MnSO4 + H2O + [O]
absorbed in NaOH solution or due to
 2HI + [O]  H2O + I2 precipitate of AgI with silver nitrate solution
2KI + MnO2 + 3H2SO4 2KHSO4 + MnSO4+2H2O +I2 which does not dissolve in NH4OH.
(a) Violet vapours with starch produce blue colour. NaI + AgNO3  AgI + NaNO3
I2 + Starch  Blue colour Yellow ppt.

(b) Aqueous solution of the iodine gives yellow

S .No. Obse rva tion Infe re nce Confirm a tory Te sts

1. Colourless gas with pungent Cl – (a) B ring a glass rod dipped in NH 4 OH on the mouth of
s mell which fumes in air. [Add (Chloride) test tube; white fumes are formed.
a pinc h of M nO 2 in the
(b) B ring a glass rod dipped in silver nitrate solution on
s olution   pale green gas is the mouth of tes t tube; white c urdy ppt. is formed
evolved. on the rod.
(c) Chrom yl chloride te st : To the substanc e in a dry
test tube add three tim es its weight of powdered
K 2 Cr2 O 7 and conc. H 2 S O 4 . Heat the contents .
Red vapours are evolved. P as s the vapours in a
test tube c ontaining NaOH solution. Now add
acetic acid and lead

2. Reddish brown fumes whic h B r– (a) Take aqueous extrac t of the subs tanc e ( or extract
intensify on addition of MnO 2 . (Bromide) with dilute HNO 3 ) and add silver nitrate s olution. A
V apours passed in water, light yellow prec ipitate appears .
mak e it yellow.
(b) To a small amount of the subs tanc e add dilute
H 2 S O 4 .W arm and cool. A dd 1 m L c hloroform or
carbon tetrachloride and then chlorine water with
constant shaking. The c hloroform layer bec omes
orange-brown.
3. V iolet pungent fumes evolved I– (a) P lace a piece of filter paper m oistened with s tarc h
which m ay condens e as blac k (Iodide) solution on the m outh of the test tube. The paper
s pecks on the cooler parts of turns blue.
the test tube.[The violet fumes
(b) Take aqueous extrac t of the subs tanc e ( or extract
intensify on addition of MnO 2 .]
with dilute HNO 3 ) and add AgNO 3 solution. Y ellow
precipitate is formed whic h is ins oluble in NH 4 OH
solution.
(c) To the s mall amount of the s ubstanc e add dill.
H 2 S O 4 and 1 m L of either chloroform or carbon
tetrachloride and then chlorine water, shak e,
Chloroform layer attains violet colouration.
4. Light brown vapours having NO – 3 Take an aqueous ex tract of the s ubstanc e in a tes t
s mell. Intensify on adding (Nitrate) tube and add freshly prepared FeS O 4 solution. A dd
c opper turnings. conc. H 2 S O 4 by the s ide of the test tube without
disturbing the solution-a brown ring is form ed at
the junc tion of two liquids.
5. Colourless, odourless gas C 2 O 24 – (a) Take the substance, add dil. H 2 S O 4 and heat till
which burns with blue flame at (Oxalate) there are no m ore effervesc enc es . Now add MnO 2
the mouth of the test tube and
(solid)-bris k efferves cences .
turns lime water milky.
(b) Calcium chloride tes t
 (c) When the given substance is treated with (v) Oxalate :-When oxalate is heated with conc.
dilute H2SO4, CHCl3 or CCl4 and chlorine H2SO4, a mixture of CO and CO2 is given
water, chlorine replaces iodine which off. The CO burns with blue flame.
dissolves in CHCl3 or CCl4 layer giving it violet Na2C2O4 + H2SO4Na2SO4 + H2C2O 4
colour.
H2C2O4 + [H2SO4]  CO + CO2
2KI + Cl2  2KCl + I2
+ H2O + [H2SO4]
I2 +CHCl3  Violet layer
Note : Group III
Excess of chlorine water should be avoided
Some anions are identified by their characteristic
as the layer becomes colourless with the
chemical reactions. These radicals are sulphate,
conversion of iodine into iodic acid.
borate, phosphate and fluoride.
[Cl2 + H2O 2HCl + O] × 5 (i) Sulphate : Dissolve a little amount of the
I2 + H2O+ 5[O] 2HIO3 substance (salt or mixture) in dil. HCl and
add barium chloride solution and formed white
I2 + 5Cl2 + 6H2O 2HIO3 + 10HCl
precipitate of BaSO4. A white precipitate
(iv) Nitrate : Light brown fumes of nitrogen insoluble in conc. HNO3 is formed.
dioxide gas are evolved on heating the nitrate Reactions with explanations
with concentrated H2SO4. White precipitate of barium sulphate is obtained
NaNO3 +H2SO4  NaHSO4 + HNO3 when soluble sulphate is treated with barium
4HNO3 2H2O +4NO2 +O2 chloride solution.
These fumes intensify when copper turnings are Na2SO4 + BaCl2  2NaCl + BaSO4
White ppt.
added.
The white precipitate is insoluble in conc. HNO3.
Cu + 4HNO3Cu(NO3)2 + 2NO2 + 2H2O
Certain chlorides e.g., NaCl and BaCl2 when
Ring Test : When the aqueous solution of the present in large quantities, may form a white
substance is treated with freshly prepared precipitate which dissolves on dilution with water.
solution of ferrous sulphate and conc. H2SO4, Silver and lead, if present, may be precipitated
a brown ring is formed on account of the as silver chlorides and lead chloride by the
formation of a complex at the junction of two addition of barium chloride. To avoid it, barium
liquids. nitrate may be used in place of barium chloride.
NaNO3 + H2SO4 NaHSO4 + HNO3 (ii) Borate : To a small quantity of the substance
(salt or mixture), add a few mL of ethyl
6FeSO4 + 2HNO3 + 3H2SO43Fe2(SO4)3
alcohol and conc. H2SO4. Stir the contents
+ 4H2O + 2NO with a glass rod. Heat the test tube and bring
[Fe(H2O)6]SO4.H2O + NO[Fe(H2O)5NO]SO4 +2H2O the mouth of the test tube near the flame.
Ferrous sulphate penta aqua nitrosyl The formation of green edged flame indicates
iron (I) sulphate (Brown ring) the presence of borate.
Note : Reactions with explanations :
When borate is heated with ethyl alcohol and
(a) Ring test is not reliable in presence of nitrite,
H2SO4, ethyl borate vapours come out which
bromide and iodide. burn with green edged flame.
(b) The nitrates can be tested by boiling nitrate 2Na3BO3 + 3H2SO4 3Na2SO4 + 2H3BO3
with Zn or Al in presence of concentrated H3BO3 +3C2H5OH (C2H5)3BO3 + 3H2O
NaOH solution when ammonia is evolved Ethyl borate
which can be detected by the characteristic In place of ethyl alcohol, methyl alcohol can
odour. also be used. This test should be performed
Zn + 2NaOH Na2ZnO2 + 2H in a test tube and not in a porcelain basin
Al + NaOH + H2O NaAIO2 + 3H because copper or barium salts, if present,
will come in contact with the flame which
NaNO3 + 8H NaOH + 2H2O + NH3
also give green flame.
 (iii) Phosphate : Take about 0.2 g of the (a) The test should be performed in perfectly dry
substance in a test tube and add 2 mL conc. test tube, otherwise waxy white deposit will
HNO 3 . Heat and add 2 mL ammonium not be formed on the rod.
molybdate solution. Again heat. A canary (b) HgCl2 and NH4Cl also produce a deposit
yellow precipitate indicates the presence of under these conditions, but this deposit is
phosphate. crystalline in nature.
Reactions with explanations Identification of acidic radicals with sodium
The canary yellow precipitate is due to the carbonate extract
formation of ammonium phosphomolybdate. A large number of acidic radicals can be
Ca3(PO4)2 + 6HNO33Ca(NO3)2+ 2H3PO4 confirmed by using sodium carbonate extract of
H3PO4+12(NH4)2MoO4+21HNO3 (NH4)3PO4 .12MoO3 the mixture. On part of the given substance is
(Canary yellow ppt.) mixed with about 3 parts of sodium carbonate
+21NH4NO3 + 12H2O and nearly 10 to 15 mL of distilled water. The
Arsenic under similar conditions also yields a contents are then heated for 10-15 minutes and
yellow precipitate of (NH 4 ) 3 .AsO 4 .12MoO 3 filtered. The filtrate is known as sodium carbonate
(ammonium arsenomolybdate). So in presence extract or soda extract.
of As, phosphate is tested in the filtrate of second During the heating of mixture with sodium
group. carbonate, double decomposition takes place,
(a) The precipitate of ammonium phosphomolybdate i.e., exchange of partners takes place.
dissolves in excess of phosphate. Thus the For example,
reagent (ammonium molybdate) should always CaC2O4 + NaCO3  CaCO3 + Na2C2O 4
be added in excess.
Insoluble Sodium oxalate
(b) HCI interferes in this test. Hence, if the test (soluble)
of phosphate is to be performed with the PbSO4 + Na2CO3  PbCO3 + Na2SO4
solution containing HCI, the solution should
Insoluble Sodium sulphate
be boiled to remove HCI.
(soluble)
(c) Reducing agents such as sulphites, BaCl2 + Na2CO3  BaCO3 + 2NaCl
sulphides etc., interfere as they reduce Insoluble Sodium chloride
Mo(VI) to molybdenum blue (Mo3O8.xH2O).
(soluble)
The solution therefore, turns blue. In the
Thus, carbonates of the cations of the mixture
presence of reducing agents, the solution
are formed which are mostly insoluble in water
should be boiled with HNO3 as to oxidise
them before the addition of ammonium and are obtained in the residue. On the other
molybdate. hand, sodium salt of the anions (acidic radicals)
of the mixture are formed which being soluble in
(iv) Fluoride : Take a small amount of the
substance in a dry test tube and add an water are obtained in the filtrate.
equal amount of sand. Mix the contents and Mixture
add conc. H2SO4. Heat the contents and
place a glass rod moistened with water over Boiled with excess of Na2CO3 in water
the mouth of the test tube. A waxy white
Filter
deposit on the rod is formed.
Reaction with explanations Residue
Filtrate
The fluoride with conc. H 2SO 4 forms H 2 F 2 (Sodium carbonate extract)
(hydrofluoric acid) which attacks silica forming Sodium carbonate extract (filtrate) contains :
silicon tetrafluoride, [Link] vapours of SiF4 are (i) Sodium salt of acidic radicals present in the
hydrolysed by H2O into gelatinous silicic acid mixture.
which is deposited on the rod. (ii) Unused sodium carbonate and
2NaF + H2SO4 Na2SO4 + H2F2 (iii) Some soluble compound like (NH4)2CO3,
SiO2 + 2H2F2 SiF4 + 2H2O K2CO3, NaAlO2 etc.
3SiF4 + 4H2O H4SiO4 + 2H2SiF6 The sodium carbonate extract is basic in nature
Silicic acid (white) and before it is used for the detection and
 identification of a particular acidic radical, it is (ii) Sulphite : Acidify the soda extract with dilute
first neutralised by the addition of small quantity HCl and add barium chloride solution followed
of an appropriate acid. The acid is added to the by bromine water and heat the contents.
extract till the effervescences cease to evolve. Appearance of white precipitate indicates the
Neutralisation is done according to the following presence of sulphite.
scheme - Na2SO3 + BaCl2 BaSO3 + 2NaCl
Radicals to Acid used for Reagents for Br2 + H2O 2HBr +O
be tested neutralization testing
BaSO3 +O  BaSO4
Chloride Dilute HNO3 AgNO3
White ppt.
Bromide Dilute HNO3 AgNO3
(iii) Sulphate : Acidify the soda extract with dilute
Iodide Dilute HNO3 AgNO3 HCl or dilute HNO3 and add barium chloride
Sulphate Dilute HCl BaCl2 solution. A white precipitate is obtain. A white
Oxalate Acetic acid CaCl2 precipitate insoluble in concentrated HCl and
Sulphite Dilute HCl BaCl2 concentrated HNO3 indicates the presence
of sulphate.
Advantages of preparing sodium carbonate Na2SO4 + BaCl2  BaSO4 + 2NaCl
extract : white ppt.
(i) Many salt are insoluble in water and dilute (iv) Nitrite : Acidify soda extract with acetic acid
[Link] preparation of sodium carbonate and add concentrated solution of cobalt
extract affords a convenient method for chloride. Then add potassium chloride.
bringing the anions of the mixture in solution. Warm the contents and wait for sometime.
Appearance of yellow precipitate indicates the
(ii) It removes the basic radicals (usually
presence of nitrite.
coloured) which could have interfered in the
CoCl2 + 2NaNO2 Co(NO2)2 + 2NaCl
usual tests of some of the acidic radicals.
NaNO2+ CH3COOHCH3COONa + HNO2
(iii) The residue can be used for the test of basic 2HNO2 H2O + 2NO + [O]
radicals of I to VI groups as it can be easily
2Co(NO2)2 + 2NaNO2 + H2O + [O]2Co(NO2)3 + 2NaOH
dissolved in dil. HCl or conc. HCl. Such a
Co(NO2)3 + 3NaNO2Na3[Co(NO2)6]
solution does not involve the problem of
Colourless and soluble
removing interfering radicals like oxalate,
Na3[Co(NO2)6] + 3KCl K3[Co(NO2)6 +3NaCl
fluoride, borate and phosphate. Potassium cobaltinitrite
Test of various acidic radicals with sodium (Yellow and insoluble)
carbonate extract : (v) Chloride : Acidify sodium carbonate extract
(i) Sulphide : (a) Take sodium carbonate extract with dilute nitric acid and add silver nitrate
and add few drops of NaOH and then freshly solution. A white precipitate of silver chloride
prepared sodium nitroprusside solution. is formed which dissolves in ammonium
Appearance of violet colour indicates the hydroxide.
presence of sulphide. NaCl + AgNO3  AgCl + NaNO3
Na2S + Na2[Fe(CN)5NO] Na4[Fe(CN)5NOS] White ppt.

Sodium nitroprusside (Violet colour) (vi) Bromide : (a) Acidify the sodium carbonate
(b) To soda extract, add lead acetate solution. A extract with dilute HNO3 and add silver nitrate
black precipitate indicates the presence of solution. A light yellow precipitate of silver
sulphide. bromide is formed which is sparingly soluble
in ammonium hydroxide.
Na2S + Pb(CH3COO)2 PbS + 2CH3COONa
NaBr + AgNO3  AgBr + NaNO3
Lead sulphide (black)
(c) To soda extract add cadmium carbonate. A Silver bromide
yellow precipitate indicates the presence of (Pale yellow ppt.)
sulphide. (b) Take the second part of the sodium carbonate
Na2S +CdCO3  CdS + Na2CO3 extract and add CHCl3 or CCl4 and then
Cadimium sulphide chlorine water. Shake the contents. The
(yellow ppt.) chloroform layer turns brown.
 2NaBr + Cl2  2NaCl + Br2 different groups and confirmation of the basic
Br2 +Chloroform  Brown layer radicals by specific tests.
Note : In place of chlorine water, conc. HNO 3 (a) Preparation of the original solution
can be used.
The following solvents should be tried strictly
(vii) Iodide : (a) Acidify sodium carbonate extract
in the order given below.
with dilute HNO 3 and add silver nitrate
solution. A yellow precipitate of silver iodide (i) Cold water (ii) Hot water
appears which does not dissolve in (iii) Dilute HCl (iv) Concentrated HCl.
ammonium hydroxide.
(i) Take about 0.1 g of salt or mixture in a test tube
AgNO3 + NaI  AgI + NaNO3
and shake it with 3.4 mL cold distilled water.
yellow ppt.
(ii) If the substance is insoluble, heat to boil the
(b) Take the second part of the soda extract and
add chloroform or carbon tetrachloride and contents and shake.
then chlorine water. Shake vigorously. The (iii) If the substance does not dissolve, take fresh
chloroform layer turns violet. quantity about 0.1 g of salt or mixture in a test
2NaI + Cl2 2NaCl+I2 tube and add about 3 mL dilute HCl and shake.
I2 + Chloroform  Violet layer If the substance is insoluble, boil the contents.
Note : In place of chlorine water, conc. HNO3 (iv) If the substance is still insoluble, treat fresh
can be used.
amount of 0.1 g of salt or mixture with 2mL
(viii) Oxalate : Acidify the sodium carbonate
of conc. HCl. Heat to boiling, dilute with
extract with acetic acid and add CaCl2
solution. A white precipitate is obtained. Filter 5 mL distilled water and again heat. This
and dissolve the precipitate in dilute H2SO4 treatment will dissolve most of the
and add few drops of potassium permaganate substances.
solution. The colour of KMnO4 is discharged. After selecting a suitable solvent for
This indicates the presence of oxalate. the given salt or mixture, take about 10 mL
Na2C2O4 + CaCl2  CaC2O4 + 2NaCl
of the solvent in a boiling test tube, heat to
white ppt.
boiling, add the solid substance little by little.
CaC2O4 +H2SO4  H2C2O4 + CaSO4
Continue heating and adding the mixture till
Oxalic acid
a concentrated solution is obtained. Dilute
2KMnO4 + 3H2SO4 K2SO4 2MnSO4 +3H2O + 5[O]
the solution with equal amount of water.
COOH
| + [O] 2CO 2 +H 2 O If the solution is to be prepared in
COOH concentrated HCl, take about 1.0 g of solid
Note: In presence of fluoride, a white precipitate of substance in a basin, add 5 mL of
CaF2 is also formed by the addition of CaCl2 concentrated HCl. Evaporate to dryness. Add
solution. But CaF2 does not dissolve in dil. 1 mL of concentrated HCl to solid residue
H2SO4 and does not discharge the colour of and 20 mL of distilled water. The solution
KMnO4. thus obtained is called the original solution.
Identification Of Basic Radicals Note :
Wet test analysis for basic radicals includes the (i) When the salt or mixture is soluble in cold
following steps. dilute HCl, it shows that basic radicals Pb2+,
(a) Preparation of the original solution of the salt Hg22+ and Ag+ are absent.
or mixture. (ii) Lead chloride, PbCl2, is soluble in hot solution
(b) Separation of basic radicals into different but insoluble in cold [Link], when the
groups. hot solution is cooled, if a white substance
(c) Analysis of the precipitates obtained in appears, it shows the presence of Pb2+.
(iii) Sometimes, a white precipitate or milkiness Group Bas ic Com pos ition a nd colour
Group
is formed when the solution prepared in re a gent ra dic a l of the pre c ipita te
concentrated HCl is diluted, even when no 1. D ilu te H C l Ag + Ag C l : w h ite Chloride
member of first group is present. This may Pb 2+
Pb C l 2 : w hite ins oluble in
c old dilute
be due to formation of the oxychlorides of
H g 22+ H g 2C l 2 : w h ite HCl
antimony, bismuth and tin.
2. H 2S in Hg 2+ H gS : b la ck
BiCl3 + H2O  BiOCl + 2HCl p re s ence
Pb 2+ Pb S : b lack
white ppt. o f d ilute
3+
HCl Bi Bi 2S 3 : b la ck
The precipitate disappear if little concentrated
C u 2+ C uS: b lack
HCI is added. In such a case, H2S can be
C dS: ye llo w Sulphides
C d 2+
passed through milky solution. ins oluble in
As 3+ As 2S 3: ye llow dilute HCl
2BiOCl + 3H2S  Bi2S3 +2HCl + 2H2O
3+
Sb Sb 2S 3: o ra nge
(iv) A white crystalline precipitate of NaCl and
BaCl2 may be formed from the concentrated Sn 2+ Sn S : b ro w n

solution by the addition of concentrate HCl Sn 4+ Sn S 2 : ye llow

due to common ion effect. Such precipitated 3. N H 4OH in Fe 3+ Fe (OH ) 3:
dissolve on dilution. p re s ence
re d dis h b ro w n Hy drox ides
o f N H 4C l are
(v) The original solution should not be prepared in Cr 3+
C r (OH ) 3:
ins oluble in
concentrated nitric acid and concentrated H2SO4. gre en NH4 OH
These act as oxidising agents and converts H2S Al 3+ Al (OH ) 3: w h ite
into S in second group. Nitric acid converts 4. H 2S in Zn 2+ Zn S:
sulphides of Ba, Sr and Pb into insoluble p re s ence gre en is h w h ite Sulphides
are
sulphates. Similarly sulphuric acid converts the o f N H 4OH MnS:b uff / p in k ins oluble in
Mn 2+
salts of Ba, Sr and Pb into insoluble sulphates. NH4 OH
C o 2+ C oS : b la ck
(b) Separation of basic radicals into groups N i 2+ N iS : bla ck
For systematic analysis, the basic radicals 5. (N H 4) 2C O 3 Ba 2+ Ba C O 3 : w h ite
have been classified into groups. Each group in 2+ Carbo nates
Sr SrC O 3 : w h ite
has a reagent, which shows the presence of p re s ence are inso luble
o f N H 4OH C a 2+ C aC O 3 : w h ite
the basic radical belonging to that particular
6. N a 2H PO 4 Mg 2+ Mg (N H 4) PO 4:
group. It is necessary that the radical is
w hite
completely removed in the respective group
Ze ro N a OH N H4 Am m on ia g as
by using excess of group reagent, g ro u p is evo lved .
otherwiseits presence creates difficulty in
higher group.
(c) Detection of basic radicals
Group I
Radicals: Pb2+, Ag+, Hg22+
Group reagent : Dil. HCl
Procedure : Take cold dilute original solution and
add few drops of dilute HCl. If white precipitate
appears, add more of dilute HCl as to complete
precipitation of basic radicals of first group. Filter,
keep the filtrate for subsequent groups.
 Wash the precipitate with cold water. Transfer Wash the precipitate with hot water. Take small
precipitate in a test tube and add about 10 mL part of the precipitate in a test tube and add
of water, boil. If the precipitate dissolves, Pb2+ is about 5 mL of yellow ammonium sulphide
present and if is does not dissolve, it may have solution,warm upto 60o C with shaking.
Ag+ or Hg 22  . If the precipitate does not dissolve, If the precipitate does not dissolves, Group IIA
filter it. radical may be present.
When the precipitate Solid residue If the precipitate dissolves group IIB radical may
dissolves in hot water (insoluble in hot water), add hot
NH4OH be present.

Insoluble in yellow Soluble in yellow

Divide the filtrate in four Black precipitate isSolid residue ammonium sulphide ammonium sulphide
parts obtained. Dissolve dissolves.
the black ppt. in Divide the IIA Group HgS Black IIB Group As2S3 Yellow
(i) First part-cool
under tap water - aqua-regia, solution into two PbS Black Sb2S3 Orange
white crystalline parts. First part Bi2S3 Black SnS Brown
ppt. of PbCl2. + dil. HNO3
CuS Black SnS2 Yellow
A white ppt.
appeare CdS Yellow
(ii) Second part evaporate off most Second Part + Note :
+K2CrO2soln.  of the acids, dilute KI Soln. A
yellow ppt. of with water and yellow ppt. (i) Before passing H2S, the acidic concentration
PbCrO4 divide into two Ag+ confirmed
parts.
of the solution should be properly adjusted.
If the solution is too acidic, lead and cadmium
will not be precipitated. On the other hand if
(iii) Third part + KI Part I : Add
solution  stannous chloride too little HCl is used, zinc will also be
yellow [Link] solution. A white precipitated. The proper hydrogen ion
PbI2 precipitate appears
which turns grey. concentration is 0.25 N to 0.5 N with respect
to HCl.
(iv) Fourth part + Part II : Add copper
(ii) The original solution must be free from any
dilute H2SO4  turnings. A grey
white ppt. of deposit is formed oxidising agent otherwise H2S gets oxidised
PbSO4, soluble on copper
with precipitation of free sulphur. This is done
in ammonium Hg2+ confirmed
acetate. by heating the mixture with concentrated HCl
Pb2+ confirmed for sufficient time during preparation of original
solution. This treatment will also remove
Group II
sulphite, nitrite from the mixture which can
Radicals : Hg2+, Pb2+ Bi3+ Cu2+, Cd2+ Group IIA
oxidise H2S.
As3+, Sb3+, Sn2+, Sn4+, Group IIB
(iii) Hydrogen sulphide should be passed slowly
Group reagent : H2S gas in presence of dil. HCl
in hot solution to get granular and easily
Procedure : Warm a part of the filtrate of first group
filterable precipitate.
or original solution containing dilute HCl (if first
group is absent) and pass H 2 S gas. If a Group IIA
precipitate (black or brown or yellow or orange) Procedure : Take the precipitate ( if insoluble in
appears, pass H2S through whole of the solution. yellow ammonium sulphide) in a test tube
Filter, dilute the filtrate, warm and again pass and add 5 mL of dilute HNO3. Boil for few
H 2 S. Filter. Repeat this process till the minutes. If insoluble, filter it.
precipitation is complete. Keep the filtrate for
subsequent groups.
Insoluble Soluble–It may have Pb2+, Cu2+,Bi3+ or Cd2+ (ii) Yellow ammonium sulphide is used only for
(black) HgS. Divide the solution into tw o parts.:
Dissolve it in First part : Add dilute H2SO4 and alcohol. one radical, i.e., Sn2+ which is not soluble in
aqua-regia and The appearance of w hite precipitate confirms ordinary in ammonium sulphide. Yellow
divide into tw o the presence of lead. In case no precipitate,
parts. use second part of filtrate. ammonium sulphide consists excess of
Part I: Add Second part of filtrate + excess of NH4OH sulphur and is formulated as (NH 4 ) 2S x,
SnCl2 solution solution w hite precipitate (then filter) or blue
commonly as (NH4)2S2. This converts SnS
a w hite coloured solution or colourless solution.
ppt. Which fist into SnS2 which then dissolves forming
changes into
thio complex. In case Sn 2+ is absent,
greyish
coloured ppt. ordinary ammonium sulphide can be used in
Part II: Cu
place of yellow ammonium sulphide.
turnings
greyish deposit Group IIB
on copper
Procedure: Take the remaining precipitate (if the
turnings.
Hg2+(ic) precipitate is soluble in yellow ammonium
confirmed
sulphide) and add 1 mL of concentrated HCl
Blue coloured Colourless and boil. If the precipitate is insoluble, filter
White precipitate
solution solution
Dissolve the Acidify the Pass H2S and test for arsenic and in case dissolves,
ppt. in dilute HCl solution w ith through soln. test for antimony and tin.
and divide into acetic acid 
three parts : and add Appearance
Part I : K4[Fe(CN)6] of yellow ppt. Insoluble in Soluble in conc. HCl
[Link]
Add solution Soln. A Cd2+present
stannite solution chocolate Dissolve the yellow Dilute the solution with water. Divide
black ppt. choloured ppt. ppt. In conc. the solution in two parts.
Part II : Cu2+present HNO3. Add
Dilute w ith ammonium
First part : Add Second part : Add
molybdate and
w ater  w hite NH4OH and pass iron fillings and heat
again heat
ppt. H2S orange for 10 minutes.
yellow ppt.
Part III : ppt. Filter into a solution
As3+ confirmed of mercuric
Add a little 10% Sb3+ confirmed
chlorideA white
thiourea soln.
ppt. turning grey.
yellow
Sn2+ confirmed
colouration
Bi3+present

Note :(i)Sodium stannite is prepared by taking 1 mL Group III

of stannous chloride and adding to it drop by Radicals : Fe3+, Al3+, Cr3+,
drop NaOH till the precipitate formed
dissolves. Group reagent : NH4OH + NH4Cl
SnCl2 + 2NaOHSn(OH)2 + 2NaCl Procedure : Boil off H2S from the filtrate of II group
ppt.
or take original solution, if first and second
Sn(OH)2 + 2NaOHNa2SnO2 +2H2O
Sodium stannite
group radicals are absent. Add few drops of
(soluble) concentrated HNO3 and boil the solution. Add
10 g solid ammonium chloride and ammonium
hydroxide slowly till the solution smells of
 ammonia. If the precipitate appears, filter. The Black pre cipitate Buff colour e d White
NiS or CoS pre cipitate ,M nS pre cipitate ZnS
filtrate should be kept for subsequent groups.
Wash the ppt. With Dissolve in HCl Dissolve the
Reddish brown Green White precipitate hot w ater and (dil.) A dd NaOH to ppt. in dilute HCl
ppt. Fe(OH)3 precipitate Al(OH)3 dissolve it in aqua- the clear solution and add NaOH
Cr(OH)3 regia and evaporate and then Br 2 drop by drop.
Dissolve the ppt. In ppt. + NaOH + Dissolve the ppt. In dil. to dryness. Extract w [Link] and The precipitate
dilute HCl and Br2 water HCl. Add NaOH solution the residue w ith f ilter. The ppt. is f ormed
divide into two parts Yellow solution  White ppt. Appears w ater or dilute HCl. treated w ith dissolves in
: acidify the yellow which then dissolves in Divide it into tw o conc. HNO3 and NaOH. Pass H2 S
Part I + K4Fe(CN)6 solution with excess of NaOH. Treat parts. PbO2 or Pb 3 O4 gas through this
soln. Prussian acetic acid and this solution with solid Part I + dimethyl (red lead) solution 
blue solution or ppt. add lead acetate ammonium chloride glyoxime + The contents are A ppearance of
Part II + KCNS soln.Yellow Gelatinous white NH4 OHOrange ppt. heated. Keep the w hite ppt.
soln.Red ppt. precipitate. Part II + NaHCO3 + test tube f or Zn 2+ confirm e d
colouration. Cr3+confirmed Al3+ confirmed Br 2 w ater  sometime 
Fe3+ confirmed Black ppt. Purple coloured
Ni2+ confir m e d solution.
M n 2+ confirm e d
Note :(i) H2S must be completely removed, otherwise
the sulphides of the IV group will be
precipitated here. Group V
(ii) A very small amount of HNO3 should be used, Radicals : Ba2+, Sr2+, Ca2+
otherwise manganese from divalent state Group reagent : (NH4)2CO3 in presence of NH4OH
(Mn2+) is oxidised to trivalent state (Mn3+) Procedure: Take the filtrate of fourth group. Boil off
which may get precipitated as Mn(OH)3. H2S gas and concentrate to about 1/2 of its
(iii) Precipitation should be done in hot condition volume. Add a little solid NH4Cl and NH4OH
and large excess of NH4OH should not be followed by NH4OH followed by (NH4)2CO3
used. Ammonium chloride should always be solution. Appearance of white precipitate
added before the addition of ammonium shows the presence of V group. Filter and
hydroxide.
keep the filtrate for VI group. The white
Group IV
precipitate may be either of BaCO 3 or
Radicals : Ni2+, Co2+, Mn2+, Zn2+
[Link] the precipitate in minimum
Group reagent : H2S gas in presence of NH4Cl and
NH4OH quantity of acetic acid. Divide the solution
Procedure: Take the filtrate of third group, into three parts.
concentrate it by heating. Add ammonium Ist part + K2CrO4 If Ba2+ is absent, If Ba2+ and Sr2+
hydroxide and again heat the solution. Pass soln use 2nd part. Add both are absent,
H2S gas. If the precipitate appears pass H2S Yellow precipitate (NH4) 2SO4 use 3rd part. Add
gas for sufficient time and then filter. Keep Ba2+ present solution  (NH4) 2C2O4 
the filtrate for subsequent groups. White precipitate White precipitate
Sr2+ present Ca2+ present

