5 6145477749600419914
5 6145477749600419914
5 6145477749600419914
Practical Chemistry
JEE Syllabus
Detection of extra elements (N,S, halogens) in organic compounds;
Detection of the following functional groups: hydroxyl (alcoholic and
11
CHAPTER
phenolic), carbonyl (aldehyde and ketone), carboxyl and amino groups in
organic compounds, Chemistry involved in the preparation of the following:
Inorganic compounds: Mohr’s salt, potash alum, Organic compounds:
Acetanilide, p-nitroacetanilide, aniline yellow, iodoform, Chemistry involved
in the titrimetric excercises - Acids bases and the use of indicators, oxalic-
acid vs KMnO4, Mohr’s salt vs KMnO4, Chemical principles involved in the
qualitative salt analysis: Cations - Pb2+ , Cu2+, AI 3+, Fe3+, Zn2+, Ni2+, Ca2+, Ba2+,
Mg2+, NH4+. Anions- CO32-, S2-, SO42-, NO2-, NO3-, CI-, Br, I. (Insoluble salts excluded),
Chemical principles involved in the following experiments:
1. Enthalpy of solution of CuSO4
2. Enthalpy of neutralization of strong acid and strong base. .
3. Preparation of lyophilic and lyophobic sols.
4. Kinetic study of reaction of iodide ion with hydrogen peroxide at room
temperature.
Group I Iodoform
Radicals which are detected by dilute H2SO4 or dilute HCl, by liberating a gas Mohr's salt
(i) Carbonate (ii) Sulphite Potash alum
(iii) Sulphide (iv) Nitrite Redox Titrations
(v) Acetate
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Group II
Radicals which are detected by concentrated H2SO4
(i) Chloride (ii) Bromide
(iii) Iodide (iv) Nitrate
(v) Oxalate
Group III
Radicals which do not give any characteristic gas with dilute and concentrated H2SO4
(i) Sulphate (ii) Phosphate
(iii) Borate (iv) Fluoride
(i) Cl– Colourless gas with pungent smell which fumes in air.
C2H5OH and
BO33– Green edged flame of (C2H5)3BO3.
conc. H2SO4
3.
Conc. HNO3 and
PO43– A canary yellow precipitate of (NH4)3PO4.12MoO3.
(NH4)2MoO4
Sand and Waxy white deposit of silicic acid i.e. H4SiO4 or
F– Si(OH)4.
conc. H2SO4
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(ii) A colourless gas with suffocating odour having smell of burning sulphur - Sulphite ion (SO32–)
(iii) A colourless gas with smell of rotten eggs - Sulphide ion (S–2)
Na 2 S H2 SO 4 Na 2 SO 4 H2S
(Salt)
Further addition of excess of CO2 through lime water, milky solution turns colourless due to the formation
of calcium bicarbonate.
2. For Sulphite ion (SO32–) : If SO2 gas is a result of group analysis then it gives suffocating smell of
burning sulphur. When acidified potassium dichromate paper is exposed to the gas it attains green colour
due to the formation of chromic sulphate, confirms SO32– ion.
Salt (Na2SO3) + H2SO4 — Na2SO4 + H2O + SO2
4. For Nitrite ion (NO2–) : When salt containing nitrite ion is treated with dilute H2SO4, it yields a colourless
gas (NO) which in contact with oxygen of the air becomes brown due to the formation of NO2 gas. This
NO gas in dil. FeSO4 solution gives brown coloured salt.
And when a mixture of iodide and nitrite is acted upon by dil. H2SO4, the iodide is decomposed giving
violet vapours of iodine.
2NaNO2 (Salt) + H2SO4 — Na2SO4 + 2HNO2
2KI + H2SO4 — K2SO4 + 2HI
I2
2HNO2 + 2HI — 2H2O + + 2NO
Violet
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5. For Acetate ion (CH3COO–) : If salt is with acetate ion then on reaction with dil. H2SO4 decomposes
to give acetic acid vapours which possess smell of vinegar. These acetate salt (soluble in water) when
treated with neutral FeCl3 solution gives blood red colouration of ferric acetate.
2CH3COONa (Salt) + H2SO4 — 2CH3COOH + Na2SO4
Group : II
Group acidic radicals : Cl–, Br–, I–, NO3–, C2O42–
Group reagent : Conc. H2SO4
Procedure : Take salt and add conc. H2SO4 and warm gently.
