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Indirapuram, Ghaziabad
The systematic procedure of a mixture of inorganic salts involves the following steps.
(a)
Preliminary tests
(i)
(iii)
(v)
(vii)
(b)
(c)
Physical examina+tion
Flame test
Charcoal cavity test
Concentrated sulphuric acid test
(ii)
(iv)
(vi)
(viii)
Dry heating
Borax bead test
Dilute acid test
Individual ions test
(b) Smell
Take a pinch of the
mixture between your
fingers and rub with a
drop of water.
Observations
Blue or Bluish green
Greenish
Light green
Dark green
Dark brown
Pink violet
Light pink, flesh colour or dull
earthy colour
White
Inference
Cu2+ or Ni2+
Ni2+
Fe2+
Cr3+
Fe3+
CO2+
Mn2+
Ammoniacal smell
Vinegar like smell
Smell like that of rotton eggs
NH4+
CH3COOS2-
(c) Density
(i) Heavy
(ii) Light fluffy powder
(d) Deliquescence
Note : (i)
(ii)
This test is performed by heating a small amount of the mixture in a dry test tube.
Observations
Inference
1. Gas evolved
(a)
(b)
(i)
CO32 Or C2O42
Hydrated S2
SO32
Cl
CH3COO
NH4+
White sublimate
Black sublimate accompanied by
violet vapours
Decrepitation
Br
I
NH4+
I
Cl
Sublimate formed
(a)
(b)
3.
NO2 or NO3
Fusion
Zn2+
Pb2+
Cd2+
CH3COO indicated
Ba2+, Sr2+, Ca2+, Mg2+, Al3+, etc.
Hydrated CuSO4 indicated
Co2+, Fe2+, Fe3+, Cr3+, Cu2+, Ni2+,
Mn2+ indicated.
Flame Test
Colour of flame
With naked eye
1. Brick-red (not persistent)
2. Crimson-red (persistent)
3. Persistent grasy-green
(Appears after prolonged heating)
4. Golden yellow
5. Pink-violet
6. Bright-bluish green
7. Green flashed
8. Dull bluish-white
Inference
Through blue glass
Light yellowish green
Crimson
Green
Invisible
Pink
Visible
White
Calcium (Ca)
Strontium (Sr)
Barium (Ba)
Sodium (Na)
Potassium (K)
Copper (Cu)
Zn slats, Mn salts
Lead (Pb)
ANION ANALYSIS
Preliminary Test:
(a)
(b)
Treatment with sulphuric acid gives an acid of the anion. The acid may decompose or get
oxidized evolving a gas which can be identified by any of its characteristic property or
reaction.
Group based on their reaction with
(i)
(ii)
(iii)
Ion
CO32
NO2
S2
SO32
Experiment
(a) Salt +dil.
Observation
Colourless, Odourless gas
with brisk effervescence
Reactions
CaCO3 + H2SO4 CaSO4+H2O +CO2
(a) Salt + 2
ml. Dil H2SO4
(a) Salt + 2
ml. Dil H2SO4
H2S+(CH3COO)2 PbPbS+2CH3COOH
It turns green
{Cr2 (SO4)3}
Br
(c) Addition of
pinch of MnO2
HCl + NH4OHNH4Cl+H2O
MnO2+4HClMnCl2+2H2O+3Cl2
NaBr+H2SO4NaHSO4+HBr
Turns yellow
(b) Pass above
gas through starch
solution
H2SO4(conc)+2HBrSO2+Br2
+2H2O
Fumes increase
MnO2+2HBr+H2SO4 MnSO4
+2H2O+Br2
KI+ H2SO4(conc)KHSO4 + HI
2HI+H2SO4 2H2O+I2 + SO2
Turns blue
(b) Pass above
gas through starch
solution.
Fumes increase
(c) Add MnO2
NO3
4HNO3(conc)+Cu2NO2+2H2O
+Cu(NO3)2
CH3COO
C2O42
CH3COONa+H2SO4NaHSO4
+CH3COOH
COONa
|
+H2SO4 Na2SO4+CO2
COONa
+ CO + H2O
Ca(OH)2 + CO2 CaCO3 + H2O
Water Extract (W.E.): Salt +H2O + Heat (if required ) to get a clear solution.
If Insoluble in water prepare S.C.E.
Sodium carbonate extract (S.C.E.): One part salt + three parts Sodium carbonate
(Na2CO3 + 20 ml. H2O + Boil (Reflux) for 10-15 minutes in a conical flask and
filter.)
Note:
(a)
(b)
(c)
(d)
An insoluble salt when treated with sodium carbonate undergoes double decomposition.
Sodium Salts of the anion are water soluble and can be analysed while the interfering
cations are rejected as insoluble carbonates.
This extract can not be prepared for carbonates.
Excess sodium carbonate can be destroyed by acidifying the extract before the test
Observation
Reaction
White ppt.
(MgCO3)
Na2CO3+MgSO4MgCO3+Na2SO4
NO
effervescence
Residue+Dil H2SO4
Brisk
effervescence
(CO2)
Blue solution.
NaNO2+H2SO4 HNO2+NaHSO4
A dark blue
colouration.
2KI+2H2SO4+2HNO22KHSO4+ I2+2NO+2H2O
Purple or violet
colouration
Na2S+Na2[Fe(CN)5NO]Na4[Fe(CN)5NOS]
(Violet)
Black ppt.
(PbS)
Na2S+(CH3COO)2PbPbS+2CH3COONa
(Black)
(c) Cadmium
carbonate test:
W.E. / S.C.E. + (1ml.)
suspension of cadmium
carbonate
SO32
Barium chloride
test:
W.E. / S.C.E. + (1ml.)