Group VI
Radicals : Mg2+
Group reagent : Na2HPO4 in presence of NH4OH
Procedure: Take the filtrate of V group and add a
little NH4OH and then Na2HPO4 solution.
Scratch the walls of the test tube by a glass
rod and allow to stand. Appearance of white
precipitate confirms the presence of Mg2+.
Test of NH 4 : Take the mixture in a test tube
and add 2-3 mL NaOH solution and heat. If
the smell of NH3 is observed, it confirms the
presence of NH 4 [Link] confirmation can
further be done by the following test.
(i) Bring a rod dipped in HCl near the mouth of
Hg22  (mercurous)
test tube; white dense fumes are formed.
(ii) Take aqueous solution of mixture and add (i) Hg2Cl2 turns black with NH4OH.
Nessler’s reagent. Appearance of brown
colour or precipitate confirms the presence Hg2Cl2 + 2NH4OH Hg + Hg(NH2)Cl +NH4Cl +2H2O
Black
of NH 4 radical.
Chemical Reactions Involved in the Tests of (ii) The black residue dissolves in aqua-regia
Basic Radicals forming mercuric chloride.
Group I 3HCl + HNO3 NOCl + 2H2O + 2Cl
When dil. HCl is added to original solution, 2Hg(NH2)Cl + 6Cl  2HgCl2 + +4HCl + N2
insoluble chlorides of lead, silver and mercurous Hg + 2Cl  HgCl2
are precipitated. (iii) The solution of HgCl2 forms white coloured
Pb(NO3)2 + 2HCl  PbCl2 + 2HNO3 precipitate with stannous chloride.
AgNO3 + HCl  AgCl + HNO3 2HgCl2 +SnCl2  Hg2Cl2 + SnCl4
Hg2(NO3)2 + 2HCl  Hg2Cl2 + 2HNO3 white ppt.
Pb2+ (lead) Hg2Cl2 +SnCl2  2Hg +SnCl4
(i) PbCl2 is soluble in hot water and on cooling Grey ppt.
white crystals are again formed. (iv) The solution of HgCl2 with copper turning
(ii) The solution of PbCl 2 gives a yellow forms a grey deposit.
precipitate with potassium chromate solution HgCl2 +Cu  Hg +CuCl2
which is insoluble in acetic acid but soluble Grey ppt.
in sodium hydroxide. Group II
PbCl2 + K2CrO4  PbCrO2 + 2KCl When hydrogen sulphide is passed in acidified
Yellow ppt. solution, the radicals of second group are
PbCrO4 + 4NaOH Na2PbO2 + Na2CrO4 + 2H2O precipitated as sulphides. The precipitated is
(iii) The solution of PbCl 2 forms a yellow treated with yellow ammonium sulphides. The
precipitate with potassium iodide solution. sulphides of IIB are fist oxidised to higher
sulphides which then dissolve to form
PbCl2 + 2KI  PbI2 + 2KCl
thiocompounds.
yellow ppt.
Ag2S3 +2(NH4)2S2  2(NH4)2S + As2S5
(iv) White precipitate of lead sulphate is formed
with dilute H2SO4. The precipitate is soluble Sb2S3 +2(NH4)2S2  2(NH4)2S + Sb2S5
in ammonium acetate. SnS + (NH4)2S2  (NH4)2S + SnS2
PbCl2 + H2SO4  PbSO4 + 2HCl As2S5 + 3(NH4)2S  2(NH4)3AsS4
Ammonium
PbSO4 + 2CH3COONH4 Pb(CH3COO)2 thioarsenate
+ (NH4)2SO4 Sb2S5 + 3(NH4)2S  2(NH4)3SbS4
Ag+ (silver) Ammonium Soluble
thioantimonate
(i) AgCl dissolves in ammonium hydroxide.
SnS2 +(NH4)2S  (NH4)2SbS3
AgCl + 2NH4OH Ag(NH3)2Cl +2H2O Ammonium
Diammine silver (I) chloride thioantimonate
(ii) On adding dilute HNO3 to the above solution,
white precipitate is again obtained. In case, the precipitate does not dissolve in yellow
ammonium sulphide, it may be either HgS or
Ag(NH3)2Cl + 2HNO3 AgCl + 2NH4NO3
PbS or Bi2S3 or CuS or CdS. The precipitate is
white ppt.
heated with dilute HNO3. Except HgS, all other
(iii) On adding KI to the above solution, yellow
sulphides of IIA are soluble.
precipitate is obtained.
3PbS + 8HNO3  3Pb(NO3)2 + 2NO +3S + 4H2O
Ag(NH3)2Cl +KI  AgI + KCl + 2NH3
Bi2S2 + 8HNO3  2Bi(NO3)3 + 2NO +3S + 4H2O
Yellow ppt.
3CuS + 8HNO3  3Cu(NO3)2 + 2NO +3S + 4H2O
3CdS + 8HNO3  3Cb(NO3)2 + 2NO +3S + 4H2O
 Hg2+ (mercuric) Cu(NH3)4(NO3)2 +4CH3COOH  Cu(NO3)2
HgS is dissolved in aqua-regia. +4CH3COONH4
3HgS +2HNO3 + 6HCl 3HgCl2 +3S +2NO+ 4H2O 2Cu(NO3)2 + K4[Fe(CN)6]  Cu2[Fe(CN)6 + 4KNO3
The solution is divided into two parts. Chocolate ppt.
Part I : Stannous chloride solution reduces HgCl2 Cd2+ (cadmium)
first into white Hg 2Cl2 and then to grey H2S is passed through colourless solution. The
metallic mercury. appearance of yellow precipitate confirms the
Part II : Copper displaces Hg from HgCl2 which presence of cadmium.
gets coated on copper turning as a shining Cd(NH3)4 (NO3)2 + H2S  CdS + 2NH4NO3 +2NH3
deposit. yellow ppt.
Pb2+ (lead) Group IIB
In case the sulphide dissolves in dilute HNO3, a In case the precipitate dissolves in yellow
small part of the solution is taken dilute H2SO4 ammonium sulphide, the test of the radicals
is [Link] lead is present, a white precipitate of arsenic, antimony and tin are performed. The
lead sulphate appears. sulphide is treated with concentrated hydrochloric
Pb(NO3)2 + H2SO4  PbSO4 + 2HNO3 acid. Antimony and tin sulphides dissolves while
white ppt. arsenic sulphide remains insoluble.
In absence of lead, the remaining solution is made 3+
As (arsenic)
alkaline by the addition of excess of NH4OH. The insoluble sulphide is treated with
Bismuth forms a white precipitate of Bi(OH)3, concentrated nitric acid which is then heated with
copper forms a deep blue coloured solution while ammonium molybdate. Yellow precipitate of
cadmium forms a colourless soluble complex.
ammonium arsenomolybdate is formed.
Bi(NO3)2 + 3NH4OHBi(OH)3 +3NH4NO3
As2S5 + 10HNO3  2H3AsO4 + 10NO2 + 2H2O +5S
White ppt.
Arsenic acid
Cu(NO3)2 +4NH4OH[Cu(NH3)4](NO3)2 +4H2O
H3AsO4 + 12(NH4)MoO4 +21HNO3
Tetrammine cupric nitrate
(deep blue solution) (NH4)3 AsO4.12MoO3 +21NH4NO3 +12H2O
Cd(NO3)2 +4NH4OH [Cd(NH3)4](NO3)2 +4H2O Yellow ppt.
Tetrammine cadmium nitrate Sn2+ or Sn4+ (tin)
(colourless solution) Solution of sulphide in concentrated HCl is
Bi3+ (bismuth) reduced with iron fillings or granulated zinc.
The precipitate dissolves in dilute HCl. 2HgCl2 + SnCl2  Hg2Cl2 +SnCl4
Bi(OH)3 + 3HCl BiCl3 + 3H2O white ppt.
Part I: Add ition of excess of water to BiCl3
Hg2Cl2 + SnCl2  2Hg + SnCl4
solution gives a white precipitate due to
Grey
hydrolysis.
Sb3+ (antimony)
BiCl3 + H2O BiOCl + 2HCl
Bismuth oxychloride
Filtrate of sulphide in concentrated HCl is divided
(white ppt.) into two parts.
Part II : The solution of BiCl3 is treated with Part I : On dilution with excess of water, a white
sodium stannite solution when a black precipitate precipitate of antimony oxychloride is obtained.
of metallic bismuth is formed. SbCl3+ H2OSbOCl + 2HCl
2BiCl3 + 3Na2SnO2 + 6NaOH3Na2SnO3 + 2Bi White ppt.
Sod. Stannite Sod. stannate Part II : H2S is circulated. Orange precipitate is
+6NaCl + 3H2O formed.
Cu2+ (copper) 2SbCl3 + 3H2S  Sb2S3 + 6HCl
Blue coloured solution is acidified with acetic Orange ppt.
acid. When potassium ferrocyanide is added, a Group III
chocolate coloured precipitate is formed.
Hydroxides are precipitated on addition of excess
 of ammonium hydroxide in presence of NiS and CoS are black and insoluble in
ammonium chloride. concentrated HCl while MnS (buff coloured), ZnS
AlCl3 + 3NH4OH  Al(OH)3 + 3NH4Cl (colourless) are soluble in conc. HCl.
Gelatinous ppt. Zn2+ (zinc)
CrCl3 + 3NH4OH  Cr(OH)3 + 3NH4Cl The sulphide dissolves in HCl.
Green ppt.
ZnS + 2HCl ZnCl2 + H2S
When the solution is treated with NaOH, first a
FeCl3 + 3NH4OH  Fe(OH)3 + 3NH4Cl
white precipitate appears which dissolves in
Brownish red ppt.
excess of NaOH.
Fe3+ (iron)
ZnCl2 +2NaOH Zn(OH)2 + 2NaCl
The brownish red precipitate dissolves in dilute White ppt.
HCl. The solution is divided into two parts.
Zn(OH)2 + 2NaOH Na2ZnO2 + 2H2O
Part I : K4 [Fe(CN)6] solution is added which forms (Soluble)
deep blue solution or precipitate.
On passing H 2 S, white precipitate of zinc
Fe(OH)3 + 3HCl FeCl3 + 3H2O sulphide is formed.
4FeCl3 +3K4[Fe(CN)6]Fe4[Fe(CN)6]3 +12 KCl Na2ZnO2 + H2S  ZnS + 2NaOH
Prussian blue white ppt.
Part II : Addition of potassium thiocyanate solution Mn2+ (manganese)
gives a blood red colouration. Manganese sulphide dissolves in HCl.
FeCl3 + 3KCNSFe(CNS)3 + 3KCl MnS + 2HCl  MnCl2 + H2S
blood red colour On heating the solution with NaOH and Br2 water
Cr3+ (chromium) manganese dioxide gets precipitated.
The green precipitate is fused with fusion mixture MnCl2 +2NaOH  Mn(OH)2 +2NaCl
(Na2CO3 +KNO3). The fused product is extracted Mn(OH)2+O  MnO2 + H2O
with water or the precipitate is heated with NaOH The precipitate is treated with excess of nitric
and bromine water. acid and PbO2 or Pb3O4 (red lead). The contents
2Cr(OH)3 + 3KNO3 +2Na2CO3  2Na2CrO4 are heated. The formation of permanganic acid
+ 3KNO2 +2CO2 + 3H2O imparts pink colour to the supernatant liquid.
or 2NaOH +Br2  NaBrO + NaBr +H2O 2MnO2 + 4HNO3  2Mn(NO3)2 +2H2O+O2
NaBrO NaBr + [O] 2Mn(NO3)2 +5Pb3O4 + 26HNO3  2HMnO4
2Cr(OH)3 + 4NaOH +3[O] 2Na2CrO4 + 5H2O Permaganic acid (pink)
The solution thus obtained contains sodium + 15 Pb(NO3)2 +12H2O
chromate. The solution is acidified with acetic Note : The above test fails in presence of HCl.
acid and treated with lead acetate solution. A Ni2+ (nickel) and Co2+ (cobalt)
yellow precipitate appears.
The black precipitate is dissolved in aqua-regia.
Na 2 CrO 4 + Pb(CH 3 COO) 2  PbCrO 4
3NiS +6HCl +2HNO3  3NiCl2 +2NO +3S +4H2O
Yellow ppt.
3CoS+6HCl+2HNO3 3CoCl2 +2NO +3S +4H2O
+ 2CH3COONa
The solution is evaporated to dryness and residue
Al3+ (aluminium)
extracted with dilute HCl. It is divided into three
The gelatinous precipitate dissolves in NaOH. parts.
Al(OH)3 + NaOH  NaAIO2 +2H2O. Part I :Add NH 4 OH (excess) and dimethyl
Soluble glyoxime. A rosy red precipitate appears, if nickel
The solution is boiled with ammonium chloride is present.
when Al(OH)3 is again formed. CH3  C== NOH
NiCl2 + 2   + 2NH4OH
NaAIO2 +NH4Cl+H2O Al(OH)3+ NaCl +NH3 CH3  C== NOH
Group IV
On passing H2S through the filtrate of the third
group, sulphides of fourth group are precipitated.
 OH O Group VI
In the filtrate of V group, some quantity of
CH3 –C = N N = C –CH3
Ni + 2NH4Cl + 2H2O ammonium oxalate is added as to remove Ba,
CH3 – C = N N = C –CH3 Ca and Sr completely from the solution. The clear
solution is concentrated and made alkaline with
O OH NH4OH. Disodium hydrogen phosphate is now
Part II : Add CH3 COOH in excess and KNO2. added, a white precipitate is formed.
The appearance of yellow precipitate confirms the MgCl 2 + Na 2 HPO 4 +NH 4 OHMg(NH 4 )PO 4
presence of cobalt. Magnesium ammonium
KNO2 +CH3COOH CH3COOK +HNO2 phosphate (white ppt.)
CoCl2 +2KNO2 Co(NO2)2 + 2KCl +2NaCl +H2O
Co(NO2)2 +2HNO2 Co(NO2)3 +NO +H2O NH 4 (ammonium)
Co(NO2)3 + 3KNO2 K3[Co(NO2)6] The substance (salt or mixture) when heated with
Part III :Solution containing either nickel or cobalt NaOH solution evolves ammonia.
is treated with NaHCO3 and bromine water. NH4Cl +NaOHNaCl +NH3+H2O
Appearance of apple green colour confirms the When a rod dipped in HCl is brought on the
presence of cobalt. If no apple green colour is mouth of the test tube, white fumes of ammonium
chloride are formed.
observed, the solution is heated when black
precipitate is formed, which shows the presence NH3 +HClNH4Cl
of nickel. White fumes