Observation :
(i) Colourless gas with pungent smell which fumes in air. Addition of pinch of MnO2 in the solution gives pale
green gas. - Chloride ion (Cl–)
NaCl (Salt) + H2SO4 — NaHSO4 + HCl
MnO2 + 4HCl — MnCl2 + Cl2 + 2H2O
(ii) Reddish brown fumes which intensify on addition of MnO2. Bromide ion (Br–)
NaBr (Salt) + H2SO4 — NaHSO4 + HBr
2HBr + H2SO4 — Br2 + 2H2O + SO2
2NaBr (Salt) + MnO2 + 3H2SO4 — 2NaHSO4 + MnSO4 + 2H2O + Br2
(iii) Violet pungent fumes evolved which may condense as black spots on the cooler part of test tube. These
violet fumes intensity on addition of MnO2 - Iodine ion (I–)
2KI (Salt) + 2H2SO4 — 2KHSO4 + 2HI
2HI + H2SO4 — I2 + SO2 + 2H2O
2KI (Salt) + MnO2 + 3H2SO4 — 2KHSO4 + MnSO4 + 2H2O + I2
(iv) Light brown fumes of NO2 which intensify on adding copper turning - Nitrate ion (NO3–)
NaNO3 (Salt) + H2SO4 — NaHSO4 + HNO3
4HNO3 — 2H2O + 4NO2 + O2
Cu + 4HNO3 — Cu(NO3)2 + 2NO2 + 2H2O
(v) Colourless, odourless gas which burns with blue flame at mouth of tube - Oxalate ion (C2O42–)
Na2C2O4 (Salt) + H2SO4 — Na2SO4 + H2C2O4
H2C2O4 — CO + CO2 + H2O
Confirmatory Test
1. For Chloride ion (Cl–) : If salt contains chloride ion than it evolves HCl gas on reaction with conc. H2SO4.
(i) The HCl gas so evolved when reacted with NH4OH gives fumes of ammonium chloride.
(ii) HCl gas also gives curdy white precipitate of silver chloride with silver nitrate solution.
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(iii) When chloride salt is directly heated with conc. H2SO4 in presence of K2Cr2O7, deep red vapours
of chromyl chloride are evolved. This test is known as chromyl chloride test.
When vapours of chromyl chloride are passed through NaOH solution, solution becomes yellow due
to the formation of sodium chromate, which on reaction with CH3COOH and Pb(CH3COO)2 gives a
yellow precipitate of lead chromate.
(i) The bromide salt which is under analysis gives pale yellow precipitate of AgBr on reaction with NH4OH.
If NH4OH is taken in excess then the soluble complex of silver is formed.
(ii) Bromide salt when treated with dil. H2SO4, CHCl3 (or CCl4) and chlorine water, chlorine is able to
displace bromine due to which Br2 gas is liberated. This Br2 gas dissolves in CHCl3 or CCl4 forming
brown layer.
(i) The salt if with iodide ion when treated with conc. H2SO4 evolves iodine vapour which on reaction
with starch produce blue colour.
(ii) The iodide salt solution gives yellow precipitate of AgI with AgNO3 solution which is insoluble in
NH4OH.
AgI
NaI (Salt) + AgNO3 — Yellow ppt.
+ NaNO3
(iii) The iodide salt is treated with chlorine water, chlorine replaces iodine from salt. The iodine thus
evolved dissolves in CHCl3 or CCl4 layer giving violet colour.
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(ii) Salt of nitrate when reacted with Zn or Al in presence of conc. NaOH evolves NH3 gas which can
be detected by its characteristic odour.
Zn + 2NaOH — Na2ZnO2 + 2H
or Al + NaOH + H2O — NaAlO2 + 3H
NaNO3 (Salt) + 8H — NaOH + 2H2O + NH3
Group : III
Group acidic radicals : SO42–, BO33–, PO43– and F–
Group reagents
(i) BaCl2 - (For SO42–)
(ii) C2H5OH and conc. H2SO4 - (For BO33–)
(iii) Conc. HNO3 and ammonium molybdate - (For PO43–)
(iv) Sand and conc. H2SO4 - (For F–)
Procedure & Observation : Take salt and add above reagents one by one to observe the result.
(i) For Sulphate ion : Take salt and add BaCl2, if salt containing SO42– then precipitate of Barium sulphate
(BaSO4) is obtained which is insoluble in conc. HNO3.
Note : If sulphate salt is of silver or lead then on reaction with BaCl2 it will give AgCl or PbCl2. So
to avoid this BaNO3 can be used for instead of BaCl2 to analyse SO42– ion.
Classification is based on whether a cation reacts with these reagents by the formation of precipitate or not,
i.e. it depends upon the differences of solubilities of their salts like carbonates, sulphides etc.
Group Category of Basic Radicals
Group-I :
Cations of this group form precipitates with dilute hydrogen chloride.
(i) Lead (II) ion
(ii) Mercury (I) ion
(iii) Silver (I) ion
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Group - II :
Group - II is categorised as group-IIA and Group-IIB. The ions of this group do not react with HCl but precipitate
with H2S in dilute mineral acidic medium.
The Group-IIA sulphides of these cations are insoluble in ammonium polysulphide. The Group-IIB sulphides of
these cations are soluble in ammonium polysulphide.
Group-IIA Group-IIB
Group-III :
Group-III cations do not react with dil. HCl or with H2S in dilute acidic medium.
Group-IV :
Group-IV cations form sulphides with H2S in presence of NH4OH, these sulphides are insoluble in NH4OH.
Group-V :
Group-V cations give precipitate with ammonium carbonate in presence of NH4Cl in neutral or slightly alkaline
medium.
Group-VI :
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Group Zero :
Group zero cation i.e. NH4+ reacts with NaOH to give NH3 gas
(i) Ammonium (I) ion
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Confirmatory Test
1. For Pb+2 (lead) :
(i) PbCl2, so formed is soluble in hot water and on cooling white crystals are obtained.
(ii) Solution PbCl2 and potassium chromate gives yellow ppt.
(iv) Solution of PbCl2 with dilute H2SO4 gives white ppt of lead sulphate and precipitate is soluble in
ammonium acetate.
(i) When dil. HNO3 added to above solution, white precipitate is obtained.
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HgCl 2 Cu Hg
CuCl 2
Grey ppt .
Group - II :
Group II A : Hg+2, Pb+2, Bi+3, Cu+2, Cd+2
Group II B : As+3, Sb+3, Sn+2, Sn+4
Group reagent : H2S gas in presence of dil HCl.
Procedure : On passing H2S in presence. of dil HCl ions give.
Observation :
Yellow ppt. : CdS, As2S3, SnS2
Orange ppt : Sb2S3
Brown ppt : SnS
Black ppt : HgS, PbS, Bi2S3, CuS
These sulphides of IIA and IIB are treated with yellow ammonium sulphide.
Group IIA : precipitate does not dissolve in yellow ammonium sulphide. ppt is heated with dil HNO3, all
sulphides of IIA are soluble except HgS.
3XS + 8HNO3 3X(NO3)2 + 2NO + 3S + 4H2O
Group IIB : The sulphides of IIB are first oxidised to higher sulphides which then form thio-compounds.
As2S3 + 2(NH4)2S2 2(NH4)2S + As2S5
SnS + (NH4)2S2 (NH4)2S + SnS2
SnS2 + (NH4)2S (NH4)2SnS3
Confirmatory Test for Group-IIA Radicals : Ammonium thiostannate
1. For Hg+2 (Mercuric Ion) :
(i) Hg+2 ions in solution give white precipitate turning black on addition of SnCl2.
2Hg+2 + SnCl2 Sn+4 + Hg2Cl2
2
Pb 2 CrO 4 PbCrO4
Yellow
Pb 2 2I PbI
2
Yellow
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BiCl3 H2 O BiOCl
2HCl
White ppt
HNO
As 3
3
As 5 (H3 AsO 4 )
2. For Sn+2 or Sn+4 (Tin Ion) : Sn+2 ions in solution as SnCl2 give white precipitate with HgCl2 turning
black on standing
3. For Sb+3 (Antimony Ion) : Sb+3 ions in solution as SbCl3, on addition of water give white ppt.
SbCl 3 H2 O SbOCl
2HCl
White
Group-III
Group Basic Radicals : Fe+3, Al+3, Cr+3
Group Reagent : NH4OH + NH4Cl
Procedure : Take salt add few drops of concentrated HNO3 and boil the solution add NH4Cl and NH4OH slowly.
Observation :
Fe(OH)3 - Reddish brown precipitate
Cr(OH)3 - Green precipitate
Al(OH)3 - White precipitate
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Confirmatory Test :
1. For Fe+3 Ion :
(i) Dissolve the Fe(OH)3 precipitate in dil HCl and
(iv) Take part-II and add KCNS solution formation of red colour precipitate confirms Fe+3 ion
FeCl3 + 3KCNS [Fe(CNS)3] + 3KCl
(red colour)
2. For Al+3 Ion :
(i) Dissolve the white precipitate of Al(OH)3 in dil. HCl followed by NaOH which forms precipitate of NaAlO2,
which is soluble.
(ii) White precipitate reappears if NH4Cl is added to sodium meta aluminate, confirms Al+3 ion.
NH4 Cl NaAlO 2 H2 O NaCl Al(OH)3 NH3
(ii) Add acetic acid to the above yellow solution along with lead acetate yellow precipitate formation
confirms the presence of Cr+3.
CH COOH
Na 2 CrO 4 ( CH3COO ) 2 Pb 3 PbCrO 4 2CH3 COONa
yellow ppt .
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Group-IV
Procedure :
(i) Take salt and add H2S gas in presence of NH4Cl and NH4OH. or take filtrate of group-III concentrate it
by heating. Add NH4OH and pass H2S gas.
Observation :
Confirmatory Test :
(i) Wash the precipitate with water and dissolve in aqua-regia (or conc HCl in presence of KClO3)
MS 2HCl [O] MCl2 H2O S
( Conc .)
[M = Ni+2 or Co+2]
(iii) If it is NiCl2 then it will react with dimethylglyoxime in presence of NH4OH to give orange precipitate
which confirms the presence of Ni+2 ion.
OH O
CH3–C=N N=C–CH3
CH3–C=NOH NH4OH |
| | Ni
NiCl2 + 2 N=C–CH3
CH3–C=NOH CH3–C=N |
(dmg) OH
O
Cherry red ppt.
(iv) If NiCl2 formed then addition of Br2 water in presence of NaHCO3 gives black residue of Ni2O3
NiCl2 + 2NaHCO3 NiCO3 + 2NaCl + H2O + CO2
2NiCO3 4NaOH [O ] Ni2 O 3 2Na 2CO 3 H2O
(From Br2 / H2 O )
Black
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(v) If COCl2 is formed then it will react with NH4CNS crystals in presence of ether to give blue coloured
etheral layer.
(vi) If COCl2 is formed then addition of Br2 water in presence of NaHCO3 gives green solution confirms
Co+2 ion.
COCl2 + NaHCO3 + NaOH 2NaCl + CoCO3 + H2O
2NaHCO 3 Na 2CO 3 H2O CO 2
[O ]
CoCO 3 2Na 2 CO 3 Na 4 [CoII ( CO 3 )3 ] Na 3 [CoIII (CO 3 ) 3 ] 2Na 2 CO 3 H2O
NaHCO3 /
green
(ii) Add NaOH which converts MnCl2 into Mn(OH)2, to this add Br2 water which will oxidise Mn(CH)2 to
MnO2 (black or brown ppt.)
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Procedure :
1. Take filtrate of group IV and concentrate it by adding H2S gas.
2. Now add solid NH4Cl and NH4OH followed by (NH4)2CO3 solution.
Result :
BaCO3 - White precipitate
SrCO3 - White precipitate
CaCO3 - White precipitate
Confirmatory Test :
1. For Ba+2 ion :
(i) Take white precipitate and add CH3COOH
BaCO3 + 2CH3COOH — (CH3COO)2Ba + CO2 + H2O
(ii) Add K2CrO4 solution to it formation of yellow precipitate confirms Ba+2 ion.
(CH3COO)2Ba + K2CrO4 — BaCrO4 + 2CH3COOK
white
2. For Sr2+ ion :
(i) Take white precipitate and add CH3COOH.
SrCO3 + 2CH3COOH — (CH3COO)2Ca + CO2 + H2O
(ii) Add (NH4)2SO4 solution, formation of white precipitate confirms the presence of Sr+2.
(CH3COO)2Sr + (NH4)2SO2 — SrSO4 + 2CH3COONH4
white
3. For Ca+2 ion :
(i) Take white precipitate and add CH3COOH.
CaCO3 + CH3COOH — (CH3COO)2Ca + CO2 + H2O
(ii) Add ammonium oxalate, white precipitate formation confirms Ca+2 ion.
(CH3COO)2Ca + (NH4)2C2O4 — CaC2O4 + 2CH3COONH4
white
Group : VI
Group basic radical : Mg+2
Group reagent : Na2HPO4 in presence of NH4OH
Procedure :
1. Take filtrate of group V and add some quantity of (NH4)2C2O4 (to remove Ba+2, Ca+2, Sr+2)
2. The solution is concentrated and further NH4OH is added to make it alkaline. Addition of Na2HPO4 forms
the white precipitate.
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Group : Zero
Procedure : Take salt and heat it with NaOH, solution starts evolving ammonia.
Confirmatory Test :
1. To the above, if HCl dipped rod is brought in contact, white fumes of ammonium chloride are formed which
confirms the presence of NH4+ ion
2. To the aqueous solution of ammonium salt addition of nessler's reagent (K2HgI4) forms brown coloured
precipitate of iodide of Millon's base.
NH2
Hg
2K2HgI4 + NH4Cl + 4KOH O + 7KI + KCl + 3H2O
Hg
I
(Iodide of
Million's base)
ENTHALPY OF SOLUTION
1. Heat at neutralization : The quantity of heat evolved when one gram equivalent of an acid is completely
neutralised by one gram equivalent of a base in dilute solution.
The heat of neutralisation of a strong acid and a strong base is 13.7 kcal on the basis of electrolytic
dissociation theory it has been clearly explain that this heat of neutralisation is merely the heat of
formation of water from H+ ion of an acid and OH– ion of a base
The heat of neutralisation in case of weak acid or weak base is some what less than 13.7 kcal because
some heat is used up to dissociate the weak electrolyte. The difference in values is called the dissociation
energy of weak acid or weak base.
2. Heat of solution : The enthalpy change when one mole of the solute is dissolved completely in a large
excess of water so that further dilution of solution does not produce any heat change.
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Preparation of lyophobic sols : Substances which are termed as extrinsic colloids such as metals etc. do
not pass directly into colloidal solution when treated when water or another solvent. Such substances are converted
into colloidal solution by the following two methods.
Condensation method
(b) Dispersion method : In this method large particles of the substance are broken into particles of colloidal
dimension in the presence of dispersion medium.
(1) Mechanical dispersion : The coarse particles of the substance to be dispersed are agitated with
dispersion medium. The suspension is then passed through a colloidal mill.
(2) Electrical disintegration method (Bredig’s arc method) : Colloidal solution of metals like gold,
silver etc. are obtained by electro disintegration method. In this method electric arc is struck between
of metals immersed in the dispersion medium.
(3) Peptization : The process which involves the conversion of precipitates into colloidal solution is
called peptization. The electrolyte added is called peptizing agent.
H SO 4
ROH + CH3COOH 2 CH3COOR + H2O
(iii) Ceric ammonium nitrate test : Shake as few drops of ceric ammonium nitrate with 1 ml of organic
compound. A red colour is produced (phenol give a green or brown colour).
2ROH + (NH4)2 [Ce(NO3)6] [Ce(NO3)4(ROH)2] + 2NH4NO3
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OH OH
N2Cl– + N=N + HCl
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(ii) Sodium nitroprusside test : Treat 1 ml of organic compound with 1 ml of freshly prepared solution
of sodium nitroprusside followed by excess of NaOH solution. A wine red colour is obtained.
6. Test for phenolic group
(i) Litmus test : Place a trace of organic compound on the moist blue litmus paper. It turns red.
(ii) Neutral FeCl3 test : When phenols are treated with neutral FeCl3 solution they form coloured
complexes. The colour of complex may be violet, red, blue or green. This is a characteristics
reaction of compounds having enolic group (=C–OH). All enols respond to this test.
(iii) Aniline dye test : Dissolve a little aniline in dilute hydrochloric acid cool in ice-cold water and add
aqueous solution of sodium nitrite dropwise. To this cold solution, add organic compound already
dissolved in sodium hydroxide solution. A red or orange precipitate is obtained
NaNO2 + HCl HNO2 + NaCl
+ –
NH2 N2Cl
0°C
+ HNO2 + HCl + 2H2O
+ – NaOH
N2Cl + OH –NaCl N=N OH
–H2O
P-hydroxy azobenzene
(dye)
(iv) Bromine water test : Take aqueous or alcoholic solution of organic compound in test tube. Add
excess of bromine water. A yellowish white precipitate is obtained.
OH OH
Br Br
+ 3Br2
Br
(2, 4, 6 tribromo phenol)
(v) Ceric ammonium nitrate test : Treat a few drops of the ceric ammonium nitrate with 3-4 mL hot
aqueous solution of the organic compound. A green or brown precipitate is obtained.
(vi) Liebermann’s test : Take a little amount of the compound and fuse with a few crystal of NaNO2
in a test tube. Cool the test and add 1 ml conc H2SO4. A deep green colour is obtained, which
changes to purple, to blue and finally when poured into large excess of water, to red. When a little
NaOH solution is added to the aqueous solution, the same green, purple or blue colour reappears.
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5C
NaNO 2 HCl NaCl HNO 2
ice cold
NH2 N=N–Cl
< 5°C
+ HNO2 + HCl ice cold + 2H2O
benzene diazonium
chloride
pH = 4 – 5
N=N–Cl + H NH2 ice cold N=N NH2
P-amino azobenzene
aniline yellow
IODOFORM
Iodoform is usually prepared by the action of iodine on ethyl alcohol or acetone in presence of alkali. Its colour
is yellow.
Chemical reaction
from ethyl alcohol
CH3–CH2OH + I2 + 2NaOH CH3CHO + 2NaI + 2H2O
CH3CHO + 3NaOH + 3I2 CI3CHO + 3Na + 3H2O
from acetone
O
||
CH3COCH3 + 3I2 + 3NaOH CH3–C–CI3 + 3NaI + 3H2O
O
||
CH 3–C–CI3 + NaOH CHI 3 + CH3COONa
yellow ppt.
Preparation of Acetanilide
It is prepared by acetylation of aniline with acetic anhydride in the presence of glacial acetic acid. Its colour
is white and melting point is 114°C.
Chemical reaction
NH2 NHCOCH3
CH3 COOH
+ (CH3CO)2O Glacial
+ CH3COOH
acetanilide
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Preparation of P-nitroacetanilide
Aniline cannot be nitrated directly because nitric acid is strong oxidising agent oxidises the amino group.
Therefore amino group is first protected by acetylation process and then acetanilide formed is nitrated using
conc. HNO3 + conc. H2SO4. A mixture of o– and p-nitroacetanilide obtained.
The solution is kept hot to expel CO2 produced so as to avoid back reaction.
The stoichiometric ratio in this titration is evidently (2/5).
Suppose 20 ml of oxalic acid solution require 25 ml of 0.05 M KMnO4 solution for titration then the
25 0.05 5
concentration of oxalic acid solution 0.156 M accordingly the amount of oxalic acid (mole
20 2
wt 126) would be 0.156 × 126 = 19.656 g L–1.
(2) Titration of Mohr salt against KMnO4 : Mohr salt FeSO4 · (NH4)2SO4 · 6H2O is titrated against KMnO4
in presence of dilute sulphuric acid when FeSO4 of the Mohr salt is oxidised to Fe2(SO)3. KMnO4 solution
is added to a known volume at Mohr salt solution containing dilute H2SO4 gradually in small amounts.
Rapid addition of KMnO4 results in the formation of hydrated MnO2 · H2O which is brown in colour
The above reaction also occurs if there is insufficient quantity of H2SO4 in the titration solution.
In these titrations KMnO4 itself acts as the indictor
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Suppose 25 mL of Mohr salt solution requires15.5 mL of 0.1 M KMnO4 for titration. Applying the volumetric
correlation we have
15.5 × 0.1 = ( 25 × conc of Mohr salt) × Stoichiometric ratio
The redox reaction in the titration is
15.5 0.1 5
conc. of Mohr salt solution = 0.31M
25 1
Amount of Mohr salt = 0.31 × 392 = 121.52 gL–1
If the conc of Mohr salt solution is known, we can find out the conc of KMnO4 solution.
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