+ dil acetic acid +
BaCl2
Add dil. HCl to above
ppt.
(i) To 1st part of ppt. +
acidified KMnO4
(ii) K2Cr2O7 test:
To 2nd part of ppt. +
dil. H2SO4 (few drops)
+ K2Cr2O7
Yellow ppt.
Na2S + CdCO3 CdS + Na2CO3
White ppt.
(BaSO3)
ppt. Dissolves.
Pink colour of
KMnO4 is
discharged
Green
colouration
Cr2(SO4)3
K2Cr2O7+3Na2SO3+4H2SO4Cr2(SO4)3+2Na2SO4
+K2SO4+4H2O.
White ppt.
(AgCl),
dissolves in
NH4OH
4NaCl+K2Cr2O7+3H2SO42Na2SO4+K2SO4
+3H2O+2CrO2Cl2
CrO2Cl2 +4NaOHNa2CrO4+2H2O+2NaCl
Yellow ppt.
(PbCrO4)
Soluble in
NaOH.
Na2CrO4+(CH3COO)2PbPbCrO4+2CH3COONa
Br (Bromide Ion)
(a) Silver nitrate test:
W.E. (1ml.) + dil. HNO3
(few drops) + AgNO3
A light yellow
KBr + AgNO3KNO3 + AgBr
ppt.
AgBr + 2NH4OH [Ag(NH3)2]Br + 2H2O
Partially
soluble in
(b)Chlorine water test: NH4OH
W.E. + dil HCl + 1-2 ml
of CS2 + Chlorine Water
(excess) + shake and
Organic layer
2NaBr + Cl2 2NaCl + Br2
allow to stand
gets yellow/red/
orange/
brown colour
depending on
concentration
of bromine and
the solvent
used.
I
(a) Silver nitrate test:
Organic layer
gets violet
colour
Brown ring at
the junction of
the two layers.
6FeSO4+3H2SO4+2HNO33Fe(SO4)3
+4H2O + 2NO
FeSO4 + NO + 5H2O [Fe(NO)(H2O)5]SO4
(Brown ring)
Blue
colouration.
Blood red
coloration.
Paste has
vinegar smell
Pleasant fruity
smell.
3CH3COONa+FeCl3(CH3COO)3Fe + NaCl
Fe(CH3COO)2+H2OCH3COO(OH)2Fe
+2CH3COOH.(redppt)
(Basic Ferric aceltate)
COOH
COONa
+ 2CH3COONa
+ 2CH3COOH
COOH
COONa
2CH3COONa+H2SO4Na2SO4 +2CH3COOH
CH3COOH+C2H5OHCH3COOC2H5 + H2O
White ppt.
Pink colour of
KMnO4
discharged.
10
INDIVIDUAL IONS
SO42
(a) Barium chloride test:
W.E./S.C.E.(1ml.) + (dil.)
H2SO4 + BaCl2
White ppt.
Insoluble
in HCl(conc)
(BaSO4)
Na2SO4+BaCl22NaCl+BaSO4
White ppt.
Soluble in
ammonium
acetate
solution (PbSO4)
Na2SO4+(CH3COO)2PbPbSO4
+2CH3COONa
PbSO4+2CH3COONH4(CH3COO)2Pb
+(NH4)2SO4
A deep yellow
ppt.
Na3PO4+HNO3+(NH4)2MoO4(NH4)3PO4.
12MoO3+NH4NO3 +H2O
White ppt.
Na2HPO4+MgCl2+NH4OHMg(NH4)PO4
+2NaCl + H2O
PO43
(a) Amm. Molybdate test:
W.E./S.C.E. (1ml.) + 2ml.
Con. HNO3 + boil +
Ammonium molybdate excess
+ boil
(b) Magnesia mixture test:
W.E. NH4Cl(S) + MgCl2+ Boil
and Cool + NH4OH
11
CATION ANALYSIS
Confirmatory / Wet Tests:
Classification of Cations :
For the sake of qualitative analysis the cations are classified into six groups on the basis of
the difference in solubility product values of their chlorides, sulphides, hydroxides and
carbonates under different conditions of acidity and alkalinity.
Group
Group Reagent
Zero
I
II
No
Dilute HCl
H2S in the presence of
dil. HCl
III
IV
VI
Cations
NH4+
Pb2+ (white)
Pb2+ (black),
Hg2+ (black),
Cd2+ (yellow),
Cu2+ (black),
As3+ (Yellow)
NH4OH in the
Fe3+ (brown), Al3+
presence of NH4Cl
(white)
H2S in the presence of NI2+ (black), Co2+
NH4OH
(Black), Mn2+ (light
brown), Zn2+ (white).
(NH4)2CO3 in the
Ca2+ (white),
presence of NH4OH
Sr2+(white), Ba2+
(white).
No
Mg2+
Form in which
cations are
precipitated
Chlorides
Sulphides
Hydroxides
Sulphides
Carbonates
Preparation of Original Solution (O.S.) for wet Tests of Basic Radicals : A clear
transparent solution.
Original Solution (O.S.) (Salt + Solvent)
Solvents:
(i)
(iii)
Note: (i)
(iii)
(iv)
(v)
(ii)
Proceed in water.
(ii)
12
Hot water
Dil. HCl
Note:
(i)
(ii)
(iii)
Filter
Filtrate
ppt. Group IV (Zn2+, Ni2+, Mn2+&Ca2+)
+ Boil off
(as sulphides)
H2S + NH4Cl + NH4OH + (NH4)2 CO3 + warm
Filtrate Group VI
(Mg2+and K+)
Observation
Reactions
NH4Cl+NaOHNH3+H2O+NaCl
Brown ppt.
(NH2.HgO.HgI)
K2HgI4+2NH3NH2HgI+NH4I
+2KI
2NH2HgI+H2ONH2.HgO.HgI+NH4I
(Brown)
Group: I (Pb2+)
Experiment
O.S. + dil. HCl
Boil the white ppt. With 5 to 10
ml. Of water and divide the
solution into two parts.
Potassium iodide test:
First part + KI
Potassium chromate test:
Second part + K2CrO4
Note:
(i)
(ii)
Observation
White ppt. (PbCl2)
White ppt. In soluble
in hot water.
Reactions
Pb2+ + 2Cl PbCl2
If O.S. is prepared dil. HCl the first group is absent. That means no ppt formation.
Pb does not precipitate completely in group I . A part of it gets precipitated in group
II as PbS
Group : II
Group: A- Pb2+ , Cu2+
Group: B As3+
Black (Pb2+ , Cu2+)
O.S. / G-I Filtrate + (acidify with dil HCl + warm) + H2S ppt
Yellow (As3+)
Chemical Reactions involved in case of passing H2S through O.S.
PbCl2 + H2S 2HCl + PbS (Black)
CuCl2 + H2S 2HCl + CuS (Black)
2AsCl3 + H2S 2HCl + As2S3 (Yellow)
14
Group: IIA
(a)
(b)
In case of Yellow ppt. + Yellow ammonium sulphide and warm Soluble (As3+)
Experiment
Pb2+
Dissolve the white
ppt. In hot
ammonium acetate
solution Divide it
into two parts.
Observation
Reaction
ppt. Dissolves
(CH3COO)2 Pb
PbSO4+2CH3OONH4(CH3COO)2Pb+(NH4)2SO4
(a) Potassium
iodide test:
First part + KI
(b) Potassium
chromate test:
Second Part +
K2CrO4
Yellow ppt.
(PbCrO4)
Pb(NO3)2 + K2 Cr.O4 2KNO3 + PbCrO4
(Yellow)
Cu2+
Potassium
ferrocynide test:
Blue solution +
acetic acid +
Potassium
ferrocyanide
Chocolate brown
ppt.
Group: II B (As3+)
Experiment
As3+
Yellow ppt. + conc.
HNO3.
Divide the solution
into two parts
Observation
Reactions
ppt. Dissolves
As2S3+10HNO3 2H3AsSO4+10NO+3S+2H2O
15
First part +
ammonium
molybdate + Heat
(b) Magnesia
mixture test:
Second part +
NH4OH + Magnesia
mixture
(MgSO4+ NH4OH
+NH4Cl)
Yellow ppt.
H3AsO4+12(NH4)MoO4+21HNO3 (NH4)3AsO4
12 MoSO3+21NH4NO3+12 H2O
White ppt.
H3AsO4+MgSO4+3NH4OHMg(NH4)AsO4
+(NH4)2SO4+3H2O
H2S should be completely boiled off before adding NH4OH otherwise G IV cations
will also precipitate
Ferrous ions are oxidized to ferric by addition of conc. HNO3 because ferrous ion are
not completely precipitated as hydroxides.
Experiment
Fe3+
Dissolve ppt. In dil.
HCl.
Divide into it into
two parts.
(a) Potassium
ferrocynide test:
First part +
potassium
ferrocyanide.
Observation
Reactions
ppt. Dissolves
Prussian blue
colouration
4FeCl3+3K4[Fe(CN)6]Fe4[Fe(CN)6]3+12KCl(aq)
(Prussian Blue)
16
(b) Potassium
sulphocynide
test:
Second part +
potassium
sulphocynide
Al3+
Lake Test:
White ppt. + dil.
HCl (few drops to
acdifiy) + blue
litmus (few drops)
+ NH4OH dropwise
till solution becomes
ammonical
Blood red
colouration
Blue floating
ppt. In a
colourless
solution.
Observation
Reaction
Blue residue
(Anhydrous
Chloride of Cobalt)
3CoS+2HNO3+6HCl3CoCl22NO+3S+4H2O
Yellow ppt.
CoCl2+2KNO22KCl+Co(NO2)2
KNO2+CH3COOH CH3COOK+HNO2
Co(NO2)2+2HNO2Co(NO2)3+H2O+NO
Yellow residue.
Green coloured
solution.
18
Mn2+
Dissolve some buff
coloured ppt. in dil.
HCl and boil in H2S
(a) Sodium
hydroxide Br2 test:
Add NaOH Solution
and warm.
Add Br2 in White ppt
(b) Lead peroxide
test:
Buff ppt. + Conc.
HNO3 + PbO2 (Boil
and Cool)
Zn2+
Dissolve dirlty white
ppt. in dilute HCl and
boil of H2S. Cool and
divide the solution into
two parts.
(a) Sodium
hydroxide test:
First part + NaOH
solution.
(b) Potassium
ferocynide test:
Second part +
Potassium ferrocyanide
solution.
ppt. dissolves.
White ppt.
turning brown
/black
Pink coloured
solution (HMnO4)
ppt. dissolves,
19
Experiment
Ba2+
Observation Reactions
Potassium
chromate
test:
First part + Pot. Yellow ppt.
Chromate
solution.
Sr2+
Amm.
Sulphate test:
Second part +
White ppt.
1 ml. Of
ammonium
sulphate
solution and
warm.
Ca2+
Amm. Oxalate
test:
Third part + 1- White ppt.
2 ml. Of
ammonium
Oxalate
solution.
NH4OH (few
drops) and
scratch the
sides.
20
Group VI (Mg2+)
O.S./G.V filtrate (concentrate ) and divide the solution
Experiment
Mg2+
Amm.