CoCl2 + 2NaHCO3 Co(HCO3)2 +2NaCl To the aqueous solution of ammonium salt when
Co(HCO3)2 + 4NaHCO3 Na4Co(CO3)3 +3H2O Nessler’s reagent is added, brown coloured
+3CO2 precipitate is formed.
Br2 + H2O  2HBr + [O] NH2
2Na4Co(CO3)3+ H2O +[O]  2Na3Co(CO3)3+ 2NaOH
Sod. cobalt carbonate Hg
(green colouration) 2K2HgI4+NH4Cl + 4KOH 
NiCl2 +2NaHCO3  NiCO3 +2NaCl + H2O +CO2 Hg
2NiCO3 + [O]  Ni2O3 + 2CO2 I
Black Millon's base of Iodide
Group V (Brown ppt.)
Ammonium carbonate precipitates V group
radicals in the form of carbonates. These Examples based on identification of
basic radicals
carbonates are soluble in acetic acid.
BaCO3 + 2CH3COOH (CH3COO)2Ba + CO2+ H2O
SrCO3+2CH3COOH(CH3COO)2Sr+CO2 + H2O Ex.1 The presence of NH 4 radical in solution can
CaCO3 + 2CH3COOH (CH3COO)2Ca + CO2 + H2O be detected by -
Ba2+ (barium) (A) Fehling’s solution
Barium chromate is insoluble and precipitated (B) Benedict’s solution
by the addition of potassium chromate solution. (C) Schiff’s reagent
Ba (CH3COO)2 +K2CrO4BaCrO4 +2CH3COOK (D) Nessler’s reagent
Sr2+ (strontium) Sol. (D)
Strontium sulphate is insoluble and precipitated K2HgI4 + NH 4 + 4KOH 
by the addition of ammonium sulphate solution.
Sr(CH3COO)2 + (NH4)2SO4  SrSO4+ 3CH3COONH4 NH2
white ppt. Hg
Ca2+ (calcium) O + 7KI + K+ + 3H2O
Calcium oxalate is insoluble and precipitated by Hg
the addition of ammonium oxalate. I
Ca(CH3COO)2+(NH4)2C2O4  CaC2O4 +2CH3 COONH4 Brown ppt.
white ppt. (Millon’s base of Iodide)
Ex.2 Which of ;the following ions forms ppt. with (C) NH4SCN

KI - Fe3+ + 3SCN  [Fe(SCN)3] 
(A) Mg2+ (B) Pb2+ red colour
2+ 
(C) Hg (D) Cu2+ 2Cu2+ + 4SCN  Cu2(SCN)2  + (SCN)2

white
Sol. (B,C,D)
(D) NH4SCN
Pb2+ + 2I–  PbI2 Co2+ + 4SCN¯ 
 [Co(SCN)4]
2-
Yellow ppt.
blue colour
Hg2+ + 2I–  HgI2 2Cu2+ + 4SCN¯ 
 [Cu2(SCN)2]  +(SCN)2
white
Cu2+ + 2I–  CuI2  Cu2I2 + I2
Ex.3 Which sulphide is insoluble in dilute acids Identification of acidic radicals
but soluble in alkalies - Ex.1 A salt which gives violet vapours on heating
(A) PbS (B) CdS with conc. H2SO4 is -
(C) As2S3 (D) Sb2S3 (A) A sulphate (B) A bromide
Sol. (C) (C) An iodide (D) A nitrate
2As2S3 + 4NaOH  Sol. (C)
NaAsO2 + 3NaAsS2 + 2H2O KI + H2SO4  KHSO4 + HI;
(Soluble)
Ex.4 When dimethyl glyoxime solution is added 2HI + H2SO4  I2 + 2H2O + SO2
to an aqueous solution of nickel chloride in
presence of ammonium hydroxide - Ex.2 In which of the following tests, Cl  ion is
(A) A black ppt. is formed tested by observing the colour of a precipitate
(B) A blue ppt. is formed
(C) A rosy-red ppt. is formed which does not contain Cl  ions at all -
(D) No. ppt. is formed (A) Chromyl chloride test
Sol. (C)
(B) Lassaigne’s test
CH3  C  NOH
(C) Silver mirror test
NiCl2 + 2 | + NH4OH
CH3  C  NOH (D) Fehling solution test
Sol. (A)
CrO2Cl2 + 4NaOH 
Na2CrO4 + 2NaCl + 2H2O
 + 2NH4Cl
yellow

Na2CrO4 + Pb(CH3COO)2 

Red ppt. of nickel dimethyl glyoxime PbCrO4 + 2CH3COONa
Ex.5 Name one common reagent that can yellow ppt.
precipitate or react and differentiate following Ex.3 A mixture when rubbed with an organic acid
pairs - smells like vinegar. It contains -
(A) Ag+ and Ba2+ (B) Cu2+, Pb2+
(C)Fe3+, Cu2+ (D) Co2+ and Cu2+ (A) Sulphur (B) Nitrate
Sol. (A) K2Cr2O 4 (C) Nitrite (D) Acetate
2Ag+ + CrO 2 4   Ag2CrO4  Sol. (D)
red
2CH3COONa + H2C2O4 
Ba2+ + CrO 24 
 BaCrO4 
yellow CH3COOH + Na2C2O4
(Vinegar)
(B) K2CrO4
Cu2+ + CrO 24  Ex.4 An inorganic mixure was treated with excess
 CuCrO4 
chocolate of dil. H2SO4. Effervescence were produced.
Pb2+ + CrO 24  The solution was heated till
 PbCrO4  effervescences ceased. After this a small
yellow
pinch of MnO 2 were added. Fresh
effervescences were produced. Select the
correct statement/s -
 (A) Mixture contains CO32 ions (C) BaCl2

(B) Mixture contains C2O2 BaCl2 + SO32  BaSO3  + 2Cl¯

4 ions
White ppt. soluble in conc. HCl
(C) Mixture contains SO32 ions 2
BaCl2 + SO 4  BaSO4  + 2Cl¯
(D) Mixture contains both CO32 and White ppt. insoluble in conc. HCl

C2O2
4 ions Ex.7 The action of dil. acid on an iron salt produce
a gas with a strong odour. The gas burns
Sol. (D) with a blue flame to produce moisture, a
Effervescences on heating the mixture with yellow residue and traces of another gas,
dil. H2SO4, it is due to decomposition of which has a familiar smell.
carbonate. Identify the gas produced from iron salt and
dil. acid.
Na2CO3 + H2SO4 
Sol. (i) From the persual of the data’s provided,
Na2SO3 + CO2 + H2O the gas evolved may be H2S -
When evolution of CO2 occurs again after 2H2S + O2  2H2O + S
adding MnO2 , it is due to decomposition of (yellow residue)
oxalate. 2H2S + 3O2  2H2O + 2SO2
Na2C2O4 + 2H2SO4 + MnO2  (familiar smell)
(ii) Hence the salt is FeS and the dil. acid is
Na2SO4 + MnSO4 + 2H2O + 2CO2 H2SO4
Ex.5 Few drops of a salt solution are shaken with FeS + H2SO4  FeSO4 + H2S
chloroform, chlorine water. Chloroform layer
becomes violet. Solution contains -
6. Chemical Principles involved in the following
(A) NO2 ion (B) NO3 ion experiments ::

(C) Br- ion (D) I ion (1) Enthaply of solution of CuSO4
Sol. (D) “The enthalpy of solution of a substance in a
2KI + Cl2  2KCl + I2; particular solvent is defined as the enthalpy
change (i.e. amount of heat evolved or absorbed)
I2 + CCI4  violet solution. when 1 mole of the substance is dissolved in
such a large volume of the solvent that further
Ex.6 Name one common reagent that can
addition of the solvent does not produce any more
precipitate or react and differentiate following
pairs - heat change.”
(A) I¯ and Cl¯ (B) I¯ and Br-¯ Under such conditions the solution is said to be
at infinite dilution or simply called a dilute
(C) SO32 and SO2
4 solution.
Sol. (A) AgNO3 Theory:- As the heat of solution stated above

Ag+ + I  AgI  cannot be determined directly, two more heats of
Yellow solution (i) integral heat of solution and (ii)
 differential heat of solution have been introduced.
Ag+ + CI  AgCI 
Integral heat of solution at a particular
White
concentration is the heat change when 1 mole of
(B) Cl2 water + CHCl3 : solute is dissolved in pure solvent to produce a

