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Principles Related to

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.

ANALYSIS OF ACIDIC RADICALS


THIS CHAPTER
Acidic radicals are categorised into three groups. There is no as such scheme
which permits the separation of the common anions into major groups. The INCLUDES
classification may studied in two parts :  Analysis of Acidic
1. Those involving the identification by volatile products obtained on treatment Radicals
with acids, and
 Analysis of Basic
2. Those dependent upon reactions in solution. Radicals
The part (1) is subdivided into  Enthalpy of solution
(i) Gases evolved with dilute HCl or dil H2SO4 and  Preparation of
Lyophilic and
(ii) Gases or vapours evolved with conc. H2SO4.
Lyophobic Sols
The part (2) is subdivided into
 Detection of
(i) Precipitation reactions and functional groups
(ii) Oxidation and reduction in solution  Methods of
Group Category of Acid Radicals
preparation

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

Group Group reagent Group radicals Colour & Observation


Brisk effervescence in cold with evolution of
(i) CO32– colourless and odourless gas.
Colourless gas with suffocating odour (smell of
(ii) SO32–
burning sulphur)
Dil. H2SO4 or
1. (iii) S–2 A colourless gas with smell of rotten egg.
dil HCl

(iv) NO2– A light brown gas.

(v) CH3COO– Colourless vapours with smell of vinegar.

(i) Cl– Colourless gas with pungent smell which fumes in air.

Reddish brown fumes which intensify on addition of


(ii) Br–
MnO2.
Violet pungent fumes evolved which intensify on
2. Conc. H2SO4 (iii) I–
addition of MnO2 and condense as black.
Light brown vapours with pungent smell and intensify
(iv) NO3–
on addition of Cu turnings.
Colourless, odourless gas burns with blue flame at
(v) C2O42–
the mouth of test tube and turns lime water milky.

BaCl2 SO42– White precipitate of BaSO4, insoluble in conc. HNO3.

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

Identification of Acid Radicals


Group : I
Group acidic radicals : CO32–, SO32–, S–2, NO2–
Group reagent : dil. HCl or dil H2SO4
Procedure : Take some quantity of substance and add dil. HCl or dil. H2SO4.
Observation :
(i) Brisk efferrescence in cold with evolution of colourless and odourless gas - Carbonate ion (CO32–)

Na 2 CO3  H2SO 4  Na 2SO 4  H2 O  CO 2 


 
(Salt)

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(ii) A colourless gas with suffocating odour having smell of burning sulphur - Sulphite ion (SO32–)

Na 2 SO 3  H2SO 4  Na 2SO 4  H2 O  SO 2 


 
(Salt)

(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)

(iv) A light brown gas - Nitrite ion (NO2–)

NaNO 2  H2SO 4  Na 2SO 4  2HNO 2




(Salt)

3HNO2 — H2O + 2NO + HNO3


3NO + O2 — 2NO2 (Brown)
Confirmatory Test :
1. For Carbonate ion (CO32–) : If CO2 gas formed during above procedure, is passed through lime water;
the lime water turns milky with the formation of calcium carbonate, confirms CO32– ion.
Salt (Na2CO3) + H2SO4 — Na2SO4 + H2O + CO2

CO 2  Ca(OH) 2  CaCO 3  H2O




white ppt.

Further addition of excess of CO2 through lime water, milky solution turns colourless due to the formation
of calcium bicarbonate.

CaCO 3  H2O  CO 2  Ca(HCO 3 )2


 
soluble

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

K 2Cr2O 7  H2 SO 4  3SO 2  K 2 SO 4  Cr2 (SO 4 )3  H2 O



green

3. For Sulphide ion (S–2)


: If dil. H2SO4 on reaction with salt gives H2S gas, which on exposure to this
gas the lead acetate paper turns black due to the formation of lead sulphide, confirms S–2 ion.
Salt (Na2S) + H2SO4 — Na2SO4 + H2S 

(CH3 COO)2 Pb  H2S  


PbS
  2CH3COOH
Black

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.

FeSO 4 .7H2 O  NO  [Fe(H2 O)5 NO].SO 4  2H2O



Brown

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

FeCl3  3CH3 COONa  (CH3 COO)3 Fe  3NaCl



Blood red

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.

HCl  NH4OH  NH4 Cl  H2 O



 
White fumes

(ii) HCl gas also gives curdy white precipitate of silver chloride with silver nitrate solution.

HCl  AgNO 3  AgCl  HNO 3



ppt.

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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.

NaCl (Salt) + H2SO4 — NaHSO4 + HCl

K2Cr2O7 + 2H2SO4 — 2KHSO4 + 2CrO3 + H2O

CrO 3  2HCl  CrO 2Cl2  H2 O



Chromyl chloride

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.

CrO2 Cl2  4NaOH  Na 2CrO 4  2NaCl  2H2O



Yellow

Na 2 CrO 4  Pb(CH3COO) 2  PbCrO 4  2CH3COONa



Yellow ppt.

Note : Test is not given by HgCl2, SnCl2, AgCl, PbCl2.

2. For bromide ion (Br–) :

(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.

NaBr (Salt)  AgNO 3  AgBr  NaNO 3



pale yellow

AgBr  2NH 4 OH [Ag(NH3 )2 ]Br  2H2 O


 
Excess

(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.

2KBr (Salt) + Cl2 — 2KCl + Br2

Br2 + Chloroform — Brown layer

3. For Iodide ion (I–) :

(i) The salt if with iodide ion when treated with conc. H2SO4 evolves iodine vapour which on reaction
with starch produce blue colour.

I2 + Starch — 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.

2KI (Salt) + Cl2 — 2KCl + I2


I2 + CHCl3 — Violet layer

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4. For Nitrate ion (NO3–) :


(i) Brown ring test : If salt under analysis contains nitrate ion, to confirm it, aqueous solution of the
salt is treated with freshly prepared solution of ferrous sulphate and conc. H2SO4, a brown ring
complex is formed.
(NaNO3) Salt + H2SO4 — NaHSO4 + HNO3

6FeSO4 + 2HNO3 + 3H2SO4 — 3Fe2(SO4)3 + 4H2O + 2NO

[Fe(H2 O)6 ]SO 4 .H 2O  NO  [Fe(H 2O)5 NO].SO 4  2H2O



Brown ring

(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.

Na 2 SO 4  BaCl 2  2NaCl  BaSO 4 



White

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.

Analysis of Basic Radicals


Basic Radicals i.e. cations are classified into six groups on the basis of their behaviour against some reagents.

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

(i) Mercury (II) ion (i) Arsenic (III) ion

(ii) Bismuth (III) ion (ii) Antimony (III) ion

(iii) Copper (II) ion (iii) Tin (II) ion

(iv) Cadmium (II) ion (iv) Tin (IV) ion

Group-III :

Group-III cations do not react with dil. HCl or with H2S in dilute acidic medium.

Group-III cations precipitate with ammonium hydroxide

(i) Iron (III) ion

(ii) Aluminium (III) ion

(iii) Chromium (III) ion

Group-IV :

Group-IV cations form sulphides with H2S in presence of NH4OH, these sulphides are insoluble in NH4OH.

(i) Zinc (II) ion

(ii) Manganese (II) ion

(iii) Cobalt (II) ion

(iv) Nickel (II) ion

Group-V :

Group-V cations give precipitate with ammonium carbonate in presence of NH4Cl in neutral or slightly alkaline
medium.

(i) Barium (II) ion

(ii) Strontium (II) ion

(iii) Calcium (II) ion

Group-VI :

Group-VI cation reacts with Na2HPO4 to form precipitate

(i) Magnesium (II) ion

(ii) Sodium (I) ion

(iii) Potassium (I) ion

(iv) Lithium (I) ion

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Group Zero :
Group zero cation i.e. NH4+ reacts with NaOH to give NH3 gas
(i) Ammonium (I) ion