Phosphate test:
To a part of the
solution + solid
NH4Cl and
NH4OH in slight
excess. +
Ammonium
Hydrogen
phosphate
solution and rub
the sides of the
test tube with a
glass rod.
Observation Reaction
White ppt.
MgCl2+NH4OH+(NH4)2HPO4Mg(NH4)PO4 +2NaCl
(white) +H2O
Note: The precipitation of Mg2+ as Mg (NH4) PO4 is rather slow. Scratching(rubbing) is done and the
time is allowed before filtration.
21
VIVA - VOCE
QUALITATIVE ANALYSIS (XI & XII)
Q.1. What do you mean by qualitative and quantitative analysis?
Ans. Qualitative analysis deals with the identification of mere presence of acidic or basic radicals
in inorganic salts or presence of extra elements such as N, O, P, S or halogens in an organic
compound or testing the presence of functional group in an organic compound.
Quantitative
analysis
on
the
other
hand
helps
to
estimate
the
amount/concentration/percentage of these elements present.
Q.2. Give an example to differentiate between qualitative and quantitative a
analysis.
Ans. When a given salt eg. Lead salt is analysed say with KI; appearance of yellow ppt. will
indicate the qualitative presence of lead ions but in case if an alloy containing lead is
dissolved in nitric acid and the amount of lead present is estimated by weighing the exact
amount of lead iodide precipitated to calculate the percentage of lead in the alloy; it will be
called as quantitative analysis.
Q.3. What is a radical?
Ans. An atom or group of atoms having a distinct positive or negative charge on it is called a
radical; for example NH+4, Cu+2, Br, SO2-4 etc.
Q.4. What is an acid radical?
Ans. Radicals carrying negative charge on them are called acid radicals eg. Cl-, NO3etc. They are
also called anions.
Q.5. What is a basic radical?
Ans. Radicals carrying positive charge on them are called basic radicals eg. Fe+2, NH4+. They are
also called cations.
Q.6. What type of bond is present in an inorganic salt?
Ans. Electrovalent or ionic bond is present in an inorganic salt.
Q.7. Why do inorganic compounds ionize when dissolved in water?
Ans. Due to the presence of ionic species in inorganic salts; each ion is solvated by water in
aqueous solution and hence dissolve.
Q.8. Name some basic radicals that impart colour to the salt.
Ans. Mainly the basic radicals of transition metals import colour to the salt. For example salts of
Ni+2, Cu+2, Fe+2 etc. are coloured.
Q.9. What can you conclude if the given salt is white?
22
Ans. We can infer that the salt does not contain transition metal ions i.e. Cu+2, Ni+2, Co+2, Mn+2,
Fe+3 and Fe2+ are absent. Not only the salt but salt solution also should be colourless as
anhydrous CuSO4 is white but its solution is blue.
Q.10. What is the colour of iron salts?
Ans. Ferrous salts are generally green and ferric salts are brown.
Q.11. What is the colour of nickel salts?
Ans. Bluish green or green.
Q.12. Give one example of red salt.
Ans. Cobalt nitrate is red in colour.
Q.13. Generally what is the colour of manganese salts?
Ans. Light pink or flesh coloured.
Q.14. What are deliquescent salts?
Ans. Salts which absorb moisture from the atmosphere and dissolve in it are called deliquescent
salts e.g. MgCl2, FeCl3, ZnCl2.
Q.15. What are efforescent salts?
Ans. Salts which give out water of crystallization are termed as efflorescent salts eg. FeSO4.7H2O
or Na2CO3.10H2O loses water of crystallization to become FeSO4xH2O(3<x<7) and
Na2CO3.H2O (on losing 9 molecules of water of crystallization).
Q.16. Why a salt or mixture containing lead turns black in colour, when placed for a long time in
open?
Ans. This is due to the formation of black lead sulphide which is formed by the reaction of lead
with H2S present in the atmosphere.
Q.17. Why does ferrous sulphate; green in colour turns yellowish brown after some time?
Ans. Due to aerial oxidation ferrous ions get oxidized to ferric ions and hence the change in
colour occurs.
Q.18. Name a few salts which produce crackling sound when heated.
Ans. Lead nitrate, sodium chloride, barium nitrate.
Q.19. Why do ionic compounds generally dissolve in water?
Ans. Ionic compounds dissolve in water because water being a polar solvent, having high
dielectric constant, stabilize the ions of the ionic compound by hydrating them.
23
(Colourless)
anhydrous copper sulphate
Q.24. Name the type of salt which produced a pale brown gas on heating.
Ans. Nitrate or Nitrite salts of metals.
Q.25. Name the type of salt which on heating produces a colourless, odourless gas that turns lime
water milky.
Ans. Carbonate salts of alkaline earth metals.
Q.26. What is the colour of the residue when zinc salt is heated?
Ans. Yellow when hot, white when cold.
Q.27. Name the gases that turn lime water milky.
Ans. CO2 and SO2.
Q.28. How can you distinguish between CO2 and SO2 gas?
Ans. (a)
(b)
CO2 is colourless and odourless gas while SO2 has pungent smell.
SO2 turns acidified dichromate paper green while CO2 does not.
Q.29. What information you get when the dry salt on heating gives a violet sublimate?
Ans. It is an iodide salt.
Q.30. Explain what happens when CO2 passes through lime water. What change further occurs
when excess of CO2 is passed??
24
Ans. Initially when CO2 is passed through lime water, it turns milky due to the formation of
insoluble calcium carbonate. If excess of CO2 is passed soluble bicarbonate are formed and
hence milkiness disappears.
CO2+ Ca(OH)2 CaCO3+H2O
White ppt.
CaCO3+CO2+H2O Ca(HCO3)2
Soluble Calcium bicarbonate
Q.33. Is there any other wire that can be used for flame test?