2I¯ + Cl2  I2 + 2Cl solution of the given concentration. Thus, if
(violet in CHCl3 layer) 1 mole of solution is dissolved in 500 g of water,
 the heat change gives the value intergral heat of
2 Br¯ + Cl2  Br2 + 2Cl
solution if the concentration of 2 molal.
(orange in CHCl3 layer)
 The differential heat of solution HD.S., may water + Heat taken by the flask, stirrer ect.
be defined as the heat of solution of one mole of or 50 (T2–T3) = 50 (T 3 –T1) +W (T 3–T1)
solute in such a large quantity of solution of Where W is the heat capacity of the flask stirrer
known concentration that addition of 1 more mole etc.
of solute does not change the concentration Or (W + 50) (T 3–T1) = 50 (T2–T3)
appreciably. If on dissolving dm moles of the
50(T2 – T3 )
solute in the finite amount of solution the heat Or (W +50) = (T3 – T1 )
change in Sq, then differential heat of solution
will be.  50(T2 – T3 ) 
Or  – 50  cal/degree
HD.S. = Sq / dm  (T3 – T1 ) 
Direct experimental measurement of the (B) Adjust the temperature of distilled Heat water to
differential heat of solution is not possible. It can room temperature (t1ºC) by slightly warming or
however, be determined indirectly from the cooling, as required. Take100 ml. of this water
knowledge of integral heat of solution. in the flask.
HD.S. = (dm H1.5)/dm (C) Take any one of the compounds mentioned above
Where m H1.5 is the integral heat of solution at room temperature (t1ºC). Accurately weight
of concentration m molal. about 1 g of the solid and add it to the distilled
water taken in the flask all at once stirring
As is obvious from the definitions the integral
vigourously so as to dissolve the substance in
and differential heats of solution approach each
minimum time. Note the higher or lowest
other with decreasing concentration and become
temperature (t2 ºC) reached during the process of
identical when the concentration is zero.
solution.
Requirements :- Dewar’s vacuum flask ring
Calculations :-
stirrer of glass tubing, watch glass and a 50 ml.
beaker. The amount of heat evolved or absorbed in
dissolving 1 g of the solid given as
Chemicals :- CuSO4 (solid)
Q = (W + 100) ( t2–t1)
Procedure :- (A) Determination of water
equivalent (w) of the vacuum flask. Where W = water equivalent of the flask.
Take a Dewar’s flask of about 300-500 ml Let the molecular mass of the substance be
capacity and fit in a cork on its mouth. The cork M g mol–1, then the heat of solution
should have two holes one for he thermometer H = – M × Q Calories.
and the other for the stirrer. Add a known mass (2) Enthalpy of neutralization of strong acid and
of water in the flask. Wait for some time and strong base:-
note down its temperature T 1. Also take the Principle :-
known mass of hot water whose temperature is “The amount of heat evolved when one gram
T2 (T 2 should be higher than T1 by at least 20o).
equivalent of an acid is neutralized by one gram
Add this hot water into the cold water taken in
equivalent of the base is called heat of
the flask. Stir the mixture and note the final
neutralisation.”
temperature T3. Note down the observations and
Since all strong acids and bases are completely
calculate the water equivalent or heat capacity of
the Dewar’s flask with accessories as follows :- ionised their heat of neutralisation has a constant
value, which is 13.7 K cal. This is because in all
Observations :-
reactions 1 g equivalent of unionised water
Suppose mass of cold water taken = 50 g
molecules is formed. For example consider the
Temperature of cold water = T 1oC
neutralisation of HCl with NaOH
Let the mass of hot water taken =50g (Say)
H+ + Cl– +Na+ + OH– Na++Cl–+ H2O + Q Cal.
Temperature of hot water = T 2oC
Disregarding the ions common on both the sides
Resultant temperature of the mixture = T 3oC
the net ionic equation can be written as
Calculations :-
H+ + OH–  H2O + Q Cal (Q = 13.7 K Cal.)
Heat given by hot water= Heat taken by cold
In order to determine the heat of neutralisation
 equal volumes of acid and alkali of same strength Experiment (1)
are mixted in a calorimeter or a Dewar’s flask Prepare colloidal solution of (i) arsenious
and the resultant heat evolved is calculated by sulphide, (ii) antimony sulphide(iii)
recording the maximum rise in temperature cadmiumsulphide,(iv) sulphur, (v) ferric
obtained in the reaction. hydroxide, (vi) silver,(vii) molybdenum blue
Requisiter:- Polythene bottle, thermometer stirrer, and (vii) gelatin.
water bath, two beaker’s Theory:- Many a hydrophobic solutions can
Chemicals :- 100 ml of 0.5 N HCl and easily be prepared by chemical methods of
100 ml of 0.5 N NaOH condensation, in which colloidal particles of a
Procedure:- sparingly soluble substance are produced.
(1) The above chemicals are taken into two different Lyophilic solutions, on the other hand are easily
beakers. prepared by agitating the substances with the
(2) Both the beakers are kept in water bath till the appropriate dispersion medium.
solution attain the same temperature. Requirements:- Dialysing apparatus, arsenius
(3) HCl solution is transferred into polythene bottle. oxide tartar emitic, cadmium sulphate, ferric
Immediately NaOH solution is added into the chloride, sodium thiosulphate, source of H2S,
polythene bottle. Stirring is done to mix HCl and
silver nitrate, tannic acid, sodium carbonate,
NaOH. The higest temperature attained is noted.
gelatine, ammonium molybdate, stannous
Calculations :-
chloride, potassium ferrocyanide, oxalic acid,
Assuming that the density of the solution is same wash bottles.
as that of water (i.e., 1g/cm 3) and the sp. heat
Procesure :-
of the solution is nearly equal to that of water
(i.e., 4.184 Jk –1 g–1) and neglecting the heat (i) Aresenius sulphide sol. Boil 1-2 g of pure
capacity of the polythence bottle the result is arsenius oxide with about 500 cm 3 of distilled
calculated as follows- water for about 10-15 minutes. After prolonged
Suppose the initial temperature of the acid and boiling cool the solution to room temperature and
the base = t1oC. filter the undissolved As2O3, if any. Dilute this
Final temperature of the solution after mixing = t2oC solution to 500 cm 3 with distilled water and pass
 Rise in temperature = (t2 –t1) oC a low current of H2S (freed from HCl by passing
Total mass of the solution = 100+100= 200 g through a tube containing soda lime, and then
through 3-4 wash bottles containing distilled water)
 Heat produced = Mass × Sp. heat × rise in temp.
into the solution until it is saturated. Then pass
= 200 × 4.184 × ( t2 –t1)J
a stream of pure hydrogen washed through 3-4
= x KJ (say.)
wahs bottles containing distilled water, so as to
This is the heat produced by neutralisation of
remove the excess of H2S. Filter the solution to
100 ml of 0.5 NHCl.
remove the coarse precipitate of AS 2 S 3, if
 Heat produced by neutralisation of 1000 ml. or 1L
necessary.
of 1N HCl. ( Containing 1 gm equivalent of HCl)
(ii) Antimony sulphide sol. Prepare about 250
x 1
=  1000  Joules cm 3 of 1% solution of tartar emitic in distilled
100 0.5 water and take it in a dropping funnel. Place
(3) Preparation of lyophilic and lyophobic sols :-
about 250 cm 3 of distilled water in a flask and
Principle:- The word lyophilic means liquid-loving pass in it a stream of H2S. The gas must be
and lyophobic means liquid-heating. Lyophilic freed from HCl by passing through a soda lime
solutions can be prepared easily by directly tube and then through 3-4 wash bottles containing
mixing with the liquid dispersion medium. On the distilled water. Add the tartar emitic solution
other hand, lyophobic solutions cannot be drop by drop into water through which H2S is
prepared directly. They can be prepared only by
bubbled. Under these conditions, antimony
special chemical methods of condensation, in
sulphide formed due to double decomposition is
which will colloidal particles of a sparingly soluble
not precipitated but remains in the dispersed state
substance are produced.
with particle size in the colloidal range. A deep
orange coloured colloidal solution of Sb2S3 will
thus be obtained. Free the sol from the excess (vii) Molybdenum blue solution: Prepare a dilute
of H2S by passing a stream of pure hydrogen solution of ammonium molybdate by dissolving a
through it. Then dialyse the sol in order to remove small crystal of the salt in about 250 cm 3 of
the electrolytic impurities. water on warming. To the hot solution add, with
(iii) Cadmium sulphide sol. Prepare about 0.25 M stirring, drop by drop about 0.1 M SnCl2 solution.
solution CdSO4 (mol. wt. 208.4) in distilled Reduction of ammonium molybdate occurs
water and add to it drop-wise a concentrated instantaneously giving a blue sol of molybdenum.
solution of ammonia until the hydroxide (viii) Prussian blue solution: Add slowly 3%
precipitated redissolves. Then bubble in slowly
solution of potassium ferrocyanide into a 3%
pure H2S for about 5-6 minutes. Filter the solution
solution of ferric chloride. After few minutes filter
to remove the coarse precipitate of CdS, if any.
off the precipitate of ferric ferrocyanide and wash
Finally, dialyse the negatively charged CdS sol
it well. Place the precipitate into a filter paper
so obtained to remove the electrolytic impurities.
and pour slowly about 50% solution of oxalic
(iv) Sulphur sol. Dilute 40 cm 3 of 0.1 M Na2S2O3
acid until the precipitate is peptised. Dialyse the
to about 250 cm 3 and add to it drop-wise, with
dark blue solution so obtained to remove the
stirring, 2 cm3 of 2M HCl. Allow to stand for a few
oxalic acid.
minutes and dialyse the sulphure sol so obtained
in order to remove NaCl formed during the (ix) Gelatin solution: Take about 100 cm 3 of
reaction. distilled water and heat it to 80-90oC. Add to it
(v) Ferric Hydroxid sol (a) Prepare about 2% about 2 g of powdered gelatin and dissolve it.
solution of FeCl3 in distilled water and add Allow the solution to cool to room temperature .
gradually 25 cm of the solution to 250 cm 3 boiling
3 This gives you a clear solution of gelatin.
distilled water . A deep red coloured sol of ferric (4) Kinetic Study of reaction of iodide ion with H2O2
hydroxide is instantly produced owing to the at room temperature.
hydrolysis of FeCl 3. Cool the sol to room Experiment (2)
temperature and dialyse it to remove the chloride Study the kinetics of decomposition of H2O2
ions. catalysed by iodide ion.
(b) Prepare approximately 1 M solution of Theory:- Hydrogen peroxide decomposes
ammonium carbonate and place it in a dropping according to the equation
funnel. Prepare nearly a half saturated solution of
2H2O2  2H2O +O2
FeCl3 in distilled water, and add to it the
The reaction is catalysed by iodide ions. The
ammonium carbonate solution drop with constant
reaction is found to be kinetically of first order,
stirring until the precipitate formed just ceases to and so the rate determing step appears to involve
redissolve. Filter, if necessary and dialyse the 1 molecule of H2O2 ; thus
solution in a cellophane tube against distilled
slow
water until only of trace of chloride ions can be H2 O 2  I–  H2 O  IO –
detected in the water. which is followed by
(vi) Silver solution: To 500 cm 3 of distilled water
Rapid
add 20 cm 3 0.1 M silver nitrate solution and 5-10 IO –  IO –  
 2I–  O 2
cm 3 of 1 % solution of tannic acid. Heat the
d[H2O 2 ]
contents to 70-80 oC and add 10 cm 3 of 1% Rate = –  k ' [H2O 2 ][I– ]
dt
solution of sodium carbonate in portions with
continuous stirring. Finally, silver carbonate is As the concentration of iodide ion ramain
formed which is then reduced instantly by tannic constant, so the rate expression becomes
acid to metallic silver. Silver remains in the Rate = k [H2O2] {k’ [I–] = k}
dispersed state giving a quite clear tea coloured The progress of decomposition can be followed
silver solution. Then, dialyse it to remove the measuring the volume of oxygen evolved from
electrolytic impurities. time to time.
Requirements. Gas burette, 5 and 10 cm 3
pipettes, stop clock thermostat or water trough k2 E  T2 – T1 
log   
as thermostat, 1.5% H2O2, 0.1 M KI and 0.1 M KCl. k1 19.147  T1T2 
Procedure(i) Place 5 cm 3 of 1.5 % H2O2 ( if100
Experiment (3)
cm 3 gas burette is used) in a small conical flask
as reaction vessel and add to it some glass Study the kinetics of reaction between
beads. By means of a stopper, connect the vessel bromic and hydrobromic acids and determine
to a gas burette and suspend it in thermostat at 25 the order of the reaction.
or 30oC. Also thermostat about 15 cm 3 of each of Theory:- The overall reaction take place as
0.1 M KI and 0.1 M KCl placed in two test tubes. follows :
(ii) Set the gas measuring apparatus as shown BrO3– + 5Br– + 6H+3H2O + 3Br2
in fig. and adjust the water reservoir so that the The progress of the reaction can easily be
water level stands at 0.1 cm 3 of the gas burette. followed by titrating the liberated bromine with
(iii) Remove the stopper of the reaction vessel, sodium thiosulphate solution.
add to it 5 cm 3 of KI solution using a pipette, Na2S2O3 + 4Br2+ 5H2ONa2SO4+ H2SO4 + 8HBr
shake well and stopper the vessel. Connect it to
The disappearance of yellow colour gives the end
the gas burette. Start the stop watch, adjust the
point of the titration.
pressure in gas burette to atmospheric one (by
Requirements. Thermostat, two large glass
making the water levels in gas burette and
stoppered conical flask, 0.1 M solution of bromic
reservoir to stand at the same height) and record
and hydrobromic acids, 0.01 M sodium
the volume reading. Record the volume of the
thiosulphate solution.
gas collected at intervals of 1-2 minutes adjusting
each time the pressure in the gas burette to Procedure. (i) Place 250 cm 3 of 0.1 M
atmosphetric one. Continue to record the reading hydrobromic acid and 200 cm 3 water in a large
until the rate of formation of gas becomes less glass stoppered conical flask suspended in
than1 cm 3/ min. thermostat at 25oC. Also thermostat bromic acid
solution in another vessel. After about 20-25
(iv) Without disconnecting the reaction vessel from
minutes, add 50 cm 3 of bromic acid solution to
the gas burette, heat it in a boiling water bath for
the reaction vessel, stopper the flask and mix
a few minutes so as to complete the decomposition
thoroughly the contents . The total volume of the
of H2O2. When the gas ceases to evolve, cool the
mixture is 500 cm 3.
reaction vessel back to the temperature of the
experiment . Adjust the pressure in the pressure (ii) Withdraw 50 cm3 samples after 5,10,15,20,30,
in the gas burette to atmoshpheric one and record 40,50, 70, 90 minutes, and rapidly titrate each
the final volume V of oxygen. samplewith 0.01M sodium thiosulphate solution
to the disappearance of yellow colour. Record
(v) Repeat the experiment with 5 cm 3 of 1 : 1
the titre values.
mixture of 0.1 M Kl and 0.1 MKCl ( ionic strength
is kept constant). (iii) Similarly, repeat the experiment with another
reaction mixture containing 250 cm 3 of 0.1M
(vi) In order to determine the energy of activation,
hydrobromic acid, 50 cm 3 of 0.1 M bromic acid
repeat the experiment at higher temperatures,
and 450 cm 3 of water (total volume = 750 cm 3).
35 and 40oC.
The concentrations of the reactants in the second
(vii) The initial concentration of H 2 O 2 is
experiment will be two- third(2/3) of those in the
proportional to V and the concentration at any
first set.
time t to (V–Vt). Thus, a plot of log the (V–Vt)
(iv) In order to study the salt effect for the reaction
against t ( abscissa) will be linerar graph, the
proceed in the same way with a mixture
K
slope of which will be – . Hence calculate K. containing 250 cm 3 of 0.1 M HBr, 50 cm 3 of
2.303
0.1 M bromic acid, 250 cm 3 of 2 M sodium
Then using following equation calculate the energy
sulphate solution and 200 cm 3 water (total volume
of activation.
=750 cm 3).
Calculation. Multiply the titres value for 2nd
 and 3rd mixtures by 3/2 to make the result Ex.2 Enthalpy of netutralisation of HCl with NaOH
comparable. Plot the concentration of bromine is x. The heat evolved when 500 ml of 2 N HCl
are mixed with 250 ml of 4 N NaOH will be-
(x) in terms of tires of sodium thiosulphate
against time (abscissa) for the three mixtures. (A) 500 x (B) 100 x
Calculate the order of the reaction from the (C) x (D) 10 x
relationship t0.5/ t’0.5 = (2/3)n–1, t0.5 and t’0.5 are the
Ex.3 The decomposition of H2O 2 catalysed by
times needed for half change in first and second iodide ion is reaction of -
(third) mixture. Titre readings 18.7 and 12.5 cm 3
will correspond to the half reaction in first and (A) zero order (B) First order
second (third) mixtures respectively. (C) second order (D) None
Compare the results of second and third Ex.4 Which of the following is a hydrophilic colloidal
mixtures to show the salt effect. As the reaction solution?
involves the ions of opposite sign, the reaction (A) Barium sulphate solution
will be considerably slowed in presence of the
(B) Aresenius sulphide solution
salt. ( Negative salt effect).
Example Chemical Principles involved in the (C) Starch solution
based on following experiments.....
(D) Silver iodide solution
Answers : 1 [D] 2 [C] 3 [B] 4 [C]
Ex.1 Heat of neutralisation of strong acid against
strong base is constant and equals to -
(A) 13.7 kcal (B) 57 kJ
4
(C) 5.7×10 J (D) all of the above
Colour of some compounds :-
Colour Compounds

Green CuSO4.5H2O, Cu(OH)2,Cd2[Fe(CN)6] (Light Blue), CoCl2 (Anhydrous), Fe4[Fe(CN)6]3 (Prussian blue),
Fe2[Fe(CN)6]3 (Turnbull’s blue), K3 [Fe(CN)6] (Light Blue), CrO5, CoO•Al2O3 (Thenard blue)

Yellow AgBr, AgI, Ag2CO3, Ag3PO4, Ag2AsO3, CdS, PbI2, PbCrO4, PbO (Massicot), Na2CrO4, BaCrO4,
As2S3, FeCl3 (aq.), FeCl3.6H2O (Solution), K3 [CO(NO2)6] = Indian yellow, Cs3[Co(NO 2)6],
Rb3[Co(NO2)6], SnS2 (Artificial gold), FeS2 (Fool’s gold), As2S5, BiI3, HoBr, Cu2I2, K4[Fe(CN)6]
(pale yellow)

Black [Link](CN)2, [Hg(NH2)Cl + Hg], HgS, PbS, CuS, Bi2S3, Cu2S, CoS, Ag2S, FeS, NiS, Na2S, Hg2O,
Ag2O, MnO2, CuO, Ni2O3, BiI3, Co3O4, FeO, Ni2O3

Blue CuSO4.5H2O, Cu(OH)2, Cd2[Fe(CN)6] (Light Blue), CoCl2 (Anhydrous), Fe4[Fe(CN)6]3 (Prussianblue),
Fe2[Fe(CN)6]3 (Turnbull’s blue), K3 [Fe(CN)6] (Light Blue), CrO5, CoO•Al2O3 (Thenard blue)

Chocolate Cu2 [Fe(CN)6]

Orange HgO (orange-red), KO2, Sb2S3, Sb2S5, K[BiI4] (Solution), K2Cr2O7, BiOI

1
NH2, ZnSO 4.7H2O, Al(OH)3, Zn(OH)2, CaSO4. H2O, Pb(OH)2
White Hg 2
Cl

[Pb(OH)2.2PbCO3] (White lead), Pb(CN)2, AgCN, Cd(CN)2, Zn(CN)2, AgCl, Hg2Cl2, HgCl2, Cu2Cl2,
PbCl2, PbBr2, ZnCl2.H2O [Butter of Zinc (Killed Salt)], KCl, NH4Cl, SnCl4.5H2O (butter of tin)
Ag2SO3 , Hg2SO3, SrSO3,BaSO3,PbSO3,CaSO4. 2H2O ZnS, ZnO (Philospher wool’s), BaSO4,
PbSO4, Hg2SO4

Pink KMnO4, NaMnO4, HMnO4, Mn(OH)2, CoCl2.2H2O, (NH4)2SnCl6, CoO. MgO (Cobalt Pink)

Brown CdO, SnS, KI3, [Link] (Brown ring), [Fe(H2O)5NO]SO4. (Brown Complex)

Canary (NH4)3PO4.12MoO3, (NH4)3AsO4.12MoO3

yellow

Buff Co(CN)2, MnS

Colour change on heating :

Colour change on heating :

Oxide/Hydrated salts Colour

On Cold On Heating

ZnO White Yellow

SnO2 White Yellowish brown

Bi2O3 Yellow Brown

Pb3O4 Red Chocolate

HgO Red Black

HgI2 Crimson Yellow

Fe2O3 Brown Black/Red

FeCl3.6H2O Yellow Brownish Black

Ex.1 In Lassaigne’s test for nitrogen, the blue Ex.4 During qualitative test of nitrate radical, a brown
colour is due to the formation of– ring is formed. The ring formed is due to the
(A) Ferric ferrocyanide formation of -
(B) Potassium ferrocyanide (A) FeSO4NO
(C) Sodium ferrocyanide (B) (FeSO4)2NO
(D) Sodium cyanide Ans.(A)
(C) FeSO4(NO)2
Sol. In Lassaigne’s test substance is heated (D) [Fe(H2O)5NO]SO4
strongly with sodium metal then water extract Sol. (D)
is boilded with alkaline FeSO 4 solution and NaNO3 + H2SO4  NaHSO4 + HNO3
after cooling FeCI3 solution and excess of 6FeSO4 + 2HNO3 + 2H2SO4 
HCI is added in it. If prussian blue or green 2Fe2[SO4]3 + 2NO + 4H2O
ppt. is obtained then Nitrogen is confirmed –
FeSO4 + NO + 5H2O  [Fe(H2O)5NO]SO4
Na + C + N  NaCN Nitrosyl ferrous sulphate

FeSO4 + 2NaOH  Fe(OH)2 + Na2SO4

Ex.5 Acidified K 2 Cr 2O 7 changes to green on
reaction with -
6NaCN+Fe(OH)2 
Na4[Fe(CN)6]+ 2NaOH (A) SO2
(B) FeSO4
3Na4[Fe(CN)6] + 4FeCl3 
(C) KI and then adding hypo
sodium ferrocyanide Fe4[Fe(CN)6]3+12NaCl
(D) NaCl + conc. H2SO4
prussian blue or green
(ferric ferrocyanide) (E) All
Sol. (E)
Ex.2 In sodium fusion test of organic compounds, SO2  SO 2
4
the nitrogen of an organic compound is
converted to– Fe2+  Fe3+
(A) Sodamide
(B) Sodium cyanide All these oxidised hence Cr2O 2
7 is reduced
(C) Sodium nitrite 3+
to Cr (green)
(D) Sodium nitrate Ans. (B) 
I  I2
Sol. Na + C + N   fusion
 NaCN 
Cl  Cl2

Ex.3 A compound which does not give a positive Ex.6 An inorganic compound gives a white ppt.
test in the Lassaigne’s test for ‘N’ is– with a solution of AgNO3, a white ppt. with
(A) Glycine dil. H2SO4 and impart green colour to flame.
(B) Phenyl hydrazine The probable compound is -
(C) Urea
(A) CuCl2 (B) BaCl2
(D) Azobenzene Ans. (D)
(C) Cu(NO3)2 (D) PbCl2
Sol. (B)

2AgNO3 + BaCl2  2AgCl + Ba(NO3)2

Sol. Azobenzene
BaCl2 + H2SO4  BaSO4 + 2HCl
does not give positive test in Lassaigne ’s White ppt.
test for N.
Barium imparts green colour to flame.
Ex.7 Excess of NaOH added will separate - Ex.11 CrO 2 2
4 (yellow) changes to Cr2O 7 (orange)
(A) Al(OH)3, Zn(OH)2 at pH = x and vice versa at pH= y. x and y
(B) AlCl3, ZnCl2
can be -
(C) Fe(OH)3, Mg(OH)2
(D) Fe(OH)3, Al(OH)3 (A) 6,5 (B) 6,8
Sol. (D) (C) 8,9 (D) 7,7
AlCl3 NaOH Sol. (B)
 Al(OH)3
Cr2O 2 -  2CrO 2 + H O
 NaAlO2 (soluble)
NaOH 7 + 2OH 4 2

orange yellow

ZnCl +  2CrO 2 + H O

2  Zn(OH)
2 Na2ZnO2(soluble)
NaOH NaOH
2Cr2O 2
4 + 2H 7 2
Fe(OH)3 NaOH
 Fe(OH)3 (insoluble)
Ex.12 Green coloured solute (A)    white ppt
AgNO3
Mg(OH)2 NaOH
 Mg(OH)2 (insoluble)

(B)   H2O2, KOH
Ex.8 An inorganic salt in its aq. solution produced
a white ppt. with NaOH which dissolves in ( CH 3COO ) 2 Pb

excess of NaOH, Also its aq. solution Yellow solution (C) (   yellow ppt
CH COOH )
3
produced light yellow ppt. with AgNO 3 , (D). Which is correct -
sparingly soluble in NH4OH. The probable salt
is - A B C D
(A) AlBr3 (B) AlI3 (A) AgCl KCl PbI2 PbI2
(C) AlCl3 (D) ZnCl2 (B) AgCl KCl PbCrO4 Pb2Cr2O7
Sol. (A) (C) AgCl CrCl3 PbCrO4 PbI2
AlBr3 + 3NaOH  Al(OH)3 + 3NaBr (D) CrCl3 AgCl K2CrO4 PbCrO4
White ppt.
Sol. (D)
Al(OH)3 + NaOH  NaAlO2 + 2H2O

CrCl3 + H2O2 + KOH 
Soluble  K2CrO4 (yellow)

3AgNO3 + AlBr3  3AgBr + Al(NO3)3 CrO 2 2 +  PbCrO (yellow ppt)
4 + Pb 4
light yellow ppt.
Cl¯ + K2Cr2O7 + H2SO4  CrO2Cl2
Ex.9 This reagent gives white ppt with KI followed 
by hypo addition - CrO2Cl2 + KOH  K2CrO4
(A) CuSO4 (B) HgCl2
(C) FeCl3 (D) A , B true
Sol. (A) Ex.13 Sometimes yellow turbidity appears on
2CuSO4 + 4KI  Cu2I2 + I2+ 2K2SO4 passing H2S gas even in absence of second
White ppt. group basic radicals. This happens because-
(A) Sulphur is present in the mixture
Ex.10 A compound produced blue mass in cobalt
nitrate test and formed a brown ring with (B) Fourth group radicals are precipitated
FeSO 4 and conc. H 2 SO 4. The probable (C) H2S is oxidised by some acid radicals
compound is - (D) Third group radicals are precipitated
(A) Al(NO3)3 (B) Zn(NO3)2 Sol. (C)
(C) Cu(NO3)2 (D) MgCl2
This is due to oxidation of H2S into S by
Sol. (A)
Al(NO3)3 decomposes to Al2O3 which forms NO 2 , SO 32 or ferric salt
a blue mass (Thenard blue) with cobalt oxide
obtained from decomposition of Co(AlO 2)3 e.g. 2FeCl3 + H2S  2FeCl2 + 2HCl + S
Blue mask
Al2O3 + CoO = CoO . Al2O3 or Co(AlO2)2
blue mask
Ex.14 White fumes liberated on treating a white solid Ex.15 A yellow fuming liquid (A) undergoes partial
with conc. H2SO4 and SiO2 leaves a white decomposition to produce Cl2 gas and another
deposit on a glass rod moistened with water. product whose acidic solution
The white solid could be - produced an orange ppt. with H2S. The liq.(A)
(A) NaCl (B) NaF is -
(C) NH4Cl (D) NaBr (A) SbCl3 (B) SbCl5
Sol. (B) (C) AsCl3 (D) AsCl5

SiO2 + NaF + H2SO4  Sol. (B)
 SiF4
SbCl5 SbCl3 + Cl2
3SiF4 + 4H2O  2H2SiF4 + H4SiO4
2SbCl3 + 3H2S  Sb2S3 + 6HCl
White deposit (orange ppt.)
 Questions
based on Group- I Acidic Radical Q.8 Sodium carbonate extract is a mixture of -
(A) [Salt + Na2CO3 + HCl]
Q.1 Which of the following gives a suffocating
gas when treated with dilute HCl - (B) [Salt + Na2CO3 + H2O]
(A) carbonate (B) sulphite (C) [Salt + CaCO3 + HCl]
(C) sulphate (D) borate (D) [Salt + Na2CO3 + HNO3]

Q.2 The mixture when rubbed with organic acid Q.9 For the test of sulphite, the soda extract is
acidified with -
smells like vinegar obtain. It contains -
(A) dil HCl (B) dil HNO3
(A) sulphur (B) nitrate
(C) CH3COOH (D) None of these
(C) nitrite (D) acetate
Questions
based on Basic Radical
Q.3 The type of analysis that deals with the Q.10 Lead sulphate is soluble in which solvent
methods which are used to determine the
(A) Ammonium acetate
constituents of a compound is -
(B) Conc. HNO3
(A) Qualitative analysis
(C) Ammonium hydroxide
(B) Titrametric analysis
(D) Conc. HCl
(C) Volumetric analysis
(D) None of the above Q.11 An alkaline solution of potassium mercuric
iodide is known as -
Questions
Group- II, III Acidic Radical (A) Nessler’s reagent
based on
(B) Lassaigne’s reagent
Q.4 The chromyl chloride test is meant for which (C) Fenton’s reagent
of the following ions ?
(D) None of the above
(A) Cl– ions
(B) both Cl– and Br– ions
Q.12 A solution on treatment with aqueous
(C) I– ions ammonia turns blue. It contains -
(D) Cl– and CrO42– ions (A) Cu2+ (B) Ni2+
(C) Co2+ (D) Mn2+
Q.5 Violet vapours are given out when ........... is
treated with conc. H2SO4 -
Q.13 The sulphide which is insoluble in 30% HNO3
(A) bromide (B) iodide is -
(C) chloride (D) nitrate (A) HgS (B) CuS
(C) PbS (D) CdS
Q.6 AgCl react with NH3 forms a complex -
(A) AgNO3 (B) Ag NH2Cl Q.14 The group reagent for the V group radicals
(C) Ag (NH3)2 Cl (D) Ag mirror is -
(A) (NH4)2CO3 (B) (NH4)2SO4
Q.7 For the test of oxalates, the soda extract is (C) NH4Cl (D) (NH4)2C2O4
acidified with -
(A) dil H2SO4 (B) dil HNO3 Q.15 K2HgI4 Is useful for detecting -
(C) CH3COOH (D) None (A) NO3– (B) PO4–3
(C) Cl– (D) NH4+
Q.16 A Black sulphide is formed by the action of Q.26 Aqueous solution of Potash Alum is -
H2S on - (A) Acidic (B) Basic
(A) CuCl2 (B) CdCl2
(C) Neutral (D) Amphoteric
(C) ZnCl2 (D) None

Q.17 Which of the following sulphides has the Q.27 The purpose of carrying out crystallization is-
maximum solubility product - (A) To prepare a substance in solid state
(A) HgS (B) PbS only
(C) CuS (D) MnS (B) [Link] a substance in state of purity

Q.18 Which sulphides are soluble only in aqua- (C) To prepare a substance in hydrated state
regia - (D) None of the above
(A) NiS (B) HgS
Q.28 Colour of potash alum Crystals -
(C) CoS (D) All of these
(A) Green (B) Blue
Q.19 Which of the sulphides is yellow - (C) Colourless (D) Black
(A) ZnS (B) CdS Detection of N, S and halogen in
Questions
(C) NiS (D) PbS based on organic compounds
Q.20 In qualitative analysis Cd is under -
(A) I group (B) II group Q.29 Sodium extract of an organic substance gives
(C) III group (D) IV group a blood red colour with FeCl3. It contains the
elements -
Q.21 In the II A group basic radical, the ions are (A) N (B) S
present - (C) N & S both (D) N or S
(A) Cu+2, Cd+2 (B) Ni+2, Zn+2
+2
(C) Pb , Al +3 (D) Cr+3, Cu+2 Q.30 Copper wire test of halogens is known as -
(A) Beilstein test
Q.22 The ion which is not precipitated by H2S in (B) Liebig test
the presence of HCl is -
(C) Lassaigne test
(A) Cu+2 (B) cd+2
(D) fusion test
(C) Pb+2 (D) Al+3

Q.23 CoCl2 is - Q.31 Violet colouration in Lassaigne test with

sodium nitroprusside, indicates the presence
(A) pink (B) black
of -
(C) green (D) colourless
(A) N (B) S
Q.24 Addition of KI to lead saturated in water gives (C) halogen (D) O
precipitate, the colour is -
Q.32 Sodium nitroprusside gives violet colour of
(A) yellow (B) black ........ with aqueous solution of Na2S -
(C) white (D) red (A) Na4[Fe(CN)5NOS]
(B) Na3[Fe(CN)5NOS]
Questions Preparation of mohr’s salt and
based on Potash alum (C) Na2[Fe(H2O)5NOS]
(D) Na4[Fe(H2O)5NOS]

Q.25 What is green vitriol ?