Group Group Reagent Basic Colour and Composition


Radicals of Precipitate
+
1. Dil HCl Ag AgCl — White
+2
Pb PbCl2 — White
2+
Hg2 Hg2Cl2 — White
+2
2. H2S in presence Hg HgS — Black
+2
of dil HCl Pb PbS — Black
+3
Bi Bi2S3 — Black
+2
Cu CuS — Black
+2
Cd CdS — Yellow
+3
As As2S3 — Yellow
+3
Sb Sb2S3 — Orange
+2
Sn SnS — Brown
+4
Sn SnS2 — Yellow
+3
3. NH4OH in presence Fe Fe(OH)3 — Reddish Brown
+3
of NH4Cl Cr Cr(OH)3 — Green
+3
Al Al(OH)3 — White
+2
4. H2S in presence Mn MnS — Buff
+2
of NH4OH Co CoS — Black
+2
Ni NiS — Black
+2
5. (NH4)2CO3 in presence Ba BaCO3 — White
+2
of NH4OH Sr SrCO3 — White
+2
Ca CaCO3 — White
+2
6. Na2HPO4 Mg Mg(NH4)PO4 — White
+
Zero NaOH NH4 NH3 gas

Identification of Basic Radicals


Group : I
Radicals : Pb2+, Ag+, Hg22+
Group Reagent : Dil. HCl
Procedure : Add dil HCl to solution of substance,
White ppt. indicates presence of Hg22+, Ag+ and Pb+2
Result : Ag+ + Cl–  AgCl 
Pb+2 + 2Cl–  PbCl2 
Hg2+2 + 2Cl–  Hg2Cl2 

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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.

PbCl 2  K 2CrO 4  PbCrO 4  2KCl


Yellow ppt.

Yellow ppt. is insoluble in acetic acid and soluble in NaOH.


PbCrO4 + 4NaOH  Na2PbO2 + Na2CrO4 + 2H2O
(iii) PbCl2 forms yellow ppt. with potassium iodide solution.

PbCl 2  2KI PbI


2  2KCl
Yellow

(iv) Solution of PbCl2 with dilute H2SO4 gives white ppt of lead sulphate and precipitate is soluble in
ammonium acetate.

PbCl 2  H2SO 4 PbSO 4  2HCl




White ppt .

PbSO4 + 2CH3COONH4  (CH3COO)2Pb + (NH4)2SO4


2. For Ag+ (Silver Ion) : AgCl dissolves in NH4OH

AgCl  2NH4 OH  [ Ag(NH3 )2 ]Cl  2H2 O


Diammine silver (I)
chloride

(i) When dil. HNO3 added to above solution, white precipitate is obtained.

[ Ag(NH3 )2 ]Cl  2HNO 3  AgCl  2NH4NO 3



White ppt .

(ii) When KI is added to complex solution, yellow ppt. is obtained.

[ Ag(NH3 )2 ]Cl  KI  AgI


  KCl  2NH3
Yellow ppt .

3. For Hg22+ (Mercurous Ion) :


(i) Hg2Cl2 turns black when treated with NH4OH.

Hg2Cl 2  2NH4 OH  Hg  Hg(NH2 )Cl  NH4 Cl  2H2O



Black

(ii) This black residue dissolves in aqua-regia forming mercuric chloride


3HCl + HNO3  NOCl + 2H2O + 2Cl
2Hg(NH2)Cl + 6Cl  2HgCl2 + 4HCl + N2
Hg + 2Cl  HgCl2
(iii) This solution of HgCl2 forms white ppt. with stannous chloride

2HgCl 2  SnCl 2 Hg2 Cl2  SnCl 4


 
White ppt .

Hg2Cl 2  SnCl 2  2


Hg  SnCl 4
Grey ppt .

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(iv) Solution of HgCl2 with copper turning forms grey ppt.

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

Hg2Cl2  SnCl 2  SnCl 4  2


Hg
black

2. For Pb+2 (Lead Ion) :


(i) Pb+2 ions is solution give white precipitate with H2SO4.
Pb+2 + H2SO4  PbSO4 + 2H+
(ii) Pb+2 ions in solution give yellow precipitate with K2CrO4 and KI.

2
Pb 2  CrO 4 PbCrO4 

Yellow

Pb 2  2I PbI
2
Yellow

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3. For Cu+2 (Copper Ion) :


(i) Cu+2 ions in solution give deep blue colour with excess of NH4OH

Cu 2  4NH4 OH [Cu(NH3 ) 4 ] 2  4H2 O



Deep Blue

(ii) Cu+2 ions give chocolate precipitate with K4Fe(CN)6


2Cu+ + K4Fe(CN)6  Cu2[Fe(CN)6] + 4K+
4. For Bi+3 (Bismuth Ion) :
precipitate dissolves in dil. HCl on addition of water give white cloudy ppt.

BiCl3  H2 O BiOCl
   2HCl
White ppt

5. For Cd+2 (Cadmium Ion) :


Cd+2 ions in solution give yellow ppt. with H2S

Cd 2  H2S  CdS  2H


Yellow

Confirmatory Test for Group IIB Radicals :


1. For As+3 (Arsenic Ion) : As+3 ions in solution give yellow precipitate with Ammonium molybdate and
HNO3.

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

SnCl 2  2HgCl 2  SnCl 4  Hg2Cl 2 


 
White

Hg2Cl2  SnCl 2  SnCl 4  2


Hg
Black

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

Fe(OH)3  HCl FeCl 3  3H2 O




(ii) Divide the solutions in two parts (I & II)


(iii) Take part I and add K4[Fe(CN)6] solution formation of prussian blue solution confirms the presence
of Fe+3.

4FeCl 3  3K 4 [Fe(CN)6 ] Fe 4 [Fe( CN) 6 ] 3  12 KCl



Pr ussian Blue

(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.

Al(OH)3  NaOH  NaAlO 2  2H2 O


Sod. meta
aluminate

(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


3. For Cr+3 Ion :


(i) Green precipitate of Cr+3 ion is insoluble in NaOH but addition of Br2 water forms yellow coloured
solution of Na2CrO4.
Br2 + H2O  2HBr + [O]

4NaOH  2Cr(OH)3  3[O]  2Na 2CrO 4  5H2 O


yellow
solution

(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 .

Note for the Group :


1. Dilute HNO3 is added to convert Fe+2 to Fe+3.
2. Amount of HNO3 is small otherwise it will convert Mn+2 to Mn+3.
3. Instead of salt, if group-II filtrate is taken for analysis of group-III then we have to boil off H2S from
group-II filtrate otherwise sulphides of group-IV if present will start precipitating.

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Group-IV

Group Basic Radicals : Ni+2, Co+2, Mn+2, Zn+2

Group Reagent : H2S gas in presence of NH4Cl and NH4OH

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.

(ii) Pass more amount of H2S when precipitate is formed.

Observation :

NiS - Black precipitate

CoS - Black precipitate

MnS - Buff coloured precipitate

ZnS - White precipitate

Confirmatory Test :

1. For Ni+2 Ion and Co+2 Ion :

(i) Wash the precipitate with water and dissolve in aqua-regia (or conc HCl in presence of KClO3)

(ii) Extract the residue with water


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.

COCl2  4NH4 CNS  ether (NH4 )2 [Co(CNS) 4 ]  2NH4 Cl



Blue

(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

2. For Mn+2 Ion :

(i) MnS precipitate dissolves in dil. HCl.

MnS + 2HCl  MnCl2 + H2S

(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.)

MnCl2 + NaOH  Mn(OH)2

Mn(OH)2 + [O]  MnO2

3. For Zn+2 Ion :

(i) White precipitate of ZnS is dissolved in dilute HCl

ZnS + 2HCl  ZnCl2 + H2S

(ii) Add NaOH drop by drop in which white precipitate reappears

ZnCl 2  2NaOH Zn( OH) 2  2NaCl


 
White ppt

(iii) This white precipitate is soluble in excess amount of NaOH.

Zn(OH)2  2NaOH  Na 2 ZnO 2  2H2O


sod. zincate

(iv) On pursing H2S gas white precipitate of ZnS reappears

Na2ZnO2 + H2S  2NaOH + ZnS


Group : V
Group basic radicals : Ba+2, Sr+2, Ca+2
Group reagent : (NH4)2CO3 in presence of NH4OH

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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.

MgCl2  Na 2HPO 4  NH4 OH  Mg(NH4 )PO 4  2NaCl  H2O



Mag. amm. phosphate
(white ppt.)

Result : Mg(NH4)PO4 - White precipitate


Confirmatory Test : Above reaction itself confirms Mg+2 ion.

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Group : Zero

Group basic radical : NH4+

Group reagent : NaOH

Procedure : Take salt and heat it with NaOH, solution starts evolving ammonia.

NH4Cl + NaOH — NaCl + NH3 + H2O

Result : Formation of NH3 gas.

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

NH3 + HCl — NH4Cl

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.

HCl(aq) + NaOH(aq)  NaCl(aq) + H2O(l) H = –13.7 kcal

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

H+(aq) + OH–(aq)  H2O(l) H = –13.7 kcal

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.

KCl(s) + H2O  KCl(aq) H = +44.0 kcal

HCl(g) + H2O  HCl(aq) H = –39.3 kcal

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PREPARATION OF LYOPHILIC AND LYOPHOBIC SOLS


Preparation of lyophilic sols : Substances which are termed as intrinsic colloids such as gelatin, rubber,
starch etc. are converted into colloidal solution when warmed with water or some other suitable solvent. The colloidal
solution thus obtained are called lyophilic sols. Such sols are reversible and quite stable.

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.

(a) Condensation method

Condensation method

Physical method Chemical methods


Double
(1) As2O3 + 3H2S As2S3 + 3H2O
Decomposition (sol)
Oxidation
Exchange of solvent Excessive cooling (2) SO2 + 2H2S 3S + 2H2O
(sol)
When a true solution is mixed A sol of ice in CHCl3 (3) FeCl + 3H O Hydrolysis
Fe(OH)3 + 3HCl
3 2
with an excess of other solvent or ether by freezing (sol)
in which the solute is insoluble the water in the (4) 2AuCl3 + 3SnCl2 Reduction 3SnCl4 + 2Au
but solvent is miscible (sol)
solvent

(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.

Detection of functional group


1. Test for alcoholic group
(i) Sodium test : Take 3-4 ml of organic compound in test tube. Add a thin slice of sodium metal. A
brisk effervescence due to the evolution of H2 gas takes place (organic compound should be free
from water)
2ROH + Na  2RONa + H2
(ii) Ester test : Warm the given liquid with acetic acid in presence of sulphuric acid. A fragrant (smell
indicates the formation of ester.

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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2. Test for carboxylic group


(i) Litmus test : Place a small quantity of organic compound or its aqueous solution on a piece of moist
blue litmus paper. It paper turns red carboxylic acid my be present.
(ii) Sodium bicarbonate test : Add a small quantity of organic compound to about 5 ml of sodium
bicarbonate solution taken in a test tube. Compound dissolves with brisk effervescences.
(iii) Take a small quantity of organic compound and add 4-5 ml of alcohol in a test tube. Add a few drops
of conc H2SO4 and warm on a water bath. A fruity smell indicates the presence of an ester.
H SO
RCOOH  R  OH 2 
4
 RCOOR  H2 O
Ester

3. Test for Amino group


(a) Test for primary amine
(i) Carbylamine test : Heat the organic compound with alcoholic KOH and chloroform in a test
tube. A highly offensive smell is evolved due to formation of isocyanides.
RNH2 + CHCl3 + 3KOH  R–NC + 3KCl + 3H2O
This test is applicable to aliphatic and aromatic primary amines.
(ii) Dye test : The test is applicable only for aromatic primary amines dissolve a small amount of
organic compound in dil HCl. Cool it in ice cold water add cold solution of sodium nitrite with
constant shaking and then add -naphthol prepared in NaOH solution. An orange-red dye is
obtained.
NaNO2 + HCl  HNO2 + HCl

NH2 N2Cl

+ HNO2 + HCl + 2H2O

OH OH

N2Cl– + N=N + HCl

-naphthol (Orange red dye)

(b) Test for Secondary amines


Liebermann’s nitroso test : Dissolve some organic compound in 3 ml of conc HCl and then add
2-3 ml of water. Cool the solution in ice cold water and then add 3-4 ml of cold dilute NaNO2 solution.
A white or yellowish emulsion is produced. Take 4-5 drops of above emulsion in test tube. Add 4-5
drops of phenol and conc. H2SO4. A blue colour develops. Addition of water changes blue colour to
red which again changes to blue on adding NaOH solution.
4. Test for aldehyde group
(i) Schiff’s test : Takes 5 mL of Schiff reagent in a test tube and shake with organic compound (do not
heat). A pink colour is formed within two minutes.
(ii) Fehling’s test : Mix equal volumes of Fehling’s (A) and Fehling’s (B) solution in a test tube. Add a
small amount of the organic compound and boil for sometime. A red precipitate of Cu2O is obtained
RCHO  2CuO  RCOOH  Cu2 O 
Red
(iii) Tollen’s test : Take about 5 ml of tollen’s reagent in a test tube add a small quantity of organic
compound and heat on a water bath. A shining silver mirror is formed on inner walls of the test tube.

RCHO + 2[Ag(NH3)2]OH + H2O  RCOONH4 + NH3 + 2NH4OH + 2Ag 


silver mirror
(iv) Benedict’s test : Take 4-5 ml of Benedict's reagent in a test tube add a few ml of the organic
compound. Heat the mixture to boiling. Formation of red ppt indicates the presence of aldehyde.
RCHO + 2Cu(OH)2 + NaOH  Cu2O + RCOO– Na+ + 3H2O

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5. Test for ketonic group


(i) Ketones unlike aldehyde do not restore the pink colour of Schiff’s reagent nor do they reduce Fehling
solution or ammonical AgNO3 solution. However they form crystalline precipitate with 2, 4-dinitrophenyl
hydrazine and also with sodium bisulphide reagent.
NO2 NO2
R R
C=O + H2N NH NO2 C=N NH NO2
R R
R R OH
C=O + NaHSO3 C
R R SO3Na
(bisulphite addition
compound)

(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.

(NH4 )2 [Ce(NO3 )6 ]  2C 6H5 OH  [Ce(NO3 ) 4 (C 6H5 OH)2 ] 2NH4NO3


Green or brown ppt

(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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PREPARATION OF ANILINE YELLOW


It is prepared by the coupling of benzene diazonium chloride with aniline in fairly acidic medium (pH 4 – 5)
at a temperature below 5°C. Its colour is yellow.
Chemical reaction

 5C
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

CI3CHO + NaOH  CHI3   HCOONa


yellow ppt

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.

NH2 NHCOCH3 NHCOCH3 NHCOCH3


(CH3CO)2O conc. HNO3 + Conc. H2SO4 NO2
+
o-nitroacetanilide
(minor) NO2
p-nitroacetanilide
(major)

Preparation of Mohr’s salt :


Mohr’s salt is prepared by dissolving an equimolar mixture of hydrated ferrous sulphate and ammonium
sulphate in minimum amount of water containing a little sulphuric acid. On vapourising the resulting solution
to crystallisation point and then keep it aside for cooling, a green crystal of ferrous ammonium sulphate
separate out.
FeSO4 · 7H2O + (NH4)2 SO4  FeSO4 · (NH4)2SO4 · 6H2O + H2O

Preparation of Potash Alum


When a solution containing an equimolar quantities of potassium sulphate and aluminium sulphate is heated
to crystallisation point and then cooled slowly colourless crystal of potash alum separate out.
K2SO4 + Al2(SO4)3 + 24H2O  K2SO4 · Al2(SO4)3 · 24H2O

SOME TYPICAL REDOX TITRATIONS


(1) Titration of oxalic acid against KMnO4 : Oxalic acid (COOH)2 · 2H2O is titrated against KMnO4 in the
presence of dilute H2SO4 keeping the temperature of oxalic acid solution between 60 – 70°C. Oxalic acid
on oxidation with acidified KMnO4 produces CO2 according to the reaction.

2MnO 4  5C 2O 24  16H  2Mn2  10CO 2  8H2 O


2 mol 5 mol

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

2KMnO 4  3MnSO 4  7H2O  K 2SO 4  5MnO 2  H2O  2H2SO 4


brown ppt

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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Principles Related to Practical Chemistry JEE/NEET

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

5Fe 2  MnO 4  8H  Mn 2   5Fe 3   4H2O


5 mol 1 mol

No. of moles of KMnO 4 1


Stroichiom etric ratio  
No. of moles of Mohr salt 5

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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