Ans. Nichrome wire.
Q.34. In the flame test, sodium imparts yellow colour to the flame while magnesium does not
impart any colour. Why?
Ans. In the electronic configuration of magnesium; the outermost ns orbitals are fully filled
(atomic no. 12 = 1s2, 2s2, 2p6, 3s2) and so very high energy is required for the excitation of
electrons. Hence, when the excited electron falls back to the ground state, the frequency of
radiation emitted does not fall in the visible region.
Q.35. What is the chemistry behind the flame test?
Ans. The metal chlorides being volatile and thermally ionisable, when heated in the flame easily
get excited (electron of the metal ions) to high levels by absorbing energy. When they come
back to their original level, emit out the energy absorbed. If the energy falls in the visible
region, the colour would be shown.
Q.36. Why cant we use glass rod instead of platinum wire for performing flame test?
Ans. This is because glass contains sodium silicate and so glass itself imparts colour to the flame.
Q.37. Why do barium salts not impart colour to the flame immediately?
Ans. Because barium chloride is less volatile, hence it imparts colour after some time.
Q.38. Why do we use conc. HCl in preparing paste of the salt for flame test?
25
Ans. Conc. HCl converts metal salts to metal chlorides. Metal chlorides are more volatile than
any other salt of metal, hence readily imparts colour to the flame.
Q.39. Which colours are shown by Ba+2, Sr+2 and Ca+2 ions during flame test?
Ans. Ba+2 salts impart grassy green colour, Sr+2 salts impart crimson red colour and Ca+2 salt
impart brick red colour.
Q.40. Can conc. H2SO4 be employed for making the paste with the salt for the flame test?
Ans. No, conc. H2SO4 will produce sulphates shich are not volatile, so are not useful for
performing flame test.
Q.41. Name the acid radicals detected by dil H2SO4.
Ans. CO32, S2, SO32, NO2.
Q.42. Why is dil.H2SO4 used instead of dil. HCl to perform the tests for acid radicals?
Ans. H2SO4 has higher boiling point (3380C) while boiling point of HCl is 1100C. So if the test is
to be performed in cold any dilute acid would be suitable but if the contents are to be
heated; HCl gas may evolve along with other gases related to the acid radical to be tested.
The smell of HCl gas will make the recognition of the other gases evolved difficult, hence
dil. H2SO4 is preferred over HCl.
Q.43. What information do you get when addition of dil H2SO4 for testing acid radicals result in
the formation of white precipitate?
Ans. It indicates that the cation present in the salt may be Pb+2, Ba+2, Sr+2 or Ca+2; which form
insoluble sulphates.
Q.44. While performing H2SO4 tests, why should the reaction mixture not be heated to boiling?
Ans. On boiling, H2SO4 itself get decomposed to give SO2 which interferes with the identification
of other gases evolved during the test.
Q.45. In case dil H2SO4 interferes in test of acid radicals due to formation of precipitate of
sulphate, how will you perform preliminary test for acid radicals?
Ans. The test can be performed using HCl.
Q.46. Name the acid radicals that can be detected by cong. H2SO4 test.
Ans. Cl, Br, I, CH3COO, NO3.
Q.47. What is the function of copper piece or paper pallet when a nitrate is heated with conc.
H2SO4?
26
Ans. When a nitrate salt is heated with conc. H2SO4, colourless vapours of HNO3 are evolved.
But when a paper pallet or Cu chips are added, carbon present in the paper or copper from
copper chips reduce HNO3 to NO2 gas and brown fumes will be observes.
Q.48. How do you test for a sulphide ion?
Ans. H2S gas having rotten eggs smell is evolved when a sulphide salt is treated with dil. H2SO4.
Further, H2S gas evolved turns moist lead acetate paper black.
Q.49. Why does NO2 turn FeSO4 solution black?
Ans. FeSO4 first reduces NO2 to NO which then combines with FeSO4 to form black coloured
nitrosoferrous sulphate. 2FeSO4+H2SO4+NO2 Fe2(SO4)3+H2O+NO
FeSO4 + NO FeSO4.NO
Q.50. What is the need for preparing sodium carbonate extract?
Ans. Sodium carbonate extract is prepared to test the presence of anions when the salt is
insoluble in water. On reacting with sodium carbonate, anion forms sodium salt of itself,
thus, comes to solution, making its identification possible.
Q.51. Why is it necessary to neutralize sodium carbonate extract before testing for SO42?
Ans. Sodium carbonate extract contains CO32ions. If these are not decomposed with dil. HCl,
white ppt. of BaCO3 can be obtained on addition of BaCl2 (even in absence of SO42),
thereby interfering in the identification of SO42.
Q.52. What is the chemical equation involved in preparation of sodium carbonate extract?
Ans. Na2CO3 + 2 MA M2CO3 + 2NaA(MA = Metal salt).
Q.53. Why treatement of a chloride with conc. H2SO4 liberates HCl while a bromide or iodide ion
give bromine and iodine gas respectively?
Ans. Conc. H2SO4 acts as a weak oxidizing agent hence HI & HBr produced during reaction of
H2SO4 and I or Br get oxidized to I2 and Br2. However conc. H2SO4 cannot oxidize HCl to
Cl2.
Q.54. What is chromyl chloride test?
Ans. Chromyl chloride test is used to confirm the presence of chloride ion. During this test the salt
is heated with solid K2Cr2O7 and conc. H2SO4. The red vapours of chromyl chloride gas
(CrO2Cl2) are evolved. These are passed through NaOH solution and the solution aquires
yellow colour due to formation of Na2CrO4. When this yellow solution is acidified with acetic
acid and lead acetate is added; yellow ppt. of PbCrO4 (lead chromate) is formed, confirming
Cl
4NaCl+K2Cr2O7 + 3H2SO4 2CrO2Cl2 + K2SO4 + 2Na2SO4 + 3H2O
CrO2Cl2 + 4NaOH Na2CrO4 + 2NaCl + 2H2O
27
28
Ans. HNO2 or Cl2 water act as oxidizing agent during layer test. Old sample of Cl2 water is not
effective because of the following changes it undergoes due to which it loses its oxidizing
properties.
Cl2 + H2O HCl + HClO
2HClO
Decompose
2HCl + O2.
Q.62. Why should freshly prepared FeSO4 be used in the ring test for nitrate?
Ans. Since ferrous sulphate can easily get oxidized to ferric sulphate, hence is not stable. So,
freshly prepared solution of FeSO4 should be used as ferric sulphate will not form complex
with NO.
Q.63. What is the formula of sodium nitroprusside?
Ans. Na2[Fe(CN)5NO].
Q.64. How are SO32and SO42distinguished?
Ans. With BaCl2 both give white ppt. SO32forms ppt. due to formation of BaSO3 and SO42 forms
ppt. due to the formation of BaSO4. But out of the two only BaSO3 ppt. dissolves in conc.
HCl and BaSO4 does not.
Q.65. What is the formula of the compound formed in ammonium molybdate test of PO34?
Ans. Yellow ppt. formed is due to the formation of ammonium phosphomolybdate (NH4)3PO4.
12MoO3.6H2O (yellow ppt.)
Q.66. Why is original solution prepared in water or HCl; and solid salt is not directly used for
identification of basic radicals?
Ans. Since the identification is based on tests from solutions, the solid must be dissolved in either
water or HCl to form solution. Also most of the mental chlorides except first group are water
soluble, hence HCl can be used to make O.S.
Q.67. Why H2SO4 cannot be used for making original solution?
Ans. Sinch H2SO4 will result in formation of sulphates of cations and most of the sulphates are
insoluble in water, we cannot use H2SO4 for making original solution.
Q.68. Why is HNO3 not used for making original solution?
Ans. HNO3 is an oxidizing agent and when H2S is passed for gp II and IV radicals, it gets oxidized
to S and will interfere in analysis.
Q.69. Why is Pb+2 present in both group I and group II?
Ans. In gp I, Pb+2 is precipitated in the form of chloride as
Pb+2 + 2HCl PbCl2 + 2H+
29
White ppt.
Hence placed in gp I.
But also PbCl2 dissolves in excess of HCl
PbCl2 + 2HCl H2[PbCl4]
Soluble
and can be precipitated as PbS by passing H2S in gp II.
Q.70. The group reagent of group II is H2S, then why is HCl added during gp II precipitation?
Ans. The addition of HCl suppresses the ionization of H2S due to the presence of H+ (common
ion to H2S), hence less soluble sulphide ions are formed which are sufficient to precipitate
gp II cations but not gp IV cations.
HCl H+ + Cl
H2S 2H+ + S2
Q.71. Which group sulphides have more solubility and hence are difficult to precipitate group II or
IV?
Ans. Group IV sulphides have higher value of solubility product and hence have higher solubility
than gp II cation sulphides.
Q.72. Define common ion effect.
Ans. Common ion effect is the suppression of dissociation of weak electrolyte in presence of a
strong electrolyte having a common ion. Eg. In presence of NH4Cl a strong electrolyte,
NH4OH )a weak electrolyte is less dissociated due to the presence of NH+4 (a common ion
between them). The theory behind it can be understand in view of Le Chateliers principle.
NH4Cl NH4+ + Cl
(i)
NH4OH
NH4+ + OH
(ii)
+
More NH4 will shift the equilibrium of reaction (ii) backward, leading to less OH
concentration.
Q.73. What is the group reagent for group III?
Ans. NH4OH in presence of NH4Cl.
Q.74. Why is NH4Cl added before addition of NH4OH in precipitation of group III cations?
Ans. As explained under common ion effect above, addition of NH4Cl will allow only group III
cations to precipitate and prevent precipitation of group V and VI cations as hydroxides.
This is in view of less OH produced, which are sufficient to exceed solubility product of gp
III cations but not sufficient to bring about precipitation of gp V cations.
Q.75. Can NaCl and NaOH be used in place of NH4Cl and NH4OH, for gp III precipitation?
Ans. No, since both of them are strong electrolytes and there will not be common ion effect,
concentration of OH would be high enough to precipitate basic radicals of higher groups.
30
Q.76. Can NH4NO3 be used in place of NH4Cl for basic radical analysis?
Ans. Yes, even NH4NO3 can regulate the concentration of OH ion by common ion effect.
Q.77. Why is excess of NH4OH added in IV gp before passing H2S gas?
Ans. OH from NH4OH consumes H+ that have come from dissociation of H2S, thereby shifting
the equilibrium of reaction (ii) to R.H.S., resulting in more S2. (Required to precipitate IV gp
cations)
NH4OH
NH4+ + OH
(i)
H 2S
2H+ + S2
(ii)
Q.78. Only OH ions are required to increase conc. Of S2 as explained in the previous question.
Why is NH4Cl added?
Ans. NH4Cl keeps the OH low (by common ion effect with NH4OH). In absence of NH4Cl, OH
ion concentration will increase so much that higher groups will be precipitated as
hydroxides.
Q.79. How is a solution of NiS or CoS prepared after they are precipitated as black ppt. in group
IV?
Ans. NiS and CoS readily dissolve in aqua regia (conc. HNO3 and conc. HCl in ratio 1:3) to form
their respective soluble chlorides and hence can be tested from their solutions.
Q.80. Can Na2CO3 be used as gp V group reagent in place of (NH4)2CO3?
Ans. No; Na2CO3 is a strong electrolyte and hence will ionize completely.
Na2CO3 (aq)
2Na+(aq) + CO32 (aq)
2
The conc. Of CO3 will be high enough to precipitate gp VI (Mg+2 as MgCO3) along with
group V.
Q.81. Why is NH4OH also added in group V?
Ans. (NH4)2CO3 always contain some ammonium hydrogen carbonate NH4HCO3 in it. NH4OH is
added to convert NH4HCO3 to (NH4)2CO3, so that Ba+2, Sr+2 and Ca+2 are completely
precipitated.
Q.82. Give an example of a basic radical which is not a metal.
Ans. NH4+.
Q.83. What is Nesslers reagent?
Ans. Nesslers reagent is an alkaline solution of K2HgI4.
Q.84. What is the name of product obtained when NH4+ reacts with Nesslers reagent?
Ans. The product is called Iodide of Millons Base;-having structure.
31
NH2
Hg
O
Hg
I
Q.85. Why are sodium, potassium and ammonium ions not included in any of the groups?
Ans. Because their hydroxides, sulphides and carbonates are soluble. For this reason NH4+ is
separately tested in zero group.
CLASS - XII
TEST FOR THE FUNCTIONAL GROUPS
Q.1. Why does carbon form many compounds?
Ans. Because of
(a)
(b)
(c)
Catenation
Capability of forming single, double & triple bonds.
High C-C bond energy.
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Ans. Alcohol and the test tube in which the test is to be performed must be dry for sodium metal
test because water also reacts with Sodium to evolve H2 gas and even in the absence of
alcohol, evolution of H2 gas may be wrongly inferred as the presence of alcoholic group.
Q.7. Which is more acidic; an alcohol or phenol?
Ans. Phenol is more acidic than alcohol.
Q.8. How can you distinguish between the hydroxyl group of alcohol & phenol?
Ans. They can be distinguished by
(i)
(ii)
(iii)
Hcl
33
Ans. Silver mirror test-since silver; a product of the reaction deposits on the inner wall of the test
tube there by turning it into a mirror as observed from outside.
Q.15. What is Fehling A and Fehling B?
Ans. Fehling A is aq. solution of CuSO4. Fehling B is aq. Mixture of sodium potassium tartarate
and NaOh.
Q.16. Name an aldehyde that do not give positive Fehling test.
Ans. Benzaldehyde.
Q.17. How can the presence of carbony1 group tested?
Ans. (i)
(ii)
2, 4-D N P test
Bisulphite test
Carbylamine test.
Q.21. Which test is given by only primary aromatic amine and not by primary aliphatic amine?
Ans. Azo dye test.
Q.22. How can you distinguish between propanone and 3-pentanone?
Ans. By iodoform test; propanone will form iodoform on treatment with I2 and NaOH but 3pentanone, which is not a methylketone will not form iodoform.
Q.23. What is Hinsberg reagent?
Ans. Benzene sulphonyl chloride C6H5SO2Cl.
Q.24. What is the red ppt. in Fehling solution test due to?
Ans. Due to the formation of cuprous oxide Cu2O.
RCHO + 2Cu+2 + 5OH Cu2O (Redppt.)+ RCOO + 3H2O (l)
34
Q.25. What is the product obtained when an alcohol is treated with ceric ammonium nitrate?
Ans. A red complex is formed as following.
ROH + (NH4)2 [Ce(NO3)6] (NH4)2[Ce(OR)(NO3)5] + HNO3
Q.26. What happens when neutral ferric chloride is added to phenol?
Ans. A coloured complex is formed as under
6C6H5OH + FeCl3 [Fe(OC6H5)6]3 + 3HCl + 3H+.
Q.27. Why should the contents of carbylamine reaction disposed off, soon after the test?
Ans. Carbylamine or isocyanide formed has very offensive smell and may also be poisonous
hence must be decomposed by adding conc. HCl in the test tube before throwing the
contents in the sink.
RNH2 + 3KOH + CHCl3 RNC + 3H2O + 3KCl
Offensive smelling
Isocyanide
HCl
OH
Phenol
N=N
Az o
dye
OH
Q.29. Formic acid gives Fehling test even though it is an acid. Why?
Ans. Fehling solution test is given by substances that are earily oxidized. Formic acid is easily
oxidized and is able to reduce Cu+2 to Cu2O (red ppt.) in alkaline medium.
Q.30. Why aldehydes can be easily oxidized in comparison to ketones?
35
O
O
Schiffs reagent?
Rochell salt?
Schiffs reagent is solution of p-rosaniline in water, the pink colour of
which is decolourised by passing SO2 gas through it.
Sodium potassium tartarate.
36
Glucose
Galactose
H+
Glucose
Fructose
Q.6. What is meant by the term reducing sugar? Give one example.
Ans. Carbohydrates which reduce the Fehlings solution or Tollens reagent to form Cu2O (red
ppt.) or Ag(mirror) are called reducing sugars eg. Glucose and fructose.
Q.7. What is Molischs reagent?
Ans. 1% alcoholic solution of Napthol.
Q.8. What are Fehling A & Fehling B solution?
Ans. Fehling A is aqueous solution of copper sulphate and Fehling B is aq. Solution of sodium
potassium tartarate and NaOH.
Q.9. What is Rochelles salt?
Ans. Sodium potassium tartarate is called Rochelles salt.
Q.10. Why is Rochelles salt added to NaOH to make Fehling solution B?
Ans. In presence of NaOH, Cu+2ions get precipitated as copper hydroxide. Hence, to keep
Cu+2ions in solution, Rochelles salt is added that forms a soluble complex with Cu+2ions.
Q.11. What is the red ppt. formed in the Fehlings solution test?
Ans. Red ppt. is Cu2O(copper(i)oxide) formed during the reaction.
Q.12. How can Tollens reagent be prepared?
Ans. Tollens reagent can be prepared by adding NaOH solution to AgNO3 solution; the graying
ppt. formed is washed with water and dissolved in NH4OH. The resulting solution contains
complex ions [Ag(NH3)2]+ is called Tollens reagent.
Q.13. Why do we get shining mirror in Tollens test?
Ans. Shining mirror is obtained due to the reduction of silver ions to metallic silver which
deposites on the walls of the test-tube forming a mirror.
Q.14. What is Benedicts reagent?
37
Ans. Benedicts reagent is a solution of sodium carbonate, sodium citrate and copper sulphate.
The chemistry of this test is similar to Fehlings test with a difference that here citratre ions
are complexing agent instead of tartarate ions.
Q.15. Are all carbohydrates sweet in taste?
Ans. No. Carbohydrates sweet in taste are called sugars eg. Glucose, fructose, sucrose and
maltose etc.
Q.16. What are non-sugars?
Ans. Carbohydrates that are not sweet in taste are called non-sugars eg. Starch, cellulose etc.
Q.17. What happens when a carbohydrate is heated with conc. H2SO4?
Ans. Conc. H2SO4 acts as dehydrating agent and leads to charring of carbohydrates.
Q.18. What are anomers? Give an example.
Ans. Pairs of optical isomers which differ in the configuration only at C1 stom are called anomers.
The two anomers of glucose are following :
HCOH
HCOH O
HOCH
HCOH
HC
CH2OH
anomer
D-glucose
HOCH
HCOH O
HOCH
HCOH
HC
CH2OH
= anomer
D-glucose
38
R= H or alkyl group
When R = H; amino acid is glycine.
O
amino acid and COOH group of another amino acid in a polypeptide or protein is called a
peptide bond.
Q.28. What are essential and non-essential amino acids?
Ans. Certain amino acids can be made by our body and are not required through diet-are called
non-essential amino acids. Amino acids that must be supplied through our diet are called
essential amino acids.
Q.29. What is Zwitter ion?
Ans. Since amino acids have both acidic and basic (NH2) groups in it, it exists as a dipolar ion
called Zwitter ion.
39
H
|
RCCOOH
|
:NH2
|
RC COO
|
NH3+
Zwitterionic structure
R CH COO
|
NH2
(II)
H+
RCHCOO
|
NH3+
(I)
RCHCOOH
|
NH3+
(III)
However at a certain hydrogen ion concentration i.e. (pH), the dipolar ion exists as a
neutral ion and does not migrate towards either electrode. The pH of the solution at which a
particular amino acid does not migrate under the influence of an electric field is called
isoelectric point.
40
(i)
(ii)
(iii)
42
Ans. After the reaction between the substance and the standard solution is practically complete;
with one extra drop the indicator shows a clear visual change in the liquid being titrated.
The stage in the titration at which this occurs is called the end point.
Q.20. What is a titrant?
Ans. The reagent of known concentration is called titrant.
Q.21. What is a titrand?
Ans. The substance being titrated is called titrand.
Q.22. How are reactions classified in volumetric analysis?
Ans. The reactions employed in titrimetric i.e. volumetric analysis falls into two main classes :
(a)
(b)
Those in which no change in oxidation state occurs; these are dependent upon the
combination of ions. It includes neutralization (acid-base) reactions, complex
formation reactions (EDTA-titrations) and precipitation reactions.
Oxidationreaction reactions; these involve a change of oxidation state; as redox
reaction between KMnO4 and Mohrs salt or Oxalic acid.
wt. x 1000
Mol.wt
V(ml)
44
e.g.
Molecular wt.
.
No. of electrons gained by 1 molecule
Eq. wt of KMnO4 =
158 (its molecular wt.) = 31.6.
5 (no. of electrons gained)
(c)
Manganate ion
The manganate ion produced further reduced to MnO2 when a reducing agent is
present.
MnO42 + 2H2O + 2e MnO2 + 4OH
Hence the complete reaction would be
MnO4 + 2H2O + 3e MnO2 + 4OH
(same reaction as neutral medium)
In acidic medium
MnO4 + 8H+ + 5e Mn+2 + 4H2O.
We see that in basic and neutral medium MnO2 a brown ppt. is obtained which will
hinder the observation of the colour change at the end point. Hence the acidic
medium is choosen for the titration.
Q.50. Why do we titrate Mohrs salt and not FeSO4 with KMnO4?
Ans. Because FeSO4 gets readily oxidized by air thereby change in the composition or
concentration of the solution would occur, introducing errors in the volumetric
measurements.
46
The rate of reaction is fairly high at room temp. hence there is not need to heat.
Fe+2 may get aerialy oxidized to Fe+3 at high temp.
47
Ans. Filter paper being organic matter reduced KMnO4 and itself gets oxidized.
Q.61. Why should KMnO4 be stored in dark place?
Ans. It slowly decomposes on exposure to sunlight.
Q.62. What is a molar solution?
Ans. A soln containing 1 g mole of the solute dissolved per litre of the soln is called a molar
solution.
Q.63. Which out of molar & molal solution will not undergo change in concentration with change
in temperature?
Ans. Molal soln will not undergo change in conc. With temp. Molality depends on wt. of solvent
and molarity depends on volume of solution. With change in temp. wt. remains same but
volume changes. Hence molal solutions concentration does not change with change in
temp.
Q.64. What is the minimum wt. that can be weighed with the chemical balance?
Ans. On a usual balance provided with a rider we can weigh 2 x 10-4 g (with rider).
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