Q.33 Prussian blue is -
(A) FeSO4.7H2O (A) Na4Fe (CN)6
(B)(NH4)2 SO4.6H2O (B) Na3Fe(CN)6
(C) K2SO4 (C) Fe4[Fe(CN)6]3
(D) Na2SO4 (D) None of these
Q.34 When sodium extract is prepared, generally Questions Detection of Functional Group
the substance ignites - based on in Organic Compounds
(A) Na (B) H2
(C) Organic compound (D) O2 Q.42 Carboxylic group changes the blue litmus to -
(A) Black (B) Red
(C) White (D) Green
Q.35 In the detection of nitrogen in sodalime test ,
the evolved gas is - Q.43 Fehling solution ‘B’ consists of -
(A) N2 (B) NO (A) NaOH + potassium tartarate
(C) NH3 (D) NO2 (B) NaOH + Sodium tartarate
(C) CuSO4 + CH3COOH
Q.36 Beilstein test for organic compounds in used (D) NaOH + Sodium potassium tartarate
to detect - Q.44 Which test is used to distinguish aldehydes
(A) nitrogen (B) halogen from Ketones?
(C) sulphur (D) carbon (A) Tollen’s test
(B) Fehlling’s test
Q.37 In Lassaigne’s test for N, S and halogens, (C) Both (A) & (B)
the organic compound is - (D) None of the above
(A) Fused with sodium
Q.45 Liebermann’s test is used for which class of
(B) Dissolved with sodamide
compounds -
(C) Extracted with sodamide (A) Alcohols (B) Phenols
(D) Fused with calcium
(C) Aldehydes (D) Ketones
Q.38 In Lasaigne’s test for nitrogen, the blue colour Q.46 Sodalime test for the detection of nitrogen is
is due to the formation of - not reliable for the group -
(A) Ferric ferrocyanide (A) – CHO (B) – NO2
(B) Potassium ferrocyanide (C) – N = N – (D) Both (B) and (C)
(C) Sodium ferrocyanide
Q.47 In the Xanthate test for the detection of
(D) Sodium cyanide
alcohol, which colour ppt. is obtained -
(A) Green (B) Red
Q.39 Positive Beilstein test shows that -
(C) Yellow (D) Brown
(A) Halogens are surely present
(B) Halogens are absent Q.48 For detection of alcohol group in the Victor
(C) Halogens may be present meyer’s test, 2º Alcohol give colour -
(D) None of the above (A) Red (B) Blue
(C) Black (D) Colourless
Q.40 In Lassaigne’s test sodium metal is used
because - Q.49 Lucas reagent is -
(A) it is very reactive (A) Ag + [Link]
(B) its melting point is low (B) Zn + Conc. HCl
(C) Cd + Conc. H2SO4
(C) its compounds are soluble in water
(D) Zn + Conc. HNO3
(D) all of the above
Q.50 Tollen’s reagent is -
Q.41 For the detection of halogen in lassaigne’s
test, the light yellow ppt indicate the presence (A) [Ag(NH3)2]OH
of - (B) [Ag(H2O)2]OH
(A) Cl (B) Br (C) [Ag(NH3)4]Cl
(C) I (D) None (D) None
Q.51 In the detection of ketones which test is
Titration, Enthalpy of Solution, Ethalpy of
used - Questions
Neutralisation,Indicator, and Lyophilic
based on
(A) Libermann’s test and Lyophobic sols
(B) Lassaigne test Q.58 The size of the colloidal particles is -
(C) Nitroprusside test (A) Between 100 nm to 1000 nm.
(D) None (B) Between 10 nm to 100 nm.
(C) Between 1 nm to 100 nm.
Q.52 Benedict’s solution provides : (D) Between 500 nm to 1000 nm.
(A) Ag+ (B) Cu2+
(C) Ba 2+ (D) Li+ Q.59 The pH range of phenol red is -
(A) 6.3 - 8.4 (B) 4.8 - 6
(C) 3.2 - 4.4 (D) 8.2 - 10
Questions Preparation of Some Organic
based on Compounds Q.60 In the titration of strong acid and weak base
suitable indicator is -
(A) phenolphthalein (B) methyl orange
Q.53 The formation of aniline yellow from
(C) No indicator used (D) Thymol blue
benzenediazonium chloride and aniline in
acidic medium is known as-
Q.61 Greater is the protective power of lyophilic
(A) Coupling Reaction colloid -
(A) leasser is its gold number
,
(B) Gomberg s Reaction (B) greater is its gold number
(C) Gattermann Reaction (C) either of the above
(D) none
(D) Sandmeyer Reaction
Q.62 The molarity of water is -
Q.54 Preparation of acetanilide involves the reagents (A) 5.55 mol/L (B) 18.0 mol/L
aniline, glacial acetic acid and ---. (C) 55.55 mol/L (D) 10 mol/L

(A) Acetone (B) Acetophenone Q.63 Enthalpy of neutralisation of strong acid and
strong base are -
(C) Acetic anhydride (D) Phenol (A) – 13.7 Kcal (B) – 57.1 Kcal
(C) + 13.7 Kcal (D) + 57.1 Kcal
Q.55 In iodoform reaction acetone is treated with-
(A) Sodium iodide Q.64 Solvent loving colloids are -
(B) Sodium hypoiodide (A) lyophobic colloid (B) lyophilic colloid
(C) Iodine (C) hydrophobic colloid (D) none
(D) None of the above
Q.65 Solvent hating colloids are -
(A) lyophobic (B) hydrophilic
Q.56 The IUPAC name of iodoform is - (C) lyophilic (D) none
(A) Methyl iodide
(B) Methyl triiodide Questions
Kinetics of Decomposition of H2O2
based on –
(C) Triiodo methane Catalysed by I ion
(D) None of the above
Q.66 The given data confirms that order of reaction
Q.57 The IUPAC name of acetanilide is - is -
(A) Aniline methyl Ketone Time 0 20 30
(B) Methyl benzamide Rate 2.8×10–2 2.8×10–2 2.8×10–2
(C) Phenylethanamide
(A) 0 (B) 1
(D) All.
(C) 2 (D) 3
Q.67 The rate constant of nth order has units - Q.71 Which of the following procedures will lead to
(A) litre1–n mol1–n sec a change in the rate constant ‘K’ of a
(B) mol1–n litre1–n sec–1 reaction -
(C) mol1–n litren–1 sec–1 (A) a change in the pressure
(D) none (B) a change in temperature
(C) change in the volume of the reaction
Q.68 Catalytic decomposition of H2O2 is .... order vessel
of reaction - (D) none
(A) zero (B) 1
(C) 2 (D) 3 Q.72 Which curve prepresents a Ist order reaction-

Q.69 Which one does not influence the rate of

reaction - t1/2 t1/2
(A) nature of reactant (A) (B)
(B) conc. of reactant a a
(C) temperature
(D) molecularity t1/2 t1/2
(C) (D)
Q.70 The rate law of the single-step reaction
a a
2A + B  2C, is given by -
(A) rate = k[A].[B] (B) rate = k[A]2.[B]
(C) rate = k[2A].[B] (D) rate = k[A]2.[B]0 Q.73 Activation energy of a reaction is -
(A) the energy released during the reaction
(B) the energy evolved when activated
complex is formed
(C) minimum amount of energy needed to
overcome the potential barrier
(D) the energy needed to form one mole of
the product
 Q.8 In order to prevent the hydrolysis of ferrous
Q. 1 Brown ring test is made for -
sulphate in the preparation of Mohr’s salt what

(A) NO3 (B) Cl is added -
(C) I¯ (D) Br¯ (A) Con.H2SO4 (B) Dil. H2SO4
(C) Water (D) Conc. HNO3
Q.2 Rate constant of a reaction (k) is 175 mol–1
litre sec–1 What is the order of reaction? Q.9 Freshly prepared chlorine water is added to
(A) first (B) second the aqueous solution of some halide salt
containing some CS 2. After shaking the
(C) third (D) zero
contents, a violet colour is appeared in CS2
layer. The halide ion in solution is -
Q.3 In Lassaingne’s test for deteraction of (A) Iodide
nitrogen, the blue colour is due to the (B) Bromide
compound - (C) Chloride
(A) Na4[Fe(CN)6] (B) NaCN (D) Iodide as well as bromide
(C) Na3[Fe(CN)6]4 (D) Fe4[Fe(CN)6]3 Q.10 Mixing of SnCl2 to HgCl2 Solutions gives ppt.
which is -
Q.4 For deteraction of sulphur in an organic (A) white turning to grey
compound, the Lassaigne’s extract is (B) black turning to white
acidified with dilute acetic acid and lead (C) white turning to red
(D) red turning to white
acetate is the added to it. The black ppt. is
obtained which is due to the formation of - Q.11 Soda extract of the salt is prepared by -
(A) PbS (B) Na2S (A) Fusing mixture of baking soda and salt
and then extracting with water
(C) PbSO4 (D) PbS2O3
(B) Dissolving NaHCO3 and salt in dil. HCl
(C) Boiling Na2 CO3 and salt in dil. HCl
Q.5 A compound which does not give a positive (D) Boiling Na2CO3 and salt in distilled water
test in the Lassaigne’s test for nitrogen is
Q.12 When H2S is passed through Hg22+, we
(A) Urea (B) Hydroxl amine
get -
(C) Glycine (D) Phenylhydrazine (A) HgS (B) HgS + Hg2S
(C) HgS + Hg (D) Hg2S
Q.6 An aqueous solution contains SO42– and Cl–
Q.13 In the second group of qualitative analysis,
ions. Which of the following aqueous solutions
H2S is passed through a solution acidified
will precipitate only SO42– ion but not Cl– ion ?
with HCl in order to -
(A) NaOH (B) KOH
(A) Limit the concentration of S2– ions
(C) BaCl2 (D) BaSO4
(B) Increase the solubility of H2S
(C) Increase the concentration of S2– ions
Q.7 When concentrated H2SO4 is added to dry
KNO3, brown fumes are evolved. These fumes (D) Add the Cl– ions.
are due to -
(A) SO2 (B) SO2 + SO3 Q.14 In the Lassaigne’s test the sulphur present
(C) NO (D) NO2 in the organic compound first changes into -
(A) Na2SO4 (B) CS2
(C) Na2SO4 (D) Na2S
Q.15 Ferric ion forms a prussian blue coloured Q.23 Which on mixing gives deep brown colour -
precipitate with K 4 [Fe(CN) 6 ] due to the (A) N2O + O2 (B) NO + O2
formation of - (C) N2O3 + O2 (D) None
(A) K3Fe(CN)6 (B) Fe4[Fe(CN)6]3
(C) Fe(OH)3 (D) KFe[(CN)6] Q.24 Redish brown (chocolate) ppt are formed with-
(A) Cu2+ and [Fe(CN)6]2–
Q.16 Manganese salt + PbO2 + conc.HNO3  (B) Ba2+ and SO42–
The solution acquires purple colour. The (C) Pb2+ and I–
colour is due to - (D) none
(A) HMnO4 (B) a lead salt
Q.25 On passing H2S in II group, sometimes a
(C) Mn(NO3)2 (D) H2MnO4 white turbidity is formed. This is due to -
(A) colloidal sulphur (B) SnS2
Q.17 In Victor meyer test reactant in the reaction (C) Bi2S3 (D) ZnS
follow the order -
(A) AgNO2, HNO2, NaOH, (Red P + I2) Q.26 For the tests of halides, the soda extract is
acidified with -
(B) (Red P + I2), AgNO2, HNO2, NaOH
(A) dil. H2SO4 (B) dil. HNO3
(C) AgNO2, NaOH, (Red P + I2), HNO2
(C) dil. HCl (D) any of the three
(D) (Red P + I2), AgNO2, NaOH, HNO2
Q.27 The colour developed when sodium sulphide
Q.18 Which of the following indicators is used in is added to sodium nitroprusside is -
the titration of oxalic acid with sodium (A) violet (B) yellow
hydroxide solution - (C) red (D) black
(A) Bromophenol blue
Q.28 All ammonium salts liberate ammonia when-
(B) Methyl red
(A) heated
(C) Methyl orange
(B) heated with caustic soda
(D) Phenophthalein (C) heated with H2SO4
Q.19 Which of the following indicators is used in (D) heated with NaNO2
the titration of KMnO4 against sodium oxalate
in an acidic medium - Q.29 If ‘a’ is the initial conc. of a substance which
reacts according to zero order kinetic and k
(A) Phenolphthalein is rate constant, the time for the reaction to
(B) Eriochrome black T go to completion is -
(C) No indicator is necessary (A) a/k (B) 2/ka
(D) Starch (C) k/a (D) 2k/a

Q.20 Ca, Ba and Sr ions are precipitated in fifth

Q.30 The term-dc/dt in a rate equation referes to-
group as their -
(A) the conc. of a reactant
(A) Oxides (B) Sulphates
(B) the decrease in conc. of the reactant
(C) Carbonates (D) Sulphides with time
(C) the velocity constant of reaction
Q.21 AgNO3 gives yellow ppt with -
(D) none
(A) KIO3 (B) KI
(C) CHI3 (D) CH2I2 Q.31 The temperature coefficient of a reaction is-
(A) the rate constt. at a fixed temperature
Q.22 Which can be used in place of NH4Cl in III
group precipitation - (B) the ratio of rate constt. at two temperatures
(C) the ratio of rate const. differing by10o
(A) NH4 NO3 (B) (NH4)2CrO4
(K35/K25)
(C) (NH4)2SO4 (D) NaCl
(D) none
Q.32 The metal ion which is precipitated when H2S Q.34 Which of the following metal sulphides has
is passed with HCl - maximum solubility in water -
(A) Zn2+ (B) Ni2+ (A) HgS,Ksp = 10–54 (B) CdS,Ksp = 10–30
(C) Cd 2+ (D) Mn2+ (C) FeS,Ksp = 10–20 (D) ZnS,Ksp = 10–22

Q.33 In Nesseler’s reagent for detection of Q.35 When H2S gas is passed in a metal sulphate
ammonia, the active speies is - solution in presence of NH4OH, a white
(A) Hg2Cl2 (B) Hg2+ precipitate is produced. The metal is
(C) Hg2I2 (D) HgI42– identified as -
(A) Zn (B) Fe
(C) Pb (D) Hg
Q. 1 When H2S is passed through an ammonical Q. 9 A salt which gives CO2 with hot conc. H2SO4
salt solution X, a white precipitate is obtained. and also decolourizes acidified KMnO4 on
Then X can be a - warming is -
(A) Co2+ solution (B) Mn2+ solution (A) HCO3 (B) CO32
(C) Ni2+ solution (D) Zn2+ solution
(C) Oxalate (D) Acetate
Q. 2 In third group, bromine water is used to test-
(A) Fe3+ ions (B) Cr3+ ions Q.10 Sodium extract is heated with conc. HNO3
3+
(C) Al ions (D) All of these
(A) silver halides are insoluble in HNO3
Q. 3 In IV group analysis NH4OH is added before
(B) Na2S and NaCN are decomposed by
passing H2S gas because -
HNO3
(A) The sulphides of IV group are insoluble in
NH4OH (C) Ag2S is soluble in HNO3
(B) The sulphides of other metals are soluble (D) AgCN is soluble in HNO3
in NH4OH
(C) The concentration of S2- ions is increased
(D) The sulphides of second group are soluble Q.11 In the brown ring test for the nitrate ion,
in NH4OH [Fe(H2O)5NO]+2 imparts the colour due to -
(A)   * Transition
Q. 4 An aq. solution containing Hg 2 ; Hg2+, Pb2+
2+
2 (B) Charge transfer transition
and Cd ions is mixed with dil. HCl. Which
will be precipitated - (C) d-d transition
(A) Hg2Cl2 (B) PbCl2 (D) *  * transition
(C) Both (A) and (B) (D) None of these

Q. 5 Disodium hydrogen phoshate is used to test- Q.12 Na 2 CO 3 cannot be used in place of

(NH4)2 CO3 for the precipitation of V group,
(A) Mg2+ (B) Na+
2+ because -
(C) Ca (D) All
(A) Na+ interferes in the detection of V group
Q. 6 In inorganic salt solution on treatment with (B) [Link] CO32– is very low
HCl gives a white precipitate of which metal (C) Na will react with acid radicals
ions -
(D) Mg will be precipitated
(A) Hg 2
2 (B) Hg2+
(C) Zn2+ (D) Cd2+ Q.13 Which gives blood red colour with ammonium
thiocyanate -
Q. 7 An inorganic salt solution gives a yellow (A) Fe3+ (B) Fe2+
preceipte with silver nitrate. The precipitate (C) Cu2+ (D) Cd2+
dissolves in dilute nitric acid as well as
in ammonium hydroxide. The solution
Q.14 Which combines with Fe2+ to form brown
contains -
complex -
(A) Bromide (B) Iodide
(A) N2O (B) NO
(C) Phosphate (D) Chromate
(C) N2O3 (D) N2O5

Q. 8 Which of the following salts will turn water Q.15 In III group precipitation NH4Cl is added before
coloured when fumes evolved on treatment adding NH4OH due to -
with conc. H2SO4 are passed in water - (A) decreasing conc. of OH–
(A) Nitrate (B) Bromide (B) prevent interference of PO43–
(C) Both (D) None (C) increase in conc. of Cl–
(D) increase in conc. of OH– ions
Q.16 Few drops of HNO3 are added to II group Q.21 The heat of neutralization of one mole of a
filtrate before proceeding to III group in order strong acid (in dilute solution) with one mole
to - of a strong base is -
(A) convert Fe2+ to Fe3+ (A) 24.6 k cal
(B) convert Fe3+ to Fe2+
(B) 13.7 k cal
(C) ppt III group
(D) none (C) dependent on the acid
(D) dependent on both the acid and the base
Q.17 A graph plotted between log t 50 %vs. Q.22 The sulphides of which one of the following
concentration is a straight line.W hat groups of elements are soluble in yellow
conclusion can you draw from the given ammonium sulphide -
graph -
(A) As, Sb and Sn (B) As, Cd and Sn
(C) Cd, Cu and Bi (D) Hg, Cu and Cd

Q.23 How do we differentiate between Fe3+ and

log t50 %
Cr3+ in group III -
log a (A) By adding excess of NH4OH solution
(B) By increasing NH4+ ion concentration
1
(A) n =1, t1/2 = (C) By decreasing OH– ion concentration
K.a
(D) Both (B) and (C)
1
(B) n=2, t1/2 = NaOH
a Q.24 salt X  
 Y (gas)
Heat
0.693
(C) n = 1, t1/2 =
K
(D) none 

Q.18 Which curve represents a zero order reaction- Gives brown (Mg3N2 + H2O)
ring test
log (a –X)

Salt X is -
X (A) NH4NO3 (B) NH4Cl
(A) (B) (C) KNO3 (D) Ba(NO3)2
t t Q.25
(KCl + K2Cr2O7 + H2SO4) Heat
2

Red Gas
1/ (a –X)
1/ (a –X)

dil NaOH
(C) (D) Pb(Ac)2
X Yellow
t t Solution
Q.19 From different sets of data of t1/2 at different The formula and colour of X are respectively-
initial concentration say ‘a’ for a given (A) CrO2Cl2, red colour
reaction, the product [t1/2 × a] is found to be (B) PbCrO4, yellow colour
constant. The order of the reaction is - (C) BaCrO4, Green Colour
(A) 0 (B) 1 (D) Cr2(SO4)3, Green Colour
(C) 2 (D) 3
Q.26 A substance on treatment with dil H2SO4
Q.20 The heats of neutralisation of four acids A, liberates a colourless gas which produces
B,C,D are – 13.7, – 9.4, – 11.2 and – 12.4 (i) Turbidity with baryta water and
kcal respectively when they are neutralised (ii) Turns acidified dichromate solution green
by a common base. The acidic character The reaction indicates the presence of -
obeys the order - (A) CO3–2 (B) S–2
(A) A > B > C > D (B) A > D > C > B (C) SO3–2 (D) NO2–
(C) D > C > B > A (D) D > B > C > A
Q.27 Match the following : Q.33 Statement - I : Aniline yellow is also called
(a) White crystalline ppt (i) Sb2S3 p-aminoazobenzene (yellow).
(b) Reddish brown ppt (ii) Cr (OH)3 Statement - II : Formula is
(c) orange ppt (iii) PbCl2
(d) yellow ppt. (iv) Fe (OH)3
(e) Green ppt. (v) K3 [Co(NO2)6]
(A) (a – i), (b – Iii), (c – ii), (d – v), (e – iv)
(B) (a – iii), (b – iv), (c – i), (d – v), (e – ii) Q.34 Statement - I : Order of reaction for the
decomposition of H2O2 is one.
(C) (a – iii), (b – iv) , (c – v), (d – i), (e – ii)
Statement - II : This reaction is catalysed
(D) (a – ii), (b – iv), (c – iii), (d – v), (e – i)
by nitrate ion.
Assertion & Reason Type Question
Q.35 Statement - I : Colour of chromyl chloride
Each of the questions given below consist vapour is deep red.
of Statement – I and Statement – II. Use the Statement - II : these vapours are formed in
following Key to choose the appropriate the chromyl chloride test which is used for
answer. the detection of chloride.
(A) If both Statement- I and Statement- II are
true, and Statement - II is the correct Q.36 Statement - I : In the titration of strong acid
explanation of Statement– I. and weak base suitable indicator is methyl
orange.
(B) If both Statement - I and Statement - II
are true but Statement - II is not the Statement - II : pH range of methyl oragne
indicator is 5.6 – 7.4.
correct explanation of Statement – I.
(C) If Statement - I is true but Statement - II Q.37 Statement - I : When methyl ketones are
is false. treated with hypohalides, they produce
(D) If Statement - I is false but Statement - II trihalogen methane.
is true. Statement - II : This reaction is called
haloform reaction.
Q.28 Statement - I : A mixture on heating with dil
H2SO4 gives a gas with burning smell which
turns lime water milky. Passage # 1
A metal sulphide (A) gives (B) gas with rotten
Statement - II : The lime water react with
egg smell and (C) a colourless sulphates,
gas to give insoluble substance and the
when treated with dil. H2SO4.(B) reacts with
mixture may contain CO3–2 or SO3–2. K2Cr2O7/H+ to form (D) a white grey element.
(D) burns in oxygen to yield (E) a colourless
Q.29 Statement - I : Addition of KCNS to Fe+3
gas. If (B) is added in (E), it gives (D) and
ions in solution gives blood red colour. colourless liquid, which turns anhydrous
Statement - II : A complex Fe(CNS)Cl2 or CuSO 4 blue. (C) gives a precipitate with
Fe(CNS)3 is formed. NH3(aq.) or NaOH which dissolves in excess
of NaOH.
Q.30 Statement - I : In IVth group Mn+2, Ni+2
Q.38 A is :
basic radicals are present.
(A) CuS (B) ZnS
Statement - II : For first group basic radical
(C) Cu2S (D) None of these
suitable group reagent is dil HCl.

Q.31 Statement - I : Colour of MnS precipitate is Q.39 B is :

pink or Buff. (A) SO2 (B) SO3
Statement - II : Colour of CaCO3 precipitate (C) H2S (D) CS2
is yellow.

Q.32 Statement - I : Victor meyer’s test is used Q.40 C is :

for the distinction between 1º, 2º and 3º
(A) CuSO4 (B) BaSO4
Alcohols.
(C) ZnSO4 (D) Na2ZnO2
Statement - II : 2º Alcohol give blue colour.
Q.41 D is : Q.43 Bottle (1) contains :
(A) Zn (B) Cu (A) Pb(NO3)2 (B) HCl
(C) S (D) B (C) Na2CO3 (D) CuSO4

Q.42 E is : Q.44 Bottle (2) contains :

(A) H2S (B) SO3 (A) Pb(NO3)2 (B) HCl
(C) SO2 (D) None of these (C) Na2CO3 (D) CuSO4

Passage # 2 Q.45 Bottle (3) contains :

There are four bottles which contains : (A) Pb(NO3)2 (B) HCl
Copper (II) sulphate Lead nitrate (C) Na2CO3 (D) CuSO4
Hydrochloric acid Sodium carbonate
By mixing samples of the contents of the Q.46 Bottle (4) contains :
bottles in pairs, a chemist made the (A) Pb(NO3)2 (B) HCl
following observations :
(C) Na2CO3 (D) CuSO4
Bottle (1) + Bottle (2) white precipitate
Bottle (1) + Bottle (4) white precipitate
Q.47 Colourless gas evolved when contents of
Bottle (2) + Bottle (4) no visible reaction Bottle (2) and Bottle (3) are mixed is :
Bottle (1) + Bottle (3) white precipitate (A) O2 (B) CO2
Bottle (2) + Bottle (3) colourles gas evolved (C) N2 (D) N2O
Bottle (3) + Bottle (4) green blue precipitate
 (Question asked in previous AIEEE & IIT-JEE)
Section : A Q.5 Which of the Following statement is incorrect with
reference to the ferrous and ferric ions- [IIT-1998]
Q.1 HgCl2 on passing H2S gives - [AIEEE-2002]
(A) HgS (B) Hg2S (A) Fe3+ gives brown colour with potassium
(C) Hg + HgS (D) HgS + H2S ferricyanide.
(B) Fe3+ gives blue precipitate with potassium
Q.2 How do we differentiate between Fe3+ and Cr3+
in qualitative analysis gp. III : [AIEEE-2002] ferrocyanide.
(A) By taking excess of NH4OH (C) Fe3+ gives red colour with potassium
(B) By increasing NH 4 ion concentration thiocyanate.
(D) Fe3+ gives brown colour with ammonium
(C) By decreasing OH– ion concentration
(D) Both (B) and (C) thiocyanate.
Q.3 Which statement is correct : [AIEEE-2003] Q.6 Identify the correct order of solubility of Na2S,
(A) Fe3+ ions give deep green precipitate with CuS and ZnS in aqueous medium - [IIT-2002]
K4[Fe(CN)6] solution (A) CuS > ZnS > Na2S
(B) On heating K+, Ca2+ and HCO3– ions, we (B) ZnS > Na2S > CuS
get a precipitate of K2[Ca(CO3)2] (C) Na2S > CuS > ZnS
(C) Manganess salts give a violet borax bead (D) Na2S > ZnS > CuS
test in the reducing flame
(D) From a mixed precipitate of AgCl and AgI Q.7 An aqueous solution of a substance gives white
ammonia solution dissolves only AgCl precipitate on treatment with dilute hydrochloric
Section : B acid, which dissolves on heating . When
hydrogen sulfide is passed through the hot acidic
Q.1 Which compound does not dissolve in hot, dilute solution, a black precipitate is obtained. The
HNO3 - [IIT-1996]
(A) HgS (B) PbS substance is – [IIT-2002]
(C) CuS (D) CdS (A) Hg22+ salt (B) Cu2+ salt
(C) Ag+ salt (D) Pb2+ salt
Q.2 An aqueous solution contains Hg2+, Hg22+ , Q.8 A gas 'x' is passed through water to form a
Pb2+ and Cd2+. The addition of HCl will precipi- saturated solution . The aqueous solution on
tate : [IIT-1997] treatment with silve rnitrate gives a white
(A) Hg2Cl2 only (B) PbCl2 only
(C) PbCl2 and Hg2Cl2 (D) PbCl2 and HgCl2 precipitate. The saturated aqueous solution also
dissolves magnesium ribbon with evolution
Q.3 Read the following statement and explanation of colourless gas 'y'. Identify 'x' and 'y'
and answer as per the option given below : [IIT-2002]
[IIT-1998] (A) x=CO2 , y = Cl2 (B) x= Cl2 , y = CO2
Assertion : Sulphate is estimated as BaSO4 (C) x= Cl2, y=H2 (D) x = H2, y = Cl2
and not as MgSO4
Reason : Ionic radius of Mg2+ is smaller than
that of Ba2+ Q.9 [X] + H2SO4  [Y] a colourless gas with irri-
(A) If both assertion and reason are correct, and tating smell, [IIT-2003]
reason is the correct explanation of the [Y] + K2Cr2O7 + H2SO4  green solution.
assertion [X] and [Y] is
(B) If both assertion and reason are correct, but (A) SO32–, SO2 (B) Cl– , HCl
reason is not correct explanation of the as 2–
sertion (C) S , H2S (D) CO32–, CO2
(C) If assertion is correct but reason is incorrect
(D) If assertion is incorrect but reason is correct Q. 10 A solution which is 10–3 M each in Mn2+, Fe2+,
Zn2+ and Hg2+ is treated with 10–16 M sulphide
Q.4 Which of the following statement is incorrect when ion, If KSP of MnS, FeS, ZnS and HgS are
a mixture of NaCl and K2Cr2O7 is gently warmed 10–13, 10–18 , 10–24 and 10 –53 respectively,
with conc. H2SO4 . [IIT-1998] which one will precipitate first : [IIT-2003]
(A) A deep red vapour is evolved. (A) FeS (B) MgS
(B) The vapour when passed into NaOH solution (C) HgS (D) ZnS
gives a yellow solution of Na2CrO4.
(C) Chlorine gas is evolved .
(D) Chromyl chloride is formed.
Q u e s. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20
A n s. B D A A B C C B A A A A A A D A D D B B
Q u e s. 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40
A n s. A D A A A A B C C A B A C B C B A A C D
Q u e s. 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
A n s. B B D C B D C B B A C B A C B C C C A B
Q u e s. 61 62 63 64 65 66 67 68 69 70 71 72 73
A n s. A C A B A A C B D B B B C

Que s. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20
Ans. A B D A B C D B A A D C A D B A B D A C
Que s. 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35
Ans. B A B A A B A B A B C C D C A

Que s. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20
Ans. D B C C A A A B C B B D A B A A C A C B
Que s. 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40
Ans. D A D A B C B A A B C A A C A C A B C C
Que s. 41 42 43 44 45 46 47
Ans. C C A B C D B
Passage - 2 Solution :
Passage - 1 Solution :
The reaction can be explained as :
ZnS + H2SO4  ZnSO4 + H2S Pb(NO3)2 + 2HCl  PbCl2 + 2HNO3
(A) (C) (B)
(1) (2) White ppt.
3H2S + K2Cr2O7 + 4H2SO4
K2SO4 + Cr2(SO4)3 + 3S + 7H2O Pb(NO3)2 + Na2CO3 PbCO3 + 2NaNO3
S + O2  SO2 (D) (1) (3) White ppt.
(D) (E) Pb(NO3)2 + CuSO4 PbSO4 + Cu(NO3)2
2H2S + SO2  2H2O + 3S (1) (3) White ppt.
2HCl + Na2CO3  2NaCl + H2O + CO2
ZnSO4 + 2OH– Zn(OH)2 + SO 24 – (2) (3) Colourless gas
HCl + CuSO4  No reaction
(2) (4)
CuSO4 + Na2CO3  CuCO3 + Na2SO4
(4) (3) (Green-blue ppt.)

SECTION - A
Q .N o . 1 2 3
Ans. A D D

SECTION - B
Ques. 1 2 3 4 5 6 7 8 9 10
Ans. A C B C C D D C A C