23

CHAPTER

Salt Analysis

Fe3+ + SCN– [Fe(SCN)]2+ or Fe(SCN)3

DETECTION OF EXTRA ELEMENTS        Blood red
Nitrogen, sulphur, halogens and phosphorus present in an organic If sodium fusion is carried out with excess of sodium, then
compound are detected by “Lassaigne’s test”. The elements thiocyanate decomposes to yield cyanide and sulphide. These ions
present in the compound are converted from covalent form into the give their usual tests.
ionic form by fusing the compound with sodium metal. Following NaSCN + 2Na NaCN + Na2S
reaction take place:
Na + C + N  ∆
→ NaCN Test for Halogens
∆
2Na + S  → Na2S (i) The sodium fusion extract is acidified with nitric acid and
Na + X  ∆
→ NaX then treated with silver nitrate. A white precipitate, soluble
C, N, S and X come from organic compound. in ammonium hydroxide shows the presence of chlorine,
a yellowish precipitate; sparingly soluble in ammonium
Cyanide, sulphide and halide of sodium so formed on sodium hydroxide shows the presence of bromine and a yellow
fusion are extracted from the fused mass by boiling it with distilled precipitate, insoluble in ammonium hydroxide shows the
water. This extract is known as sodium fusion extract. presence of iodine.
X– + Ag+ AgX
Test for Nitrogen
X represents a halogen: Cl, Br or I.
The sodium fusion extract is boiled with iron (II) sulphate and
then acidified with concentrated sulphuric acid. The formation of If nitrogen or sulphur is also present in the compound, the
Prussian blue color confirms the presence of nitrogen. Sodium sodium fusion extract is first boiled with concentrated nitric
cyanide first reacts with iron (II) sulphate and forms sodium acid to decompose cyanide or sulphide of sodium formed
hexacyanoferrate (II). On heating with concentrated sulphuric during Lassaigne’s test. Otherwise these ions would interfere
acid, some iron (II) ions are oxidised to iron (III) ions which with silver nitrate test for halogens.
react with sodium hexacyanoferrate (II) to produce iron (III)
hexacyanoferrate (II) (ferriferrocyanide) which is Prussian blue (ii) Beilstein’s test
in colour. Heated over

Organic compound Copper wire
Green flame, confirms the
6CN– + Fe2+ [Fe(CN)6]4–
presence of halogen in the organic compound.
H O
3[Fe(CN)6]4– + 4Fe3+ 
2
→ Fe4 [Fe(CN)6]3
(Prussian blue)
Train Your Brain
Test for Sulphur
(i) The sodium fusion extract is acidified with acetic acid and
lead acetate is added to it. A black precipitate of lead sulphide Example 1: The Lassaigne’s extract is boiled with conc.
indicates the presence of sulphur. HNO3 while testing for halogens. By doing so it:
S2– + Pb2+ PbS Sol. Decomposes Na2S and NaCN, if formed.
          Black Explanation: Sodium extract (Lassaigne’s extract) is
(ii) On treating sodium fusion extract with sodium nitroprusside, boiled with dilute HNO3 before testing for halogens to
appearance of a violet colour further indicates the presence decompose NaCN or Na2S present in the Lassigne’s extract
of sulphur. otherwise these will produce ppt. with AgNO3 and would
S2– + [Fe(CN)5NO]2– [Fe(CN)5NOS]4– thus interfere with the test halogens.
             Violet Example 2: The sodium extract of an organic compound
In case, nitrogen and sulphur both are present in an organic on acidification with acetic acid and addition of lead acetate
compound, sodium thiocyanate is formed. It gives blood red solution gives a black precipitate. The organic compound
colour and no Prussian blue since there are no free cyanide ions. contains:
Na + C + N + S NaSCN
 (iii) Oxidation test: Take some organic compound, 5 mL
(1) nitrogen (2) halogen of K2Cr2O7, solution and 2–3 mL of conc. H2SO4 in
(3) sulphur (4) phosphorus a test-tube. Heat the test-tube after fitting a delivery
tube. The distillate is passed into another test-tube
Sol. Lead sulphide is black containing water. Test the aqueous solution of the
Pb 2 + + Na 2S → PbS + 2Na +
distilalte for aldehyde group. A positive test indicates
black the presence of primary alcoholic group in the given
compound.
[O]
RCH2OH → RCHO + H2O
(iv) Ceric ammonium nitrate test: Shake a few drops
Concept Application of ceric ammonium nitrate with 1 mL of the organic
compound. A red colour is produced (Phenols give a
green or brown colour).
1. When N and S both are present in an organic
2ROH + (NH4)2[Ce(NO3)6] → [Ce(NO3)4(ROH)2]
compound, the sodium extract with FeCl3 gives:
+ 2NH4NO3
(1) green colour (2) blue colour
(3) yellow colour (4) red colour Distinction Between Primary, Secondary and
2. The blood red colour in the combination test of
Tertiary Alcohols
nitrogen and sulphur in organic compound is due to Lucas test: Add 3–4 drops of alcohol to 2 mL of Lucas reagent
the formation of: (anhydrous ZnCl2 + conc. HCl) in a test-tube. Shake the mixture
and allow to stand at room temperature. If a cloudy precipitate
(1) ferric sulpho cyanide (2) ferric acetate is obtained immediately then it is a tertiary alcohol, if obtained
(3) ferrous sulpho cyanide (4) ferric cyanide after 2–3 minutes then it is a secondary alcohol, while no cloudy
3. The violet colour obtained during the test of sulphur precipitate even after long standing means it is a primary alcohol.
by Lassaigne’s test is due to the formation of:
(b) Tests for phenolic group
(1) Na2[Fe(CN)5S] (2) Na2[Fe(CN)5NO]
(i) Litmus test: Place a trace of the organic compound on
(3) Na2[Fe(CN)6] (4) Na4[Fe(CN)5NOS] the moist blue litmus paper. It turns red.
(ii) Neutral FeCl3 test: When phenols are treated with
neutral ferric chloride solution, they form coloured
complexes. The colour of the complex may be violet,
DETECTION OF THE FOLLOWING red, blue or green. This is a characteristic reaction
FUNCTIONAL GROUP of compounds having enolic group. (= C—OH). All
enols respond to this test.

—
Detection of Functional Groups With relatively milder oxidizing agents such as ferric
chloride (Fe3+) a resonance stabilized phenoxyl radical
Detection of functional groups is an important step in the is formed. This radical soon undergoes dimerization
analysis of organic compounds. It largely depends on the correct which may take place by ortho-ortho, ortho-para, para-
determination of the constituent elements. para coupling reaction.
(a) Hydroxyl group OH O O O O
H H

Alcohols may be considered as neutral compounds. They
+ Fe3+
are soluble in water or dioxane.
H
(i) Sodium test: Take 3 – 4 mL of the organic compound Fe+ + H+
in a test-tube. Add a thin slice of sodium metal. A brisk O O O
H
H H
effervescence due to the evolution of hydrogen takes
place. (Organic compound should be free from water). + O O + O
H HH
2ROH + 2Na → 2RONa + H2↑
The phenoxyl radicals are highly coloured and therefore, products
(ii) Ester test: Warm the given liquid with acetic acid in
are also coloured.
presence of sulphuric acid. A fragrant smell indicates
the formation of ester. (iii) Aniline Dye test: Dissolve a little aniline in dilute
hydrochloric acid, cool in ice-cold water and add
ROH + CH3COOH 
2 4 H SO
→ RCOOCH3 + H2O aqueous solution of sodium nitrite dropwise. To
this cold solution, add organic compound already
Alcohols give crystalline esters with 3,5-dinitrobenzoyl dissolved in sodium hydroxide solution. A red or
chloride. These esters have sharp melting points and orange precipitate is obtained.
can be used for testing a given alcohol. NaNO2 + HCl → HNO2 + NaCl

Salt Analysis 161

  CuSO4.5H2O + Na2CO3 + Na3C6H5O7
Cl Benedict's
0°C Copper sulfate sodium Sodium
NH2 + HNO2 + HCl N ≡ N + 2H2O Reagent
pentahydrate carbonate citrate
In Benedict test also, Cu2+ ions are reduced to Cu+ ions
Cl in the same manner as in the case of Fehling’s reagent.
NaOH
N ≡ N+ OH –NaCl N=N OH 
H O O O
–H2O

—
—
—

—
—
Benzenediazonium Phenol p-hydroxy azobenzene (dye) + Cu (citrate)22– + Cu2O(s)
chloride C C

—
(iv) Phthalein test (Fluorescein test): Heat gently some R R
organic compound and phthalic anhydride with a An aldose Benedict's reagent Carboxylate Brick-red
few ml of conc. sulphuric acid in a test-tube. Pour (blue solution) anion precipitate
the heated mixture to about 50 ml of water taken in (iv) Tollen’s test
a beaker and then add sodium hydroxide solution till Tollens' test, also known as silver-mirror test, because
it became alkaline. A beautiful pink or purple colour when silver ion is get reduce to silver it get precipitate
appears. and produce mirror like image.
Tollens' test is used as a test to distinguish between an
OH OH aldehyde and a ketone. Tollens' reagent is a colorless,
C= O H2SO4 C +H2O basic, aqueous solution containing silver ions
+ coordinated to ammonia [Ag(NH3)2]+. And consist
O=C —O OH O=C O OH of Ag+ ions which reduce to Ag when treated with
aldehyde, and aldehyde get oxidise to carboxylic acid.
Aqueous silver nitrate which consist of silver ion
O–Na+
2NaOH in +1 oxidation state is mixed with aqueous sodium
C
hydroxide.
O AgNO3 + NaOH → AgOH + NaNO3
O=C–O–Na+
 (pink or purple) 2AgOH → Ag2O + H2O
Now aqueous ammonia is added drop-wise until the
(v) Bromine water test: Take aqueous or alcoholic precipitated silver oxide completely dissolves.
solution of the organic compound in a test-tube. Add
Ag2O + 4NH3 + H2O → 2Ag(NH3)+2 + 2OH–
excess of bromine water. A yellowish white precipitate
is obtained. Tollens' reagent oxidizes an aldehyde into the
corresponding carboxylic acid.
(c) Tests for aldehyde group O O
(i) Schiff test: Take 5 ml of Schiff’s reagent in a test-tube
—
—

—
—
and shake with organic compound (do not heat). A C + 2Ag+ + 2OH C + 2Ag + H2O
—
—

—
—
pink colour is formed within two minutes. CH3 H CH3 OH
(ii) Fehling’s test: Fehling reagent comprises of two The reaction is accompanied by the reduction of silver
solutions, Fehling solution A and Fehling solution ions in Tollens' reagent into metallic silver, which, if
B. Fehling solution A is aqueous copper sulphate the test is carried out in a clean glass test tube, forms a
and Fehling solution B is alkaline sodium potassium mirror on the test tube.
tartarate (Rochelle salt). These two solutions are mixed (d) Tests for carboxylic group
in equal amounts before test.
(i) Litmus test: Place a small quantity of the organic
R—CHO + 2CuO → RCOO– + Cu2O↓ (Fehling's) compound or its aqueous solution on a piece of moist
             (Red) blue litmus paper. If the paper turns red, carboxylic
Ketones are not easily oxidised, thus they do not reduce group may be present.
Fehling's solution or Tollen's reagent. But a-hydroxy (ii) Sodium bicarbonate test: Add a small quantity of the
ketones (compounds containing the unit organic compound to about 5 mL sodium bicarbonate
–CH(OH)—C—R) readily reduce the compounds solution taken in a test-tube. Compound dissolves with
brisk effervescences.
—
—

O RCOOH + NaHCO3 → RCOONa + H2O + CO2↑

which respond to the test.
(iii) Take a small quantity of the organic compound and
(iii) Benedicts test: Benedict modified the original Fehling’s add 4–5 mL of alcohol in a test-tube. Add a few drops
test by using a single solution which is more convenient of conc. sulphuric acid and warm on a water bath. A
for the test. Benedict’s solution is more stable than fruity smell indicates the presence of an ester.
Fehling’s reagent and can be stored for a long time. It H SO
is an alkaline solution containing a mixture of copper RCOOH + R’OH 2 4 RCOOR’ + H2O
sulphate and sodium citrate (2Na3C6H5O7 .11H2O). Ester

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 (e) Test for amino groups in organic compounds
Tests for primary amines(–NH2) Diazonium salts are unstable and lose nitrogen as
N2 gas on heating. Hence during fusion, no sodium
(i) Carbylamine test: Heat the organic compound with cyanide is formed in Lassaigne’s extract due to the
alcoholic KOH and chloroform in a test-tube. A loss of nitrogen.
highly offensive smell is evolved due to formation of
isocyanides.
RNH2 + CHCl3 + 3KОН → R—NC + 3KCl + 3H2O
This test is applicable to aliphatic and aromatic primary
amines. Concept Application
(ii) Dye test: This test is applicable only for aromatic
primary amines. Dissolve a small amount of the organic 4. A nitrogenous compound on reaction with Zn dust and
compound in dil. HCl. Cool it in ice-cold water. Add NH4Cl gives a derivative which gives a grey black
cold solution of sodium nitrite with constant shaking silver with Tollen’s reagent. The functional group in
and then add b-naphthol prepared in NaOH solution. nitrogenous compound is:
An orange-red dye is obtained. (1) —NO (2) —NO2
NaNO2 + HCl → HNO2 + NaCl (3) —NHOH (4) —CONH2
Cl NH2 NH2
NH2+HNO2+HCl N≡N+2H2O
5. and can be differentiated by:
O– O–
Cl
N≡N+ N=N (1) carbylamine reaction
+HCl (2) H2SO4
(3) diazotisation followed by b-naphthol
b–naphthol (Orange–red dye) (4) mustard oil reaction
Tests for secondary amines (–NH–) OH OH
Liebermann’s nitroso test: Dissolve some organic 6. COOH COOCH3
compound in 3 mL of conc. HCl and then add 2–3 mL of and
water. Cool the solution in ice-cold water and then add
3–4 mL of cold dilute NaNO2 solution. A white or yellow can be differentiated by:
emulsion is produced. Take 4–5 drops of the above emulsion (1) NaOH (2) Na metal
in a test tube. Add 4–5 drops of phenol and conc. H2SO4. A
(3) NaHCO3 (4) FeCl3
blue colour develops. Addition of water changes blue colour
to red which again changes to blue on adding NaOH solution.

Train Your Brain INORGANIC COMPOUNDS

When a mixture containing equimolar proportions of potassium
Example 3: Give two distinction test between Phenol and sulphate and aluminium sulphate or ferrous sulphate and
Alcohol. ammonium sulphate is crystallsed from its solution, a double salt
Sol.
Ferric chloride test: Phenol gives violet colour with is formed. The formation of double salt may be shown as follows:
FeCl3 but alcohols do not.
K2SO4 + Al2(SO4)3 + 24H2O K2SO4. Al2 (SO4)3. 24H2O or
3C6H5OH + FeCl3 (C6H5O)3 Fe + 3HCl 2KAl (SO4)2.12H2O   (Potash alum)
Phenol Ferric phenoxide (violet)
FeSO4 + (NH4)2SO4 + 6H2O FeSO4 (NH)2SO4. 6H2O
C2H5OH + FeCl3 No effect
Ferrous ammonium sulphate (Mohr’s salt)
Bromine water test: On shaking phenol with Br2 water
2+ 3+
Fe and Al ions undergo hydrolysis, therefore, while preparing
we get white precipitate of 2, 4, 6-tribromophenol
while alcohols do not give this test. aqueous solutions of ferrous sulphate and aluminium sulphate
Example 4: Hydrazine and diazonium salts do not give in water, 2–3 mL dilute sulphuric acid is added to prevent the
Lassaigne’s test. Why? hydrolysis of these salts.
Sol. In the Lassaigne’s test, nitrogen is converted to 1. Mohr’s Salt
cyanide by combining with carbon of the compound. Preparation of Double Salt: Ferrous Ammonium (Mohr’s salt)
Hydrazine does not contain carbon and hence, cyanide
cannot be formed. (i) Dissolve 3.5 g of ferrous sulphate and 1.7 g of ammonium
sulphate (weighed separately), in 5 mL of distilled water

Salt Analysis 163

 contained in a 50 mL conical flask by heating. Add about Material Required
0.5 mL of dilute sulphuric acid to the flask and concentrate • Funnel One
the solution by heating till the crystallization point is
reached. • Round bottomed flask (100 mL) One
(ii) Allow the mixture to cool to room temperature slowly. • Beaker (250 mL) One

(iii) On cooling, light green crystals of ferrous ammonium • Air condenser One
sulphate separate out. • Sand bath One
(iv) Decant the mother liquor and wash the crystals by shaking • Clamp and iron stand One
with very small amounts of 1:1 cold water and alcohol • Pumice stone One
mixture to remove sticking mother liquor. • Melting point assembly One
(v) Separate the crystals by filtration wash with alcohol, dry • Aniline 5 mL
between the folds of a filter paper and record the yield.
• Acetic anhydride/Acetyl chloride 5 mL
2. Potash Alum • Acetic acid/Pyridine 5 mL
Preparation of Double Salt: Potassium Aluminium Sulphate
(Potash Alum) Procedure
(i) Take 10 mL of distilled water in a 50 mL beaker and heat (1) Take 5 mL of aniline in a 100 mL round bottom flask and
it to about 40°C. Dissolve 6.6 g of aluminium sulphate in it add acetylating mixture containing 5 mL acetic anhydride
and add about 0.4 mL of dilute sulphuric acid. and 5 mL glacial acetic acid. Alternatively, you can use
5 mL of acetyl chloride and 5 mL of dry pyridine as the
(ii) Weigh 2.4 g of powdered potassium sulphate and transfer it
acctylating mixture.
to the above solution.
(ii) Fit an air condenser on the mouth of the round bottom
(iii) Heat the solution with constant stirring till potassium
flask after adding a few pumice stones and reflux the
sulphate dissolves completely.
mixture gently for 10-15 minutes on a sand bath.
(iv) Allow the solution to cool to room temperature slowly.
(iii) Cool the reaction mixture and pour it slowly in 150-200 mL
(v) On cooling, white crystals of potash alum separate out. of ice cold water with stirring.
(vi) Decant the mother liquor and wash the crystals by gently (iv) Filter the solid, wash it with cold water and recrystallise
shaking with 1:1 cold water and alcohol mixture. a small amount of sample from hot water containing a
(vii) Filter the crystals, dry these between the folds of a filter few drops of methanol or ethanol.
paper and note the yield. (v) Report the yield and the melting point of the compound.
Precautions Precautions
(a) Cool the solution slowly to get good crystals. Avoid rapid (a) Handle acetic anhydride and acetyl chloride carefully as
cooling. they cause irritation to the eyes and acetyl chloride also
(b) Do not disturb the solution while cooling. strongly fumes in air.
(c) Avoid prolonged heating while preparing crystals of ferrous (b) Store acetylchloride under dry conditions.
ammonium sulphate, as it may oxidise ferrous ions to ferric (c) Handle pyridine with extreme caution. Dispense it in an
ions and change the stoichiometry of the crystals. efficient fume cupboard and wear disposable glasses while
using it.
ORGANIC COMPOUNDS (d) Distil pyridine before use because it absorbs mioisture and
the reaction does not take place under moist conditions.
1. Acetanilide (e) Wash the solid 2-3 times with cold water till the filtrate is
Theory neutral to litmus.
The replacement of one hydrogen atom of the –NH2 group of (f) Determine the melting point of perfectly dried and
aniline by CH3CO– group in the presence of glacial acetic acid recrystallised sample.
gives acetanilide. In the laboratory, acetylation is usually carried
out with acetic anhydride. Acetyl chloride may also be used for 2. p-nitro acetanilide
the purpose of acetylation if acetic anhydride is not available. Theory
Acetylation with CH3COCl is usually carried out in the presence p-Nitroacetanilide is prepared by the nitration of acetanilide by
of pyridine. using a mixture of conc. nitric acid and conc. sulphuric acid as
CH3COCl nitrating reagent. The mixture of the two acids releases nitronium
NH2 NHCOCH3 ion (NO+2) which acts as an electrophile in the reaction.
Pyridine
Aniline HNO3 + 2H2SO4 NO+2+ H3O+ + 2HSO–4

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Nitronium ion attacks the benzene ring containing anilide group, 3. Aniline yellow
mainly at the para position to give p-nitroacetanilide as a major Theory
product. This is an example of aromatic electrophilic substitution p-aminoazobenzene can be prepared in a good yield by
reaction. rearrangement reaction of diazoaminobenzene with a small
Conc. HNO3 quantity of aniline hydrochloride in the presence of aniline as
NHCOCH3 Conc. H2SO4 O2N NHCOCH3 solvent. The chemistry of this conversion is as follows:

Acetanilide p-nitroacetanilide
HCl +
(Major product) N == N — NH N2Cl– + NH2

Material Required Diazoaminobenzene Benzenediazonium Aniline

chloride
• Beaker (100 mL) One
• Funnel One +
N2Cl– + NH2 N=N NH2
• Glass rod One
Aniline Aniline yellow
• Ice bath One (in excess) (p-Aminoazobenzene)
• Acetanilide 2g The above reaction is carried out only in weakly acidic conditions.
• Glacial acetic acid 2 mL Material Required
• Conc. H2SO4 5 mL • Conical Flask (100 mL) One
• Ice As per requirement • Thermometer One
• Funnel One
• Ethanol/methanol As per requirement
• Melting point assembly One
Procedure • Waterbath One
• Diazoaminobenzene 3g
(i) Dissolve 2 g of acetanilide in 2 mL of glacial acetic acid
• Aniline 7 mL
taken in a 100 mL beaker.
• Aniline hydrochloride 1.5 g
(ii) Add 4 mL of conc. H2SO4 gradually with stirring to the • Glacial acetic 9 mL
above mixture. The mixture becomes hot and clear solution
is obtained. Cool the reaction mixture in an ice bath Procedure
maintained at 0–5°C. (i) Dissolve 3 g of finely powdered diazoaminobenzene in
7 mL of aniline in a 100 mL conical flask.
(iii) Add a cold mixture of 1.0 mL conc, HNO, and 1.0 mL
(ii) Add 1.5 g of finely powdered aniline hydrochloride to the
conc. H2SO4 to the viscous reaction mixture drop by drop above mixture.
with constant stirring, so that the temperature of the mixture
(iii) Warm the mixture with occasional shaking on a water bath
does not rise above 10°C. at about 40-45°C, for a period of about one hour.
(iv) Remove the beaker from the ice bath and allow the reaction (iv) Remove the flask from the water bath and allow the reaction
mixture to attain room temperature. Let it stand at room mixture to stand at room temperature for about 30 minutes.
temperature for about 30 minutes. Stir the reaction mixture (v) Add 9 mL of glacial acetic acid diluted with an equal
continuously and pour it on 100g of crushed ice. volume of water and shake the reaction mixture thoroughly
to convert excess aniline to its acetate, which is water-
(v) Stir the mixture well and filter the compound so obtained. soluble.
(vi) Wash the compound with cold water and dry it. (vi) Allow the mixture to stand for 15 minutes with occasional
stirring.
(vii) Recrystallise a small amount of the pale yellow solid (vii) Filter p-aminoazobenzene, wash with a little cold water
from alcohol. Colourless crystals of p-nitroacetanilide are and dry between the folds of a filter paper.
obtained. Yellow ortho-nitroacetanilide formed in the small (viii) Recrystallise a small portion of crude p-aminoazobenzene
amount remains dissolved in the mother liquor. from carbon tetrachloride.
(viii) Record the yield and melting point of the pure compound. (ix) Report the yield and melting point of p-aminoazobenzene
Precautions
Precautions
(a) Maintain the temperature of the reaction mixture at about
(a) Do not allow the temperature of the reaction mixture to 40-50°C.
exceed 10°C during addition of nitrating mixture.
(b) Wash the crude product with a small volume of water
(b) Add mixture of concentrated nitric acid and sulphuric acid repeatedly.
into the solution of acetanilide slowly and carefully. (c) Note the melting point of the perfectly dry sample.

Salt Analysis 165

4. Iodoform change at pH close to the equlvalence point. We will discuss here
Theory about only two indicators - phenolphthalein and methyl orange.
Reaction involved in the formation of iodoform is as follows: 1. Phenolpthalein
2C2H5OH + 8I2 + Na2CO3 + H2O→ 2 “iodoform” + 2HCO2Na Phenolpthalein is a weak acid, therefore it does not dissociate in
+ CO2 + 10HI the acidic medium and remains in the unionised form, which is
“iodoform” + HEAT → Decomposition Products colourless.
HPh  H+ + Ph–
Preparation
Unionised Ionised
(i) You will be given a sample of I2 (iodine), approximately
Colourless Pink
1 gram, in a vial. Pour this into a beaker. Add 10 mL of 30%
Na2CO3 solution. Add 10 mL of water. Finally, add 3 mL of Ionised and unionised forms of phenophthalein are given below:
C2H5OH (ethanol). HO HO
(ii) Stir the mixture with a wooden stick. Gently heat it on a
beaker to the point of boiling, then let it cool (do NOT boil C OH–
it dry! This can fill the room with fumes!). H+
O
(iii) The mixture should start off brown but will turn bright yellow
when the reaction is complete. C

(iv) Collect the yellow product on filter paper, and allow to dry O
on pad of paper towels. The liquid from this filtration can (Colourless in acid)
be safely disposed of down the drain with large amounts of O O O–
O
running water.

C C
TITRATION
O–
Titrimetric analysis involves determination of the volume of a C O C
O
solution of accurately known concentration, which is required O–
to react quantitatively with the measured volume of the solution
 (Pink in alkali)
of a substance, concentration of which is to be determined. The
solution of accurately known concentration is called standard Phenolphthalein in acidic and basic medium
solution. The mass of the substance dissolved in the solution In the acidic medium, equilibrium lies to the left. In the alkaline
of unknown concentration is calculated from the volume of the medium, the ionisation of phenolphthalein increases considerably
standard solution used, the chemical equation and the relative due to the constant removal of H+ ions released from HPh by the
molecular masses of the reacting compounds. The reagent of OH– ions from the alkali. So the concentration of Ph– ion increases
known concentration is called titrant and the substance being in the solution, which imparts pink colour to the solution.
titrated is termed as titrand. HPh  H+ + Ph–
To carry out titrimetric analysis, standard solution is usually added NaOH → Na+ + OH–
from the long graduated tube called burette. The process of adding
H+ + OH– → H2O
the standard solution to the solution of unknown concentration
For a weak acid vs strong alkali titration, phenolphthalein is
until the reaction is just complete is called titration. The point
the most suitable indicator. This is so because the last drop of
at which reaction is completed is called equivalence point or the
added alkali brings the pH of the solution in the range in which
theoretical or stoichiometric end point. It is not possible all the
phenolphthalein shows sharp colour change.
time to take standard solution in the burette.
2. Methyl Orange
Acids and Bases
Methyl orange is a weak base and is yellow in colour in the
Titrimetric analysis can be performed on a variety of reactions. unionised form. Sodium salt of methyl orange is represented as
Titrations of bases and acids take place. In these titrations, follows:
standard solutions of acids (acidimetry) and bases (alkalimetry)
are utilized. The concentration of a solution is expressed in terms CH3
Na+–O3S N == N N
of the molarity in quantitative estimate via titrimetric analysis. It CH3
is the amount of solute dissolved in one liter of solution. The anion formed from the indicator is an active species, which
on accepting a proton (i.e acting as Bronsted Lowry base) changes
The use of Indicators in Acid Base Titration from the benzenoid form to the quinonoid form. The quinonoid
Acid base indicators are sensitive to pH change. For must acid base form is deeper in colour and thus is responsible for the colour
titrations, it is possible to select indicators which exhibit colour change at the end point. This is illustrated in the following manner:

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 CH3 B. Ionic equation
+Na–O3S N == N N
CH3 Reduction half reaction:
Benzenoid form in basic solution MnO4– + 5e– + 8H+ Mn2+ + 4H2O] × 2
(Yellow in colour)
CH3 Oxidation half reaction:
H+ ⊕
HO3S NH—N N
CH3 C2O42– 2CO22 +2e–] ×5
(Bronsted Lowry base) Quinonoid form in acidic solution 2MnO4– + 5C2O2–
4 + 16H
+ 2Mn2+ + 10CO2 + 8H2O
(Pinkish red in colour)
In these equations, MnO–4 is reduced to Mn2+ and C2O2–4 is oxidised
to CO2. The oxidation number of carbon in C2O2–4 changes from
Choice of Indicator +3 to +4.
Methyl orange is used as an indicator in the titration of a strong
In these titrations, potassium permanganate acts as a self- indicator.
acid and a weak base. When titration between strong base and
Initially colour of potassium permanganate is discharged due to its
mild acid is required, phenolphthalein is an excellent indicator.
In this example, alkali is dispensed from the burette, and acid reduction by oxalic acid. After complete consumption of oxalate
is collected in a tiration flask. The color of the solution in the ions, the end point is indicated by the appearance of a light pink
titration flask shifts from colorless to pink. colour produced by the addition of a little excess of unreacted
potassium permanganate. Further, during the titration of oxalic
The human eye can easily detect this change in color. If we
put alkali in the titration flask, the color will shift from pink to acid against potassium permanganate, warming of oxalic acid
colorless, and the accuracy in noticing the color change will be solution (50°– 60°C) along with dilute H2SO4 is required.
reduced. Any of the aforementioned indications can be employed
in the titration of strong acid versus strong base.
MOHR’S SALT VS KMnO4

Oxalic Acid vs KMnO4 Theory

Theory Like oxalic acid, ferrous ammonium sulphate also acts as a
reducing agent in the titration against potassium permanganate.
In the present experiment, potassium permanganate acts as a
powerful oxidising agent. Although KMnO4 acts as an oxidising The reaction which takes place is given below :
agent in alkaline medium also, for quantitative analysis mostly (a) Chemical equation
acidic medium is used. The oxidising action of KMnO4 in the Reduction half reaction:
acidic medium can be represented by the following equation:
2KMnO4 + 3H2SO4 → K2SO4 + 2 MnSO4 + 3H2O + 5[O]
MnO–4 + 8H+ + 5e– → Mn2+ + 4H2O
Oxidation half reaction :
The acid used in this titration is dilute sulphuric acid. Nitric acid

2FeSO 4 (NH 4 ) 2 6H 2 O + H 2 SO 4 + [O] → Fe 2 (SO 4 ) 3
is not used as it is itself an oxidising agent and hydrochloric acid
+ 2(NH4)2SO4 + 13H2O] × 5
is usually avoided because it reacts with KMnO4 according to the
equation given below to produce chlorine and chlorine which is
2KMnO4 + 8H2SO4 + 10FeSO4 (NH4)2SO4. 6H2O → K2SO4
also an oxidising agent in the aqueous solution. + 2MnSO4 + 5Fe2(SO4)3+ 10(NH4)2SO4 + 68H2O
2KMnO4 + 16 HCl → 2KCl + 2 MnCl2 + 5Cl2 + 8 H2O (b) Ionic equation
Since, oxalic acid acts as a reducing agent, it can be titrated against
Reduction half reaction:
potassium permanganate in the acidic medium according to the MnO–4 + 5e– + 8H+ → Mn2+ + 4H2O
following equation:
Oxidation half reaction: Fe2+ → Fe3++ e–] × 5
Reactions MnO4– + 5Fe2+ + 8H+ → Mn2+ + 5Fe3+ + 4H2O
A. Chemical equations The oxidation number of iron in Mohr’s salt is +2. Iron is
Reduction half reaction: oxidised during the reaction and its oxidation number changes
2KMnO4 + 3H2SO4 K2SO4 + 2MnSO4 + 3H2O + 5[O] from +2 to +3. In this titration heating of ferrous ammonium
60°C
sulphate solution is not required because reaction rate is very
Oxidation half reaction: H2C2O4 + [O] 2CO2 + [H2O] × 5 high even at room temperature. Also, at high temperatures,
2KMnO4 + 3H2SO4 +5H2C2O4 K2SO4 + 2MnSO4 + 8H2O ferrous ions may be oxidised to ferric ions by oxygen of air
                + 10 CO2 and error may be introduced in the experiment.

Salt Analysis 167

 PRELIMINARY TEST
Train Your Brain
1. Physical appearance (smell): Take a pinch of the sample of
salt between your fingers and rub with a drop of water.
Example 5: Write a net ionic equation between titration of Inference Smell
KMnO4 and Mohr's Salt.
NH4+ Ammonical smell
Sol. In this titration ferrous anamonium sulphate form CH COO– Vinegar like smell
3
which oxidised to ferric sulphate by acidic KMnO4. S2– Smell like that of rotten eggs
2KMnO4 + 3H2SO4 → K2SO4 + 2MnSO2 + 2. Dry Heating Test: This test is performed by heating a
3H2O + 5(O) small amount of mixture in a dry test tube. Quite valuable
10FeSO4.(NH4)2SO4.6H2O + 5H2SO4 + 5(O) information can be generated by carefully performing and
noting the observations here. On heating, some salts undergo
→ 5Fe2(SO4)3 + 10(NH4)2SO4 + 65H2O decomposition, thus evolving the gases or may undergo
Total reaction:
2KMnO4 + 8H2SO4 + 10Fe2SO4. characteristic changes in the colour of residue. These
observations are tabulated below along with the inferences
(NH4)2SO4.6H2O → K2SO4 + 2MnSO4 +
that you can draw.
5Fe2(SO4)3 + 10(NH4)2SO4 + 68H2O Gas evolved
Example 6: Why dil H2SO4 is added in preparation of (a) Colourless and odourless gas
mohr’s salt? CO32– ion
CO2 gas – Turns lime water milky.
Sol. To stop hydrolysis of ferrous sulphate.
(b) Colourless gas with odour
� Hydrated S2– or S2– ion
H2S gas – Smells like rotten eggs, turns lead acetate
paper black.
Concept Application � SO32– ion
SO2 gas – Characteristic suffocating smell of burning
sulphur turns acidified potassium dichromate solution
7. Aqueous solution of 6.3 gm oxalic acid of 250 ml is or paper green.
prepared. What volume of 0.1 N NaOH is required for � Cl– ion
neutralisation of 10 ml oxalic acid solution?
HCl gas – Pungent smell, white fumes with ammonia,
(1) 20 mL (2) 40 mL white precipitate with silver nitrate solution.
(3) 10 mL (4) 30 mL � NH4+ ion
8. During the titration of oxalic acid vs KMnO4 which NH3 gas – Characteristic smell, turns
substance acts as an indicator. Nessler’s solution brown.
(1) Oxalic acid (2) Methyl orange (c) Coloured gas – Pungent smell
(3) KMnO4 (4) DMG � NO2– or NO3– ion
NO2 gas – Reddish brown, turns ferrous sulphate
solution brownish black.
� Cl– ion
QUALITATIVE ANALYSIS
Cl2 gas – Greenish yellow, turns starch iodide paper
blue.
Introduction � Br– ion
The detection of cations (basic radicals) and anions (acidic Br2 vapours – Reddish brown, turns starch paper
radicals) in a salt or in a mixture is known as Qualitative Analysis. orange red.
The systematic procedure for qualitative analysis of an inorganic � I– ion
salt involves the following steps: I2 vapours – Dark violet, turns starch paper blue.
(A) Preliminary tests Residue
1. Physical appearance (colour and smell). (a) Yellow when hot, white when cold.
2. Dry heating test. Eg: Zn2+
3. Flame test. (b) Brown when hot and yellow when cold.
4. Borax bead test. Eg: Pb2+
5. Charcoal cavity test. (c) Original salt blue in color becomes white on heating.
6. Charcoal cavity and cobalt nitrate test. Eg: Hydrated CuSO4 indicated
(B) Analysis of anions (acidic radicals). (d) Coloured salt becomes brown or black on heating.
(C) Analysis of cations (basic radicals). Eg: Co2+, Fe2+, Fe3+, Cu2+, Ni2+

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3. Flame test: The chlorides of the metals are more volatile In some cases, the oxides formed partially undergo reduction
as compared to other salts and these are prepared in situ by to the metallic state producing metallic beads.
mixing the compounds with a little concentrated hydrochloric For Example:
acid. On heating, in a non-luminous Bunsen flame, they are
volatilized and impart a characteristic colour to the flame as (a) ZnSO4 + Na2CO3 → ZnCO3 + Na2SO4
these absorb energy from the flame and transmit the same as ZnCO3 → ZnO (Yellow when hot, white when cold) + CO2 ↑
characteristic colour. (b) CuSO4 + Na2CO3 → CuCO3 + Na2SO4
Metal Colour of flame
CuCO3 → CuO + CO2↑
Li Crimson red
CuO + C → Cu (Reddish scales) + CO ↑
Na Golden yellow
6. Cobalt Nitrate Test: In case the residue is white in colour after
K Violet charcoal cavity test, add a drop of cobalt nitrate [Co(NO3)2]
Ca Brick red in the charcoal cavity. A drop of water is then added and the
mass is heated in an oxidising flame. It is cooled and one or
Sr Crimson red
two drops of cobalt nitrate solution is added and then again
Ba Apple green heated in the oxidising flame. Different metal salts give
Cu Greenish blue different coloured mass.
4. Borax Bead test: On heating, borax (Na2B4O7.10H2O) forms ZnSO4 + Na2 CO3 → ZnCO3 + Na2 SO4 ;
a colourless glassy bead of NaBO2 and B2O3. ZnCO3 → ZnO + CO2
∆ ∆
Na2B4O7.10H2O 
→ Na2B4O7 
→ 2NaBO2 + B2O3 2Co(NO3)2 → 2CoO + 4 NO2 + O2 ;
On heating with a coloured salt , the glassy bead forms a ZnO + CoO → ZnO.CoO (or CoZnO2)
coloured metaborate in oxidising flame.   (Rinmann’s green)
For Example: Table: 6
In oxidising flame, cobalt salts give blue bead. S.No. Metal Colour of the Mass
CoSO4 → CoO + SO3 1. Zinc Rinmann green
CoO + B2O3 → Co(BO2)2 (Blue bead) 2. Aluminium Thenard blue
3. Magnesium Pink
However, in reducing flame the colours may be different due
4. Tin Bluish-green
to different reactions.
2Co(BO2)2 + C → 2CoBO2 + B2O3 + CO
2Co(BO2)2 + 2C → 2Co (Dark Blue bead) + 2B2O3 + 2CO Train Your Brain
Colour in oxidising flame
Metal Example 7: Black precipitate is obtained when H2S gas is
When Hot When Cold passed through a solution of copper nitrate.
Cu Green Blue (1) CuS (2) Cu2S
Fe Brown yellow Pale yellow/Yellow (3) CuNO2 (4) Precipitate not
Cr Yellow Green obtained
Co Blue Blue H 2S
Sol. Cu(NO3)2  → CuS (Black ppt)
Mn Violet/Amethyst Red/Amethyst
Example 8:______ salts do not respond to borax bead test.
Ni Violet Brown/Reddish brown
(1) Cu2+ (2) Fe3+
(3) Al 3+ (4) Co2+
Colour in reducing flame
Metal 3+
When Hot When Cold Sol. Al salts do not respond to borax bead test.
Cu Colourless Brown red Borax Bead test gives mainly test of Cu2+, Co2+, Fe3+,
Fe Bottle green Bottle green Cr3+, Mn2+ ions.
Example 9: Be and Mg do not impart colour to flame.
Cr Green Green
Why?
Co Blue Blue
(1) Due to very high IE.
Mn Grey/Colourless Grey/Colourless
(2) Due to higher ionic potential.
Ni Grey Grey
(3) Due to their greater covalent character.
5. Charcoal Cavity Test: In this test metallic carbonates when (4) All of the above.
heated in a charcoal cavity decompose to give corresponding Sol. Be and Mg do not impart colour to flame due to very
oxides. The oxides appear as coloured incrustation or residue high IE.
in the cavity.

Salt Analysis 169

 Class A
Example 10: Macth the List-I and List-II. Includes anions that are identified by volatile products obtained
List-I (Metals) List-II (Colour of flame) on treatment with acids. It is further divided into two sub groups:
(a) Gases evolved with dil HCl/dil H2SO4.
A. Li p. Brick red Example: CO32–, SO32–, S2–, NO2–
B. Na q. Golden yellow (b) Gases or acid vapours evolved with conc. H2SO4.
Example: Cl–, Br–, I–, NO3
–
C. K r. Violet
D. Ca s. Crimson red Prepartion of solution for the identification of anions:
1. Preparation of Water Extract (W.E.)
(1) A–(s); B–(q); C–(r); D–(p)
All common acetates, nitrites, nitrates and thiosulphates are
(2) A–(s); B–(q); C–(p); D–(r) soluble in water. Confirmatory tests for these anions can be
(3) A–(q); B–(s); C–(r); D–(p) performed with the water extract of the mixture. Water extract
(4) A–(q); B–(s); C–(p); D–(r) can be prepared by boiling 1-2 g of the mixture with 10-15 cm3
distilled water in a boiling tube for a minute or two. Residue, if
Sol. A→s, B→q, C → r, D → p any, is filtered. The filtrate is called water extract (W.E.).
2. Preparation of Sodium Carbonate Extract (S.E.)
If the mixture is found to be partially or wholly insoluble in water, it
is boiled with saturated sodium carbonate solution. This treatment
Concept Application converts the anions present in mixture into soluble sodium salts as
a result of double decomposition. E.g.,
H O
9. In cobalt nitrate test, which coloured mass of Zn metal BaSO 4 (s) + Na 2 CO3 (aq) 
2
→ BaCO3 (s) + Na 2SO 4 (aq)
is found? H O
PbCl2 (s) + Na 2 CO3 (aq) 
2
→ PbCO3 (s) + 2NaCl(aq)
(1) Rinmann’s green (2) Crimson red
For preparing sodium carbonate extract, take 0.5-1.0 g of
(3) Violet (4) Yellow
powdered mixture, 1.0-2.0 g of sodium carbonate and 5-10 cm3
10. On heating, CO32– salts undergo decomposition, thus of distilled water in a boiling tube or a 50 ml beaker. Heat with
evolving the ‘X’ gas.Find out the characteristics of ‘X’ stirring for 5-10 minutes. Cool the contents and filter. The filtrate
gas. is called sodium carbonate extract (S.E.). This extract is used for
(1) It is coloured gas. confirming the presence of most anions except for carbonate since
sodium carbonate has been added during its preparation.
(2) It is odoured gas.
(3) It turns lime water milky. INDIVIDUAL TESTS OF ANIONS
(4) None of these.
11. Which of the following characteristics of gas is not Class ‘A’ Radicals
correct? (a) Gases evolved with dil HCl/dil H2SO4.
(1) SO2 gas – Suffocating smell of burning sulphur 1. Carbonate (CO32-)
turns acidified potassium dichromate solution or (i) Dilute HCl: A colourless, odourless gas is evolved with brisk
paper green. effervescence due to the evolution of carbon dioxide.
(2) HCl gas – Pungent smell, white fumes with CaCO3 + H2SO4 → CaSO4 + H2O + CO2↑
ammonia. Lime water/Baryta water (Ba(OH)2) test
(3) Acetic acid vapours – Characteristic vinegar like The gas gives white trubidity with lime water and baryta water.
smell. CO 2 + Ca 2 + + 2OH − 
→ CaCO3 ↓ + H 2 O

(4) NH3 gas – Characteristic smell, turns Nessler’s
solution green. CO 2 + Ba 2 + + 2OH − 
→ BaCO3 ↓ + H 2 O

12. On Heating, borax forms a colourless glassy bead On prolonged passage of carbon dioxide in lime water, the
of _______. trubidity slowly disappears due to the formation of soluble
(1) NaBO2 and B2O3 (2) Na2B4O7 hydrogen carbonate.
(3) Na2B4O7.H2O (4) B2O3 CaCO3 ↓ + CO 2 + H 2 O  → Ca(HCO3 ) 2

The following tests are then performed with aqueous salt solution.
Note:
™ Mercury (II) chloride does not form precipitate with hydrogen
ANALYSIS OF ANIONS (ACIDIC RADICALS) carbonate ions, while in a solution of normal carbonates a
reddish–brown precipitate of basic mercury(II) carbonate
Methods available for the detection of anions are not as systematic (3HgO.HgCO3 = Hg4O3CO3) is formed.
as those used for the detection of cations. Futhermore, anions are 2–
classified essentially on the basis of process employed. CO3 + 4Hg2+ + 3H2O → Hg4O3CO3 ↓ + 6H+

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 ™ Lime water test is shown by SO2 and CO2 both but CO2 does (iii) Silver nitrate solution: Black ppt. of silver sulphide
not turn filter paper soaked in acidified K2Cr2O7, green. insoluble in cold but soluble in hot dil nitric acid.
™ Soluble bicarbonates give white precipitate with MgSO4 (aq)/ S2 − + 2Ag +  → Ag 2S ↓
MgCl2(aq) only on heating. (whites)
– ∆
Mg2+ + 2HCO3 → Mg(HCO3)2  → MgCO3 ↓ + H2O + CO2 (iv) Sodium nitroprusside solution: Turns sodium
nitroprusside solution purple
(ii) Barium chloride or Calcium chloride solution: White ppt
of barium or calcium carbonate is obtained, which is soluble Na 2S + Na 2 [Fe(CN)5 NO] → Na 4 [Fe(CN)5 NOS]
in mineral acid. 4. Nitrites (NO2–)
CO32 − + Ba 2 + 
→ BaCO3 ↓ (i) Dil. HCl or Dil. H2SO4: Adding to solid nitrite in cold yield
pale blue liquid (due to the presence of free nitrous acid
CO32 − + Ca 2 + 
→ CaCO3 ↓ HNO2 or its anhydride N2O3) and the evolution of brown
(iii) Silver nitrate solution: White ppt of silver carbonate is obtained. fumes of nitrogen dioxide, the latter being largely produced
CO32 − + 2Ag + 
→ Ag 2 CO3 ↓ by combination of nitric oxide with the oxygen of the air.
(Brown and Yellow)
NO −2 + H + 
→ HNO 2
The ppt. so obtained is soluble in nitric acid and in ammonia,
the ppt. becomes yellow or brown on addition of excess 2HNO 2 
→ H 2 O + N 2 O3
reagent and same may also happend if the mix is boiled due
3HNO 2 
→ HNO3 + 2NO ↑ + H 2 O
to the formation of silver oxide.
2. Sulphites (SO32–) 2NO ↑ + O 2 ↑  → 2NO 2 ↑
(i) Dilute HCl or Dilue H2SO4: Decomposes with the Following tests are performed with an aqueous salt solution.
evolution of sulphur dioxide. (ii) Silver nitrate solution: White crystalline ppt is obtained.

SO32 − + 2H +  → SO 2 + H 2 O NO −2 + Ag + → AgNO 2 ↓

The gas has suffocating odour of burning sulphur. (iii) Turns acidified KI - starch paper blue.
(ii) Acidified potassium dichromate solution: The gas turns 2KI + 2NO 2 
→ 2KNO 2 + I 2 ↑
filter paper moistened with acidifed potassium dichromate
solution, green, due to the formation of Cr3+ ions. Starch + I 2  → Blue colour
3SO 2 + K 2 Cr2 O7 + H 2SO 4 
→ K 2SO 4 + Cr2 (SO 4 )3 (iv) Brown ring test: When the nitrite solution is added
(Green) carefully to a conc. solution of iron (II) sulphate, acidified
with dil. acetic acid or with dilute sulphuric acid, a brown
H 2 O +
(iii) Lime water: On passing the gas through the lime water, ring, due to the formation of [Fe(H2O)5NO]SO4 at the
a milky ppt is formed. junction of the two liquids is formed.
SO 2 + Ca(OH) 2  → CaSO3 ↓ + H 2 O NO −2 + CH3COOH 
→ HNO 2 + CH3COO −
(Milky)

Precipitate dissolves on prolonged passage of the gas, 3HNO 2 
→ H 2 O + HNO3 + 2NO ↑

due to the formation of soluble hydrogen sulphite ions.
Fe 2 + + SO 42 − + NO ↑ 
→[Fe(H 2 O)5 NO]SO 4
CaSO3 ↓ +SO 2 + H 2 O  → Ca(HSO3 ) 2
(iv) Barium chloride or Strontium chloride solution: Salt
solution gives white ppt of barium or strontium sulphite.
Train Your Brain
SO32 − + Ba 2 + → BaSO3 ↓
(whites)

SO32 − + Sr 2 + → SrSO3 ↓ Example 11: Which of the following metal carbonates

(whites) liberate CO2(g) on heating?
2–
3. Sulphide (S ) (1) Na2CO3 (2) K2CO3
(i) Dil HCl or Dil H2SO4: A colourless gas with a smell of (3) Rb2CO3 (4) Ag2CO3
rotten eggs (H2S) is evolved. Sol. 2Ag2CO3 (s) → 4Ag (s) + 2CO2 (g) + O2 (g)
S2 − + 2H + 
→ H 2S ↑ Example 12: Which of the following anions are identified
The gas turns lead acetate paper black. by dil. HCl?
(CH COO) 2 Pb + H 2S  → PbS ↓ + 2CH3COOH (1) NO2–, NO3–, CO32– (2) NO2–, NO3–, SO32–
3 (Black) (3) S2–, SO32–, NO2– (4) CH3COO–, I–, CO32–
(ii) Salt solution gives yellow ppt. with CdCl2
Sol. S2–, SO32–, NO2– anions are identified by dil. HCl.
Na 2S + CdCl2  → CdS ↓ + 2NaCl
(Yellow)

Salt Analysis 171

 (b) Gases or acid vapours evolved with conc. H2SO4.
Example 13: BaCl2 solution gives a white precipitate with 1. Chloride (Cl–)
solution of a salt, which dissolves in dilute hydrochloric (i) Conc. H2SO4: Decomposes with the evolution of HCl.
acid with the evolution of colourless, pungent smelling gas. Cl– + H2SO4 → HCl + HSO4–
The gas as well as the salt both are used as bleaching agent
Gas so produced:
in the textile industries. The salt contains:
(1) Sulphite (2) Sulphide 1. Turns blue litmus paper red.
(3) Acetate (4) Carbonate 2. Gives white fumes of NH4Cl when a glass rod moistened
2+ 2– with ammonia solution is brought to the mouth of test tube.
Sol. Ba + SO3 → BaSO3 ↓ (white)
(ii) Manganese dioxide and conc. sulphuric acid: When
BaSO3 + 2HCl → BaCl2 + SO2 (colourless pungent
a solid chloride is treated with MnO2 and conc. H2SO4,
 smelling gas) + H2O
yellowish green colour is obtained.
SO32– and SO2 both act as bleaching agent. 2–
MnO2 + 2H2SO4 + 2Cl– → Mn2+ + Cl2↑ + 2SO4 + 2H2O
Example 14: Pink colour of acidified KMnO4 is decolourised
   (Yellowish green)
but there is no evolution of any gas. This may happen with
the compound containing the following acid radical: The following test are performed with the salt soluton:
– (iii) Silver nitrate solution: White, curdy ppt. of AgCl is
(1) SO32– (2) NO 2 insoluble in water and dil nitric acid, but soluble in dilute
(3) S2– (4) All of these ammonia solution.
Sol. Cl– + Ag+ → AgCl ↓
(1) 5SO32– + 2MnO4– + 6H+ → 2Mn2+ + 5SO42– AgCl ↓ + 2NH3 → [Ag(NH3)2]Cl
+ 3H2O
White ppt. reappears on acidifying.
(2) 2MnO4– + 5NO2– + 6H+ → 2Mn2+ + 5NO3–
[Ag(NH3)2]Cl + 2H+ → AgCl + NH+4
+ 3H2O
(iv) Lead acetate solution: White ppt of lead chloride is
(3) 2MnO4– + H2S + 6H+ → 2Mn2+ + 5S ↓ + 8H2O formed.
2Cl– + Pb2+ → PbCl2 ↓
             (white)
(v) Chromyl chloride test: When a mix containing chloride
Concept Application ion is heated with K2Cr2O7 and conc. H2SO4 organge red
fumes of chromyl chloride (CrO2Cl2 ) are formed.
13. What happens when dilute hydrochloric acid is added K2Cr2O7 + 4NaCl + 6H2SO4 → 2KHSO4 + 4NaHSO4
to sodium carbonate? + 2CrO2Cl2 ↑ + 3H2O
(1) Carbon dioxide and water are formed. Oragne - red fumes, chlorides of mercury, owing to their
(2) Sodium chloride, carbon monoxide and water are slight ionization, do not respond to this test and only
formed. partial conversion to CrO2Cl2 occurs with the chlorides
(3) Sodium chloride, carbon dioxide and water are of lead, silver, antimony and tin.
formed. When chromyl chloride vapours are passed into sodium
(4) Sodium chloride, carbon dioxide and hydrogen hydroxide, a yellow solution of sodium chromate is
are formed. formed, which when treated with lead acetate gives
14. The addition of dilute hydrochloric acid to a solution yellow ppt. of lead chromate.
containing the anion ‘P’ and the subsequent use of CrO2Cl2 + 2NaOH → Na2CrO4 + 2HCl
limewater can be used to identify the anion ‘P’. What (Yellow solution)
is ‘P’?
(1) Carbonate ion (2) Chloride ion Na 2 CrO 4 + (CH3COO) 2 Pb → 2CH3COONa

(3) Iodide ion (4) Sulfate ion + PbCrO 4 ↓ (yellow ppt.)
15. A solution reacts with crushed egg-shells to give 2. Bromide (Br–)
compound that turns lime-water milky. The solution (i) Conc. H2SO4: Gives reddish brown vapours of bromine.
contains:
2KBr + H 2SO 4 → K 2SO 4 + 2HBr
(1) NaCl (2) dil.HCl
(3) LiCl (4) KCl 2HBr + H 2SO 4 → 2H 2 O + SO 2 ↑ + Br2 ↑
16. An anion which has smell of vinegar, and reacts with (Reddish brown)

Iron (III) Chloride gives deep-red colouration. Anion (ii) Manganese dioxide and conc. sulphuric acid: When a
will be mix of solid bromide, MnO2and conc. H2SO4 is heated,
(1) CO32– (2) SO32– reddish brown vapours of bromine are evolved.
(3) CH3COO – (4) S2– 2KBr + MnO 2 + 2H 2SO 4 → Br2 + K 2SO 4 + MnSO 4
 + 2H2O

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 (iii) Silver nitrate solution: A pale yellow ppt. of silver This ppt. dissolves in excess of KI, forming tetra iodo
bromide is obtained. This ppt is sparingly soluble in dil mercurate (II) complex.
ammonia but readily soluble in conc. ammonia solution HgI2 + 2I– → [HgI4]2–
and insoluble in dil. HNO3. 4. Nitrate (NO3–)
Br – + Ag+ → AgBr (i) Conc. H2SO4: Gives reddish - brown vapours of nitrogen
             (white)
dioxide.
(iv) Lead acetate solution: White crystalline ppt. of lead –
4NO3 + 2H2SO4 → 4NO2 + 2SO 2– + 2H2O + O2
bromide which is soluble in boiling water. 4
(ii) Brown ring test: When a freshly prepared solution of
2Br– + Pb2+ → PbBr2 ↓
              (white) iron (II) sulphate is added to nitrate solution and conc.
H2SO4, the brown colour disappears, nitric oxide is
(v) Chlorine water: When this solution is added to a
evolved and a yellow solution of Iron (III) ions remains.
solution of bromide and chloroform, free bromine is
liberated, which colours the organic layer orange - red. 2NO − + 4H 2SO 4 + 6Fe 2 + → 6Fe3+ + 2NO + 4SO 42 − + 4H 2 O
3
2KBr + Cl2 (water) → 2KCl + Br2
Fe 2 + + NO ↑→ [Fe(H 2 O)5 NO]2 +
Br2 + Chloroform → Orange red colour
(vi) Potassium dichromate and conc. H2SO4: When a mix Action of heat: The result varies with the metal.
of solid bromide, K2Cr2O7 and conc. H2SO4 is heated and ™ Nitrates of sodium and potassium evolve oxygen (test with
the evolved vapours are passed into water, a yellowish glowing splint) and leave solid nitrities (brown fumes with
brown solution is obtained. dilute acid).
2KBr + K 2 Cr2 O7 + 7H 2SO 4 → 3Br2 ↑ +Cr2 (SO 4 )3 + 4K 2SO 4 2NaNO3 → 2NaNO2 + O2 ↑

™ Ammonium nitrate yields dinitrogen oxide and steam.
+7H 2 O
 NH4NO3 → N2O ↑ + 2H2O
3. Iodide (I–)
™ Nitrates of the noble metals leave a residue of the metal and a
(i) Conc. H2SO4: Gives violet vapours of iodine mix of nitrogen dioxide and oxygen is evolved.
2I − + 2H 2SO 4 
→ I 2 + SO 42 − + 2H 2 O + SO 2 ↑ 2AgNO3 → 2Ag + 2NO2 ↑ + O2 ↑
violet vapours
™ Nitrates of other metals, such as those of lead and copper,
(ii) Silver nitrate solution: Yellow, curdy ppt. of silver evolve oxygen and nitrogen dioxide and leave a residue of
iodide (AgI),very slightly soluble in conc. ammonia the oxide.
solution and insoluble in dil nitric acid. 2Pb(NO3)2 → 2PbO + 4NO2 ↑ + O2 ↑
I– + Ag+ → AgI
(iii) Lead acetate solution: Yellow, curdy ppt. of lead iodide, Classification of Cations
soluble in much hot water forming a colourless solution Cations are classified into six groups on the basis of their behaviour
and yielding golden yellow plates (spangles) on cooling. with some reagents and classification is based on whether a cation
2I– + Pb2+ → PbI2 ↓ reacts with these reagents by the formation of precipitate or not
             (white) (solubility difference).
(iv) Potassium dichromate and conc. sulphuric acid: Group 0:
lodine is liberated. Group Reagent : None
6I − + Cr2 O72 − + 2H 2SO 4 
→ 3I 2 ↑ + 2Cr 3+ + 7SO 42 − + 7H 2 O Ions : NH4+
(v) Chlorine water. Iodine is liberated by the dropwise Colour and ppt :
addition of chlorine water to iodide, and on addition of Group I:
CHCl3, violet coloured organic layer is obtained. Group Reagent : dil. HCl
2I– + Cl2 → I2 + 2Cl– Ions : Pb2+
I2 + Chloroform → Violet coloured layer Colour and ppt : PbCl2 white
(vi) Copper sulphate solution: Gives brown ppt. consisting of Group II A:
a mixture of copper (I) iodide and iodine and on addition Group Reagent : H2S in presence of dil. HCl
of hypo solution, brown ppt. changes to white ppt.
Ions : Pb2+, Cu2+
4I– + 2Cu2+ → 2CuI + I2
Colour and ppt : PbS, CuS
I 2 + 2S2 O32– 
→ 2I − + S4 O62 − Group III:

(vii) Mercury (II) chloride solution: Forms scarlet ppt. of Group Reagent : NH4OH in presence of NH4Cl
HgI2. Ions : Fe3+, Al3+
2I– + HgCl2 → HgI2 ↓ + 2Cl– Colour and ppt : Fe(OH)3 - Brown; Al(OH)3- White

Salt Analysis 173

Group IV: Test of Pb2+ ion
Group Reagent : H2S in presence of NH4OH and NH4Cl (i) Dilute HCl: A white ppt. in cold solution of the acid is not too
Ions : Ni2+, Co2+, Zn2+, mn+2 dilute.
Colour and ppt : CoS, NiS - Black; ZnS - White; Pb 2 + + 2Cl− 
 PbCl2 ↓
White
Group V:
 Soluble in hot water.
Group Reagent : (NH4)2CO3 in presence of NH4Cl and
 It is also soluble in conc. HCl or conc. KCl when the
NH4OH
tetrachloroplumbate (II) ion is formed.
Ions : Ba2+
PbCl2 ↓ + 2Cl−  → [PbCl4 ]2 −
Colour and ppt : BaCO3, − White
 If the ppt is washed and dil. NH3 is added, no visible
Group VI:
change occurs (difference from Hg22+ or Ag+ ions),
Group Reagent : Na2HPO4 in presence of NH4OH through a ppt. exchange reaction takes place and lead
Ions : Mg2+, Ca2+, Sr2+ hydroxide is formed.
Colour and ppt : Mg(NH4)PO4 - White (ii) NH3 solution: White ppt of Pb(OH)2 is obtained.

Group 0 Radicals Pb 2 + + 2NH3 + 2H 2 O  → Pb(OH) 2 ↓ +2H +

(white)
1. Test of NH4+ ion
Pb(OH)2 is insoluble in NH3 solution excess.
(i) Sodium hydroxide solution: Ammonia gas is evolved on
(iii) With H2S gas in neutral or dilute acid medium, black ppt. of
warming the solution containing ammonium salt and sodium
lead sulphide is obtained.
hydroxide.
NH4Cl + NaOH → NH3 + H2O + NaCl Pb 2 + + H 2S  → PbS ↓ +2H +
(Black)
The gas can be identified by the following characteristics/
When H2S gas is introduced into a mixture which contains
reactions:
a ppt. of white lead chloride, the latter is converted into lead
 Its characteristics smell. sulphide (black) in a precipitate exchange reaction.
 The evolution of the white fumes of ammonium chloride
when a glass rod dipped in dilute HCl is held in the vapour. PbCl2 ↓ + H 2S  → PbS ↓ + 2H + + 2Cl−
(white) (Black)
NH3 + HCl → NH4Cl ↑ (white fumes)
If the test is carried out in the presence of larger amounts of
 Its ability to turn filter paper moistened with Hg2(NO3)2 Cl– (KCl saturated), initially a red ppt. of lead sulphochloride
solution, black. is formed when H2S↑ is introduced.
Hg2(NO3)2 + 2NH3 → Hg (NH 2 ) NO3 + Hg + NH4NO3
  2Pb 2 + + H 2S + 2Cl− → Pb 2 SCl2 ↓ + 2H +
black (red)
(ii) Sodium hexanitrito–N–cobaltate (III) solution: NH4+ ions This, however, decomposes on dilution or on further addition
give a yellow precipitate with this reagent. of H2S and a black ppt. of PbS is formed.
3NH4+ + [Co(NO2)6]3– → (NH4)3[Co(NO2)6]↓ Pb 2SCl2 ↓ 
→ PbS ↓ + PbCl2 ↓
(Black)
(iii) Hexachloridoplatinate (IV) solution (i.e., hexachloroplatinic (red) (white)

acid): NH4+ ions give yellow precipitate with this reagent. → 2PbS + 2Cl− + 2H +
PbSCl2 + H 2S 

2NH4 ++ [PtCl6 ]2– → (NH4)2 [PtCl6]↓ (yellow) (iv) NaOH: White ppt. of Pb(OH)2 is formed.
(iv) Saturated sodium hydrogen tartrate solution (NaHC4H4O6): Pb 2 + + 2OH − 
→ Pb(OH) 2 ↓
NH4+ ions give white precipitate with this reagent . (white)

NH4+ + HC4H4O6– → NH4 (HC4H4O6) ↓

The ppt. is dissolved in excess of NaOH, when
                   (white) tetrahydroxoplumbate (II) ions are formed.
Group I Radicals Pb(OH) 2 ↓ + 2OH − → [Pb(OH) 4 ]2 −
Pb2+, are precipitated as chloride because the solubility Thus, lead hydroxide has an amphoteric character.
product of these chlorides (PbCl2) is less than the solubility (v) H2SO4 (or soluble sulphate): White ppt. of PbSO4 is
products of chlorides of all other metal ions, which remain in obtained.
solution.
Pb 2 + + SO 42 − 
→ PbSO 4 ↓
Lead chloride is slightly soluble in water and therefore, lead (White)
is never completely precipitated by adding dilute HCl to a
(vi) K2CrO4: Potassium chromate in neutral, acetic acid or
sample, the rest of the lead ions are precipitated with H2S
ammonium solution gives yellow ppt of lead chromate.
in acidic medium together with the cations of the second
group. Pb 2 + + CrO 24 − 
→ PbCrO 4 ↓ (yellow)

174 P NEET Dropper Module-6 CHEMISTRY

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(vii) KI: Yellow ppt of lead iodide is formed.
The solution becomes colourless and a white precipitate is
visible when excess of sodium thiosulphate solution is added.
Pb 2 + + 2I − → PbI 2 ↓
yellow ppt. I3– + 2S2O32– → 3I– + S4O62–
The ppt. is moderately soluble in boiling water to yield a Note: These reactions are used in quantitative analysis for the
colourless solution, from which it separates as golden yellow iodometric determination of copper.
plates on cooling. (v) Potassium ferrocyanide (Potassium hexacyanidoferrate
An excess of a more conc. solution of the reagent dissolves (II) solution: Cu2+ ions give brown/chocolate brown
the ppt. precipitate.
 [PbI4]2–
PbI2 ↓ + 2 I–  2Cu2+ + K4[Fe(CN)6] → Cu2[Fe(CN)6] ↓ + 4K+
The reaction is reversible, on cooling, ppt. reappears. Note: 2 [Fe(CN)6]3– + 3 Cu2+ → Cu3 [Fe(CN)6]2 ↓ (green)
Group II Radicals (vi) Potassium cyanide: When added sparingly, forms first a
yellow precipitate.
™ Group 2nd radicals are precipitated as sulphides because of
their low solubility products whereas sulphides of other metals Cu2+ + 2CN– → Cu(CN)2 ↓ (yellow)
remain in solution because of their high solubility products. Precipitate quickly decomposes into CuCN and cyanogen.
HCl acts as a source of H+ which decreases the concentration 2 Cu(CN)2 ↓ → 2CuCN ↓ (white) + (CN)2 ↑ (highly poisonous)
of S2– due to common ion effect. Hence, the concentration of Excess reagent dissolves the precipitate forming a colourless
S2– ion is too low that it exceeds only the solubility products soluble complex.
of the metal sulphides of IInd group. CuCN ↓ + 3CN– → [Cu(CN)4]3–
™ We can not use H2SO4 in place of HCl because some cations Complex is so stable that H2S cannot precipitate Cu(I)
of higher groups i.e. Vth group will also precipitate as their sulphide (distinction from cadmium).
sulphates like BaSO4, SrSO4, CaSO4 etc.
(vii) Potassium Thiocyanate (KSCN): Black precipitate of
1. Test of Cu2+ ion
copper (II) thiocyanate is obtained.
(i) Precipitation with H2S in acidic medium: Black precipitate
is formed. Cu 2 + + 2SCN − → Cu(SCN) 2 ↓
black
+
H
Cu2+ + H2S → CuS ↓ + 2 H+ The precipitate decomposes slowly to form white copper (I)
             (black) thiocyanate and thiocyanogen is formed.
Precipitate is insoluble in boiling dilute H2SO4 (distinction 2Cu(SCN) 2 ↓  → 2CuSCN ↓ + (SCN) 2 ↑
White
from cadmium), in NaOH, Na2S and (NH4)2S. Precipitate
dissolves in hot concentrated HNO3. Thiocyanogen rapidly decomposes in aqueous solution.
3CuS + 8HNO3 → 3Cu(NO3)2 (blue) + 2NO + 4H2O + 3S 2. Test of Pb2+ ion
When boiled for longer, S is oxidised to H2SO4 and a clear (i) Precipitation with H2S in acidic medium: Black precipitate
is formed which is soluble in hot dilute HNO3.
solution of Cu(NO3)2 is obtained.
Pb2+ + H2S → PbS ↓ (black) + 2H+
Note: KCN dissolves the precipitate forming a clear solution.
3PbS + 8HNO3 → 3Pb(NO3)2 + 2NO + 4H2O + 3S
2CuS ↓ + 8 CN– → 2 [Cu(CN)4]3– + S22– (disulphide ion)
(ii) Dilute H2SO4: White precipitate is formed which is soluble
(ii) Ammonia solution: When added sparingly, a blue precipitate in ammonium acetate.
of basic salt (basic copper sulphate) is formed with CuSO4. Pb(NO3)2 + H2SO4 → PbSO4 ↓ (white) + 2HNO3
2Cu2+ + SO42– + 2NH3 + 2H2O → Cu(OH)2.CuSO4 ↓ PbSO4 + 2CH3COONH4→(CH3COO)2Pb + (NH4)2SO4 +
+ 2NH4+  (NH4)2[Pb(CH3 COO)4]
It is soluble in excess of reagent forming a deep blue colouration. (iii) Potassium iodide: Yellow precipitate is formed which is
Cu(OH)2 .CuSO4↓ + 8NH3 → 2 [Cu(NH3)4]2+ + SO42– soluble in excess concentrated (6M) solution of the reagent.
+ 2OH– Yellow precipitate of PbI2 is moderately soluble in boiling
water to give a colourless solution.
(iii) Sodium hydroxide in cold solution: A blue precipitate is
formed. (CH3COO)2Pb + 2KI → 2CH3COOK + PbI2 ↓ (yellow)
Cu2+ + 2OH– → Cu(OH)2 ↓ (iv) Potassium chromate: Yellow precipitate is formed.
Heat
(CH3COO)2Pb + K2CrO4 → 2CH3COOK + PbCrO4 ↓
Cu(OH)2↓  → CuO↓ (black) + H O
2 (yellow)

(iv) Potassium iodide: It gives a white precipitate of Cu(I) iodide Group III Radicals
but the solution is intensely brown because of the formation
Group IIIrd radicals are precipitated as hydroxides and the

of tri–iodide ions (or iodine).
addition of NH4Cl suppresses the ionisation of NH4OH so
2Cu2+ + 5I– → Cu2I2 ↓ + I3– that only the group 3 cations are precipitated as hydroxides
            (Brown) because of their low solubility products.

Salt Analysis 175

 ™ Excess of NH4Cl should not be added, as manganese will 2. Test of Fe3+ ion
precipitate as MnO2.H2O. (i) Precipitation with NH4OH in presence of NH4Cl:
™ Concentrated HNO3 is added to oxidise Fe2+ to Fe3+, if Gelatinous reddish brown precipitate is formed which is
present. insoluble in excess reagent but soluble in acids.
1. Test of Al3+ ion NH Cl
(i) Precipitation with NH4OH in presence of NH4Cl: White Fe3+ + 3NH4OH → 4
Fe(OH)3 ↓ + 3NH4+
gelatinous precipitate is formed which is slightly soluble in Note: Precipitation of iron(II) hydroxide occurs with ammonia
excess reagent. The solubility is decreased in the presence solution. If larger amounts of ammonium ions are present, the
of ammonium salt. A small portion of the precipitate passes dissociation of NH4OH is suppressed and the concentration of
into the solution as colloidal Al(OH)3 (Aluminium hydroxide OH– ions is lowered to such an extent that solubility product of
sol), the sol is coagulated on boiling the solution or upon the iron (II) hydroxide, Fe(OH)2 is not attained and precipitation does
addition of soluble salt yielding a precipitate of Al(OH)3, not occur.
known as Al(OH)3 gel. (ii) Sodium hydroxide solution: Reddish brown precipitate is
NH Cl formed which is insoluble in excess reagent (distinction from
Al3+ + 3NH4OH → 4
Al(OH)3 ↓ + 3NH4+
(ii) Sodium hydroxide: White precipitate of Al(OH)3 is obtained. aluminium and chromium).
Fe3+ + 3OH– → Fe(OH)3 ↓
Al3+ + 3OH −  → Al(OH)3 ↓
White (iii) H2S gas in acidic solution: Fe3+ reduces to Fe2+ .
White precipitate dissolves in excess sodium hydroxide 2Fe3+ + H2S → 2Fe2+ + 2H+ + S ↓ (milky-white)
according to following reaction. If a neutral solution of iron (III) chloride is added to a freshly
Al(OH)3 + OH–  [Al(OH) ]– prepared saturated solution of H2S , bluish colouration appears
4
The reaction is reversible and any reagent, which will reduce the first, followed by precipitation of sulphur. The blue colour
hydroxyl ion concentration sufficiently should cause the reaction is due to a colloidal solution of sulphur of extremely small
to proceed from right to left with the consequent precipitation of particle size. This reaction can be used to test the freshness of
aluminium hydroxide. This may be effected with a solution of H2S solution.
ammonium chloride (the hydroxyl ion concentration is reduced (iv) Ammonium sulphide solution: Black precipitate consisting
owing to the formation of the weak base ammonia, which can be of Fe(II) sulphide and sulphur is formed.
readily removed as ammonia gas by heating) or by the addition 2Fe3+ + 3S2– → 2FeS + S ↓
of acid. In the latter case, a large excess of acid causes the
In HCl, the black precipitate of Fe(II) sulphide dissolves and
precipitated hydroxide to redissolve.
white precipitate of sulphur becomes visible.
[Al(OH)4]– + NH4+ → Al(OH)3 ↓ + NH3↑ + H2O FeS ↓ + 2H+ → H2S ↑ + Fe2+
 Al(OH) ↓ + H O
[Al(OH) ]– + H+ 
4 3 2 (v) The damp iron (II) sulphide precipitate, when exposed to air,
Al(OH)3 + 3H+ (excess)   Al3+ + 3 H O
2
is slowly oxidised to brown iron(III) hydroxide.
(iii) Dry test: Aluminium compounds when heated with sodium 4FeS ↓ + 6H2O + 3O2 → 4Fe(OH)3 ↓ + 4S ↓
carbonate upon charcoal gives a white infusible solid, which Note: From alkaline solutions of ammonium sulphide, black
glows when hot. If the residue is moistened with a little cobalt iron(III) sulphide is obtained.
nitrate solution and again heated, a blue infusible mass is
2Fe3+ + 3S2– → Fe2S3 ↓
obtained.
On acidification with hydrochloric acid, iron (III) ions are
2Al2O3 + 2Co2+ + 4NO3– → 2CoAl2O4 + 4NO2 ↑ + O2 ↑
reduced to iron (II) ions and sulphur is formed.
(thenard blue)
Fe2S3 ↓ + 4H+ → 2Fe2+ + 2H2S ↑ + S ↓
Use of excess cobalt nitrate solution should be avoided since
(vi) Potassium ferrocyanide (Potassium hexacyanidoferrate(II)):
this will produce black cobalt oxide (Co3O4) upon ignition,
which will mask the blue colour. Intense blue precipitate (Prussian blue) of iron(III)
hexacyanidoferrate(II) is formed.
(iv) Ammonium Sulphide Solution: A white precipitate,
Al(OH)3 is obtained. 4Fe3+ + 3[Fe(CN)6]4– → Fe4[Fe(CN)6]3 ↓
2Al3+ + 3S2– + 6H2O → 2Al(OH)3 ↓ + 3H2S ↑ This is insoluble in dilute acids but decomposes in
concentrated HCl. A large excess of the reagent dissolves it
(v) Sodium Acetate Solution: No precipitate is obtained in
cold, neutral solution, but on boiling with excess reagent, partly or entirely, when an intense blue solution is obtained.
a voluminous precipitate of basic aluminium acetate Sodium hydroxide turns the precipitate red.
Al(OH)2(CH3COO) is formed. Fe4[Fe(CN)6]3 ↓ + 12OH– → Fe(OH)3 ↓ + 3[Fe(CN)6]4–
Al3+ + 3CH3COO − + 2H 2 O 
→ Al(OH) 2 (CH3COO) ↓ Note:
White
™ Oxalic acid also dissolves Prussian blue forming a blue-
 + 2CH3COOH solution.

176 P NEET Dropper Module-6 CHEMISTRY

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 ™ If iron(III) chloride is added to an excess of potassium (x) Disodium hydrogen phosphate solution: A yellowish–
hexacyanidoferrate (II), a product with the composition white precipitate is formed.
of K4Fe[Fe(CN)6] is formed. This tends to form colloidal Fe3+ + HPO42– → FePO4 ↓ + H+
solutions (“soluble Prussian blue”) and can not be filtered. The reaction is reversible, because a strong acid is formed
(vii) Potassium ferricyanide (Potassium hexacyanidoferrate(III)): which dissolves the precipitate. It is advisable to add small
A brown colouration is formed. amounts of sodium acetate, which acts as a buffer.
Fe3+ + [Fe(CN)6]3– → Fe[Fe(CN)6]
Group IV Radicals
Note:
In IVth group, ammonium hydroxide increases the ionisation
™ Fe2+ gives dark blue precipitate with potassium ferricyanide. of H2S by removing H+ from H2S as unionised water.
First hexacyanidoferrate (III) ions oxidise iron(II) to iron(III),
 2H+ + S2–
H S 
when hexacyanidoferrate(II) is formed. 2
Fe2+ + [Fe(CN)6]3– → Fe3+ + [Fe(CN)6]4– H+ + OH– → H2O
These ions combine to form a precipitate called Turnbull’s Now the excess of S2– ions is available and hence the ionic
blue. products of group 4th group cations exceeds their solubility
products and will be precipitated. In case H2S is passed
4Fe3+ + 3[Fe(CN)6]4– → Fe4[Fe(CN)6]3
through a neutral solution, incomplete precipitation will
™ Composition of this precipitate is identical to that of Prussian take place due to the formation of HCl, which decreases the
blue. Earlier the composition suggested was Fe3[Fe(CN)6]2, ionisation of H2S.
hence different name.
1. Test of Zn2+ ion
3Fe2+ + 2K3[Fe(CN)6] → Fe3[Fe(CN)6]2 (ferrous ferric cyanide) + 6K+
(i) Precipitation with H2S in presence of NH4OH + NH4Cl: A
(Turnbull’s blue)
white precipitate is formed. In neutral solutions, precipitation
™ Fe(II) in ammonical solution gives red solution with DMG, is partial as H+ ions concentration produced, depressed the
colouration fades on standing due to the oxidation of the ionisation of H2S.
iron(II) complex. Fe (III) does not give such complex.
Zn2+ + H S   ZnS ↓ + 2H+
™ In complete absence of air, Fe(II) ions produce white 2

precipitate with potassium hexacyanidoferrate(II). The precipitate is soluble in dilute HCl.

Fe2+ + 2K+ + [Fe(CN)6]4– → K2Fe [Fe(CN)6] ↓ ZnS + 2H+ → Zn2+ + H2S ↑
Under ordinary atmospheric conditions a pale–blue precipitate (ii) Sodium hydroxide solution: A white gelatinous precipitate
is formed. is formed.
(viii) 
Potassium thiocyanate (Potassium sulphocyanide): In Zn2+ + 2OH– → Zn(OH)2 ↓
slightly acidic medium, a deep red colouration is produced Note: The precipitate is soluble in acids as well as in excess of
due to the formation of a non-dissociated iron(III) thiocyanate the reagent.
complex.
Zn(OH)2 + 2H+ → Zn2+ + 2H2O
Fe3+ + 3SCN– → Fe(SCN)3
This neutral molecule can be extracted by ether or amyl Zn(OH)2 + 2OH– → [Zn(OH)4]2–
alcohol. Thus, zinc hydroxide is amphoteric in nature.
Note:
[Zn(OH)4]2– + S2– → ZnS ↓ (white) + 4OH–
™ With pure Fe(II) ions no colouration is obtained.
™ Fluorides and Hg(II) ions bleach the red colour. (iii) Ammonia solution: A white gelatinous precipitate is formed
which is readily soluble in excess of the reagent and in solutions
Fe(SCN)3 + 6F– → [FeF6]3– + 3SCN–
of ammonium salts forming the tetraamminezinc (II).
2Fe(SCN)3 + 3Hg2+ → 2Fe3+ + 3Hg(SCN)2
Zn2+ + 2NH + 2H O   Zn(OH) ↓ + 2NH +
(ix) Sodium acetate solution: A deep red colouration is obtained 3 2 2 4

owing to the formation of [Fe3(OH)2(CH3COO)6]+. The

Zn(OH)  [Zn(NH ) ]2+ + 2OH–
↓ + 4NH3 
2 3 4
reaction becomes complete only if the strong acid, which
is formed, is removed by the addition of an excess reagent, (iv) Potassium ferrocyanide (Potassium hexacyanidoferrate(II))
which acts as a buffer. solution: A white precipitate of variable composition is formed.
If excess reagent is added, the composition of precipitate is
3Fe3+ + 6CH3COO– + 2H2O   [Fe (OH) (CH COO) ]+
+
3 2 3 6 K2Zn3[Fe(CN)6]2 .
+ 2H
This deep red coloured solution on dilution with water and 3 Zn2+ + 2K+ + 2[Fe(CN)6]4– → K2Zn3[Fe(CN)6]2 ↓

boiling gives reddish brown precipitate of basic ferric acetate. The precipitate is insoluble in dilute acids, but dissolves in
[Fe3(OH)2(CH3COO)6]+ + 4H2O → 3Fe(OH)2CH3COO ↓ sodium hydroxide readily.
+3CH3COOH + H+
K2Zn3[Fe(CN)6]2 + 12OH– → 2[Fe(CN)6]4– + 3 [Zn(OH)4]2–
The excess of acetate ion acts as buffer and the reaction goes
to completion.
This reaction can be used to distinguish zinc from aluminium.

Salt Analysis 177

 2. Test of Co2+ ion: 3. Test of Ni2+ ion:
(i) Precipitation with H2S in presence of NH4OH + NH4Cl: (i) Precipitation with H2S in presence of NH4OH + NH4Cl:
A black precipitate is formed. The black precipitate of CoS
A black precipitate is formed which is insoluble in cold dilute
is insoluble in dilute HCl or acetic acid but hot concentrated
HCl and CH3COOH but dissolves in hot concentrated HNO3
HNO3 or aquaregia dissolves it and white sulphur remains. On
longer heating, the mixture becomes clear because sulphur is and in aquaregia.
oxidised to sulphate. NH OH
NiCl2 + H2S 
4
→ NiS ↓ (Black) + 2HCl
2[Co(NH3)6]3+ + 3S2– → 2CoS ↓ + 12NH3 + S
                 (Black) 3NiS ↓ + 2HNO3 + 6H+ → 3Ni2+ + 2NO ↑ + 3S ↓ + 4H2O

NH OH NiS + HNO3 + 3HCl → Ni2+ + S ↓ + NOCl ↑ + 2Cl– + 2H2O.

or CoCl2 + H2S 
4
→ CoS ↓ + 2HCl
Note: Solution on evaporation to dryness gives yellow residue
3 CoS + 2HNO3 + 6H+ → 3Co2+ + 3S ↓ + 2NO ↑ + 4H2O
(NiCl2) which turns green on adding water.
2CoS + 6HCl + 2HNO3 → 3CoCl2 + 2NO + 3S + 4H2O
(ii) Dimethylglyoxime reagent: A red precipitate obtained from
Note: Solution on evaporation to dryness gives blue residue
(CoCl2) which turns pink on adding water. the solution is just made alkaline or acid solutions buffered
with sodium acetate.
(ii) Potassium nitrite solution: A yellow precipitate is formed
from neutral solution of cobalt(II) ions. NiCl2+ 2NH4OH + DMG → (C4H7N2O2)2Ni ↓ (red)
CoCl2 + 7KNO2 + 2CH3COOH → K3[Co(NO2)6]↓ + H2O or [Ni(DMG)2]
                       (yellow)  + 2NH4Cl + 2H2O
 + 2KCl + 2CH3COOK + NO ↑
™ Fe(II) ions give red colouration, bismuth gives yellow
Or
precipitate and cobalt gives brown colouration with DMG in
Co2+ + 7NO2– + 2H+ + 3K+ → K3[Co(NO2)6] ↓ + NO↑
ammonical solutions.
+ H2O.
™ Ni2+ gives black precipitate (Ni2O3) with sodium bicarbonate
(iii) Ammonium thiocyanate solution: A neutral or acid solution and bromine water on heating whereas Co2+ gives green
of cobalt(II) gives a blue colouration in amyl alcohol or ether
coloured solution, this is the point of difference.
layer when a few crystals of ammonium thiocyanate are
added. NiCl2 + 2NaHCO3 → NiCO3 + 2NaCl + H2O
Co2+ + 4SCN– → [Co(SCN)4]2– 2NiCO3 + [O] → Ni2O3 ↓ (black) + 2CO2
Note: In amyl alcohol or ether, the free acid H2[Co(SCN)4] is
formed and is dissolved by the organic solvent (distinction from
nickel). Train Your Brain
(iv) Sodium bicarbonate and bromine water test: To the test
solution, sodium bicarbonate is added in excess followed by Example 15: A gas is evolved on warming the solution
the bromine water. The mixture is slightly heated, the solution containing ammonium salt and sodium hydroxide. The gas is:
turns apple green.
(1) NH3 (2) N2O (3) NO (4) NO2
CoCl2 + 2NaHCO3 → Co(HCO3)2 + 2NaCl
Sol. NH4Cl + NaOH → NH3 + H2O + NaCl
Co(HCO3)2 + 4NaHCO3 → Na4[Co(CO3)3] + 3H2O Example 16: Which of the following gives a black ppt
+ 3CO2 when H2S is passed through an acidic solution?
Br2 + H2O → 2HBr + [O] (1) Nickel acetate (2) Copper acetate
(3) Cobalt acetate (4) Zinc acetate
2Na4 [Co(CO3)3] + H2O + [O] → 2Na3[Co(CO3)3] + 2Na OH.
Sol. Copper acetate gives black ppt when H2S is passed
   (green)
through an acidic solution. While Nickel acetate, Cobalt
Note: Green solution of sodium cobalticarbonate is obtained. acetate and zinc acetate gives black colour in alkaline
(v) Sodium hydroxide solution: Cobalt(II) nitrate in cold gives medium.
a blue basic salt.
Example 17: On boiling a dilute solution of manganese(II)
Co2+ + OH– + NO3– → Co(OH)NO3 ↓ ions with lead dioxide and a little concentrated nitric acid
                  (Blue)
and allowing the suspended solid containing unattacked
Upon warming with excess alkali, the basic salt is converted lead dioxide to settle, the supernatant liquid acquired a
into a pink precipitate of Co(II) hydroxide. violet-red (or purple) colour. This is due to formatiom
Co(OH)NO3 ↓ + OH– → Co(OH)2 ↓ + NO3– of:
                 (Pink)

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 Group V Radicals
(1) Formic acid (2) Permanganic acid In Vth group, the reagent ammonium carbonate should be added
(3) Manganic acid (4) Oxide of lead in alkaline or neutral medium. In the absence of ammonia or
Sol. Formatiom of permanganic acid ammonium ions, magnesium will also be precipitated.
5PbO2 + 2Mn2+ + 4H+ → 2MnO4– + 5Pb2+ + 2 H2O 1. Test of Ba2+ ion
(i) Precipitation with (NH4)2CO3 in presence of NH4OH
Example 18: A black sulphide is formed by the action of + NH4Cl: A white precipitate is formed which is soluble in
H2S on: acetic acid and dilute mineral acids.
(1) Cupric chloride (2) Cadmium chloride BaCl2 + (NH4)2CO3 → BaCO3 ↓ + 2NH4Cl
(3) Zinc chloride (4) Ferric chloride
BaCO3 + 2CH3COOH → Ba(CH3COO)2 + H2O + CO2
Sol. A black sulphide is formed by the action of H2S on (ii) Potassium chromate test: A yellow precipitate is formed,
cupric chloride. practically insoluble in water.
Example 19: Which one is not a radical of group IV? Ba(CH3COO)2 + K2CrO4 → BaCrO4 ↓ + 2CH3COOK
(1) Ni2+ (2) Co2+ Note:
(3) Ba 2+ (4) Zn2+ ™ Precipitate is insoluble in dilute acetic acid (distinction from
strontium and calcium) but readily soluble in mineral acids.
Sol. Ba2+ is not a radical of group IV. Group IV radicals
™ Addition of acid to K2CrO4 changes the yellow colour of the
are Ni2+, Co2+, Mn2+, Zn2+. solution to reddish–orange due to the formation of dichromate.
2H+ + 2CrO42– 
 Cr2O72– + H2O

Concept Application Group VI Radicals

1. Test of Mg2+ ion
(i) Ammonium Solution: Partial precipitation of white
17. An aqueous solution of colourless metal sulphate gelatinous Mg(OH)2.
M, gives a white precipitate with NH4OH. This is
soluble in excess of NH4OH. On passing H2S gas Mg 2 + + 2NH3 + 2H 2 O 
→ Mg(OH) 2 ↓ + 2NH 4+
(whites)
through this solution a white precipitate is formed.
The metal M in the salt is: The precipitate is very sparingly soluble in water (1.2 × 10–2g/L)
(1) Ca (2) Ba (3) Al (4) Zn but readily soluble in ammonium salts.
(ii) NaOH Solution: White precipitate of Mg(OH)2, insoluble in
18. In group 2nd radicals, we can not use H2SO4 in place excess NaOH, but readily soluble in NH4+ salts.
of HCl because
Mg 2 + + 2OH − 
→ Mg(OH) 2 ↓
(1) Some cations of higher groups i.e. Vth group will
also precipitate as their sulphates. (iii) (NH4)2CO3 Solution: In the absence of NH4+ salts, a white
(2) Some cations of higher groups i.e. IVth group will precipitate of basic magnesium carbonate is obtained.
also precipitate as their sulphates.
5Mg 2 + + 6CO32 − + 7H 2 O 
→ 4MgCO3⋅Mg(OH) 2⋅ 5H 2 O ↓
(3) Mg2+ also precipitate as a sulphate.
(4) All are correct + 2HCO3−
19. A metal salt solution when treated with dimethyl In the presence of NH4+ salts, no precipitation occurs because
glyoxime and NH4OH gives a rose red complex. The the equilibrium is shifted to left.
metal is: NH + + CO 2–  NH + HCO –
4 3 3 3
(1) Ni (2) Zn (3) Co (4) Mn
(iv) Na2CO3 Solution: White voluminous precipitate of basic
20. Match Column-I with Column-II.
carbonate as above is formed, insoluble in bases but readily
Column-I Column-II soluble in acids and in solutions of NH4+ ions.
Colour Ppt.
(v) Na2HPO4 Solution: White crystalline precipitate of
A. Black p. PbS Mg(OH)4PO4⋅6H2O in the presence of NH4Cl (to prevent
B. Yellow q. PbCl2 precipitation of Mg(OH)2) and NH3 solution.
C. White r. CdS
Mg 2 + + NH3 + HPO 24 − 
→ MgNH 4 PO 4 ↓
D. Buff light pink s. MnS
(1) A → s; B → q; C → r; D → p The precipitate is sparingly soluble in water, soluble in
(2) A → p; B → r; C → q; D → s CH3COOH and in mineral acids. The precipitate separates
slowly from dilute solutions because of its tendency to form
(3) A → p; B → q; C → r; D → s supersaturated solutions, this may usually be overcome by
(4) A → q; B → p; C → r; D → s cooling and by rubbing the test tube or beaker beneath the
surface of the liquid with a glass rod.

Salt Analysis 179

 A white flocculant precipitate of MgHPO4 is produced in
neutral solutions. CHEMICAL PRINCIPLES INVOLVED
IN THE FOLLOWING EXPERIMENTS
Mg 2 + + HPO 42 − 
→ MgHPO 4 ↓
1. Enthalpy of solution of CuSO4
In thermochemical measurements generally aqueous
Train Your Brain solutions are mixed therefore, water in the reaction medium
and the temperature changes result due to the chemical
reactions taking place in solution.
Example 20: Mg2+ + NH3 + HPO42– → X
According to law of conservation of energy, the sum of
Compound X is
enthalpy changes taking place in the calorimeter (loss
(1) MgNH4PO4 (2) Mg(OH)4PO4⋅6H2O and gain of energy) must be zero. Thus, we can write the
following equation-
(3) Both (1) and (2) (4) Mg(OH)2 6H2O
(ΔΗ1) Heat gained (ΔΗ2) Enthal-
Sol. Mg2+ 2–
+ NH3 + HPO4 → MgNH4PO4↓ by calorimeter, + by change of +
Example 21: A neutral or acidic solution of cobalt(II) thermometer and solution/water in
gives a blue colouration in amyl alcohol or ether layer stirrer calorimeter
when a few crystals of compound 'X' are added. The (ΔΗ3) Enthalpy (ΔΗ4) Enthalpy
compound 'X' is: change of added + change of reaction = 0
(1) Ammonium thiocyanate solution/ water in
(2) Ammonium cyanate calorimeter
(3) Ammonium carbonate In these reactions we take the product of density and heat
capacity of solutions, dCp, to be 4.184 J.mL–1.K–1, nearly
(4) Ammonium phosphate
the same as that of pure water.
Sol. Co2+ + 4 SCN– → [Co(SCN)4]2– (blue colour)
Solution formation often accompanies heat changes.
Example 22: NiCl2+ 2NH4OH + DMG → X  (red) Enthalpy of solution is the amount of heat liberated
 + 2NH4Cl + 2H2O or absorbed when one mole of a solute (solid/liquid)
Compound X is: is dissolved in such a large quantity of solvent
(1) Compound X is a rosy red complex. (usually water) that further dilution does not make any
(2) Compound X is a square planar complex. heat changes.
(3) Compound X is sp3 hybridized complex. 2. Enthalpy of neutralization of strong acid and strong
(4) Both (1) and (2) are correct base.
Sol. NiCl2+ 2NH4OH + DMG → (C4H7N2O2)2 Ni↓ A neutralisation reaction involves the combination of H+(aq)
(red) ions furnished by an acid and OH– (aq) ions furnished by
 + 2NH4Cl + 2H2O a base, evidently leading to the formation of H2O. Since
the reaction envisages bond formation, therefore, this
reaction is always exothermic. Enthalpy of neutralisation
is defined as the amount of heat liberated when 1 mol of
H+ ions furnished by acid combine with 1 mole of OH– ions
Concept Application furnished by base to form water. Thus:
H+(aq) + OH– (aq) → H2O (1),    Δneut H is negative
21. VIth group contains: (Acid) (Base)
(1) Mg2+ ion (2) Na+ ion where Δneut H is known as enthalpy of neutralisation. neut
+
(3) NH4 ion If both the acid and the base are strong then for the formation
(4) Both (1) and (2) are correct of 1 mol H 2 O, always a fixed amount of heat, viz,
22. A white flocculants precipitate of Mg 2+ ion with 57 kJ mol–1 is liberated. If any one of the acid or the base
phosphoric salt is: is weak or if both of these are weak, then some of the heat
liberated is used for the ionisation of the acid or base or
(1) MgHPO4 (2) Mg(H2PO4)2
both of them (as the case may be) and the amount of heat
(3) Mg3(PO4)2 (4) None of these
liberated is less than 57 kJ mol–1.
23. Which is white in colour?
3. Preparation of lyophilic and lyophobic sols.
(1) SrCO3 (2) CaCO3
Colloidal sols are divided into two categories:
(3) BaCO3
1. Lyophillic sol- Solvent attracting
(4) All compound are white in colour
2. Lyophobic sol- Solvent repelling

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 Lyophillic sols are more stable than the lyophobic sols peroxide with iodide ions increases rapidly to a point where
because in lyophillic sols, particles of dispersed phase have iodine forms intense blue complex with starch. The time
an affinity for the particles of dispersion medium. required to consume a fixed amount of the thiosulphate
Factors responsible for the stability of sols are: ions is reproducible. Since the time for the appearance of
colour is noted, the reaction is some times called a clock
1. Charge reaction.
2. Solvation of the colloidal particles by the solvent.
™ Lyophillic sols are stable due to the solvation factor.
™ Lyophobic sols are stable due to the charge on the colloidal Train Your Brain
particles. Charges can be positive or negative.
™ Examples of lyophillic sols- are Egg albumin, starch and Example 23: Choose the correct statement for kinetic study
gum. of the reaction of iodide ion with H2O2 at room temperature.
™ Examples of lyophobic sols- are freshly prepared ferric (1) Always use freshly prepared Sucrose solution.
hydroxide, aluminium hyroxide and arsenic sulphide. (2) Always keep the concentration of sodium
™ Positively charged sols- hydrated ferric oxide (when FeCl3 thiosulphate solution more than that of KI
is added to excess of hot water) solution.
™ Negatively charged sol- starch, arsenious sulphide and (3) Record the time immediately after the appearance
hydrated ferric oxide (when FeCl3 is added to NaOH solution). of blue colour.
™ Lyophillic sols are directly formed by mixing and shaking the (4) Record the time immediately before the
substance with a suitable liquid. appearance of blue colour.
™ Lyophobic sols cannot be prepared by direct mixing and Sol. Record the time immediately after the appearance of
shaking. blue colour.
™ Some methods for the colloids preparation are
(a) Chemical methods
(b) Electrical disintegration
(c) Peptization. Concept Application
™ Sols are purified by dialysis.
4. Kinetic study of the reaction of iodide ions with 24. The enthalpy of solution of anhydrous CuSO4 is
hydrogen peroxide at room temperature. -17 kcal per mole and that of CuSO4.5H2O is 4 kcal per
The reaction between iodide ions and hydrogen peroxide mole. Calculate the enthalpy of hydration of CuSO4.
occurs in the acidic medium and can be represented in the (1) 21 Kcal per mole
following manner: (2) –21 Kcal per mole
2I– + H2O2 (1) + 2H+(aq) → I2(g) + 2H2O(1) (3) 13 Keal per mole
In this reaction, hydrogen peroxide oxidises iodide ions (4) –13 Kcal per mole
(I–) to molecular iodine. If calculated amount of sodium 25. The enthalpies of solution of anhydrous CuSO4(s) and
thiosulphate is added in the presence of starch solution as hydrated CuSO4.5H2O(s) are –80 kJ per mole and
an indicator to the above reaction mixture, the liberated 20 kJ per mole respectively. Determine the magnitude
iodine reacts with thiosulphate ions as fast as it is formed of enthalpy of Hydration of 0.1 mole anhydrous
and is reduced back to iodide ions till all the thiosulphate CuSO4(s) as:
ions are oxidised to tetrathionate ions. CuSO4(s) + 5H2O → CuSO4.5H2O.
I2(g) + 2S2O2– 2– –
3 (aq) → S4O 6 (aq) + 2I (aq) (1) 10 KJ (2) 6 KJ
After the complete consumption of thiosulphate ions, the (3) 12 KJ (4) 4 KJ
concentration of iodine liberated in the reaction of hydrogen

Salt Analysis 181

 SHORT NOTES
INTRODUCTION
Qualitative analysis involves the detection of cation(s) and anion(s) of a salt or a mixture of salts.
Preliminary Test
1. Physical appearance (smell):
Table: 1
Take a pinch of the salt between your fingers and rub with a drop of water
Smell Inference
Ammoniacal smell NH4+
Smell like that of rotten eggs S2–
2. Dry Heating Test:
This test is performed by heating a small amount of mixture in a dry test tube. Quite valuable information can be generated by
carefully performing and noting the observations here. On heating, some salts undergo decomposition thus evolving the gases or
may undergo characteristic changes in the colour of residue.
3. Flame test:
Table: 2
Colour of Flame Inference
Crimson Red / Carmine Red Lithium
Golden yellow Sodium
Violet/Lilac Potassium
Brick red Calcium
Crimson Strontium
Apple Green/Yellowish Green Barium
Green with a Blue centre/Greenish Blue Copper
4. Borax Bead test:
On heating, borax forms a colourless glassy bead of NaBO2 and B2O3 .
∆ ∆
Na2B4O7.10H2O

 → Na2B4O7  → 2NaBO2 + B2O3
On heating with a coloured salt , the glassy bead forms a coloured metaborate in oxidising flame.
For example, In oxidising flame, copper salts give blue bead.
CuSO4 → CuO + SO3; CuO + B2O3 → Cu(BO2)2 (blue bead)
5. Solubility Chart:
Table: 3
S. No. Anion Solubility / Exception
1. CO3 2– Except carbonates of alkali metals and of ammonium, all other normal carbonates are insoluble.
2. SO3 2– Only the sulphites of the alkali metals and of ammonium are water soluble. The sulphite of other metals are
either sparingly soluble or insoluble.
3. S2– The acid, normal and polysulphide of alkali metals are soluble in water. The normal sulphides of most other
metals are insoluble, those of the alkaline earths are sparingly soluble, but are gradually changed by contact
with water into soluble hydrogen sulphides.
4. NO2– , NO3– Almost all nitrites and nitrates are soluble in water. AgNO2 is sparingly soluble. Nitrates of mercury and
bismuth give basic salts on treatment with water. These are soluble in dilute nitric acid.
5. Cl– Most chlorides are soluble in water. PbCl2 (sparingly soluble in cold but readily soluble in boiling water),
Hg2Cl2, AgCl, CuCl, BiOCl, SbOCl and Hg2OCl2 are insoluble in water.
6. Br– Silver, mercury(I) and copper(I), bromides are insoluble. Lead bromide is sparingly soluble in cold but more
soluble in boiling water. All other bromides are soluble in water.
7. I– Silver, mercury(I), mercury(II), copper(I), lead and bismuth(III) iodides are the least soluble in water.

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ANALYSIS OF ANIONS (ACIDIC RADICALS)
Analysis of anions (acidic radicals) can be broadly divided into two groups.
(A) GROUP ‘A’ RADICALS: It involves those anions which are characterised by volatile products by reaction with HCl/ H2SO4. It is
further subdivided into two groups as given below.
(a) Dilute Sulphuric acid/Dilute Hydrochloric acid: The anions of this group liberate gases or acid vapours with dilute sulphuric
acid/hydrochloric acid.
Table: 4
Observation Inference
Gas Radical
Effervescence with the evolution of a colourless and odourless gas which turns lime water
CO2 CO32–
milky
Evolution of colourless gas having smell of rotten egg which turns lead acetate paper
H2S S2–
black.
Colourless gas having suffocating odour (like burning sulphur) which turns acidified
SO2 SO32–
K2Cr2O7 paper green.
Evolution of reddish brown pungent smelling gas which turns
(i) FeSO4 solution brownish-black and NO2 NO2–
(ii) wet starch –iodide paper blue.
No peculiar gas is evolved. – All above are absent

(b) Concentrated Sulphuric acid group: The anions of this group liberate acid vapours or gases with conc. H2SO4.
Table: 5
Observation Inference
Gas Radical
Colourless gas with pungent smell which gives dense white fumes with a glass rod dipped in NH4OH. HCl Cl–
Reddish brown gas with pungent smell, intensity of reddish brown fumes increases on addition of a pinch
Br2 Br –
of solid MnO2. Also, it turns starch paper, orange red.
Evolution of violet vapours which turns starch paper, blue. I2 I–
Evolution of reddish brown fumes which intensifies on addition of copper turnings or bits of filter paper. Starch
iodide paper develops a blue–black spot due to the formation of a I2–starch complex. (NO2 liberated acts as NO2 NO3–
oxidising agent).

CLASSIFICATION OF CATIONS
Cations are classified into five groups on the basis of their behaviour with some reagents.
Table: 6

Group Group Reagent Ions Colour and Ppt.

Group I dil. HCl Pb2+ PbCl2, White
Group II A H2S in dil. HCl Cu2+ CuS, PbS
Group II B
Group III NH4OH in presence of NH4Cl Fe3+, Al3+ Fe(OH)3 - Brown; Al(OH)3 - White
Group IV H2S in presence of NH3 and Ni2+, Co2+, Zn2+ ZnS - White or grey; CoS, NiS - Black
NH4Cl or (NH4)2S
Group V (NH4)2CO3 in presence of Ba2+ BaCO3 - White
NH4Cl and NH4OH
Group VI No common group reagent Mg2+ Mg(NH4)PO4 - White

Salt Analysis 183

 AARAMBH (SOLVED EXAMPLES)
1. Which one of the following ions does not give borax bead 6. Which of the following gases turn starch iodide paper blue?
test? (1) CO2 (2) SO2
(1) Zn2+ (2) Cu2+ (3) NO2 (4) H2S
(3) Mn2+ (4) Fe3+ Sol. NO2 gases turn starch iodide paper blue.
Sol. Zn2+ ions does not give borax bead test, beacuse Zn2+ ion 2KI + 2NO2 —→ 2KNO2 + I2
is colourless. I2 + starch paper —→ Blue starch Iodide
Therefore, option (1) is the correct answer. Therefore, option (3) is the correct answer.
2. Metal (M) shows crimson red colour in flame test and its
7. Compound (X), on addition to copper sulphate gives a brown
halide is deliquescent. Metal (M) can be:
ppt. which turns white on addition of excess of Na2S2O3
(1) Li (2) Mg (3) Ca (4) Ba solution. Compound (X), on addition to Ag+ ion solution
Sol. Metal (Li) shows crimson red colour in flame test and its gives a yellow ppt. which is insoluble in NH4OH. Identify
halide is deliquescent. (X).
Therefore, option (1) is the correct answer. (1) CuI2 (2) KI (3) AgI (4) NaI
3. An aqueous solution of a gas (X) decolourizes an acidified Sol. X- KI
K2Cr2O7 solution. On boiling with H2O2, cooling it and then Reactions:
adding an aqueous solution of BaCl2, a white ppt. Insoluble
in dilute HCl is obtained. Identify (X). (i) 2CuSO4 + 2KI —→ 2Cu2I2 + K2SO4
(1) CO2 (2) NH3 (3) SO2 (4) Cl2 I2 + 2Na2S2O3 —→ 2NaI + Na2S4O6
Sol. X-SO2 (ii) Ag+ + KI —→ AgI + K+
Reaction: (yellow ppt.)

(i) K2Cr2O7 + H2SO4 + 3SO2 —→ K2SO4 + Cr2(SO4)3 + H2O Therefore, option (2) is the correct answer.
(ii) SO2 + H2O2 —→ H2SO4 8. A gas turns lime water milky and acidified K2Cr2O7 solution
(iii) H2SO4 + BaCl2 —→ BaSO4 ↓ + 2HCl green. Then gas is:
(White ppt) (1) HCl (2) H2S
Therefore, option (3) is the correct answer. (3) SO2 (4) CO2
4. When excess of dilute NH4OH is added to an aqueous Sol. Ca(OH)2 + SO2 —→ CaSO3(milky) + H2O
solution of copper sulphate, an intense blue colour is
K2Cr2O7 + H2SO4 + SO2 —→ K2SO4 + Cr2(SO4)3 + H2O
developed. This is due to the formation of:
(Green)
(1) [Cu(NH3)6]2+ (2) Cu(OH)2
2+
Therefore, option (3) is the correct answer.
(3) [Cu(NH3)4] (4) (NH4)2SO4
9. A salt gives white residue in charcoal cavity test but in cobalt
Sol. Cu(OH)2 .CuSO4↓ + 8NH3 —→ 2 [Cu(NH3)4]2+ nitrate test it gives pink mass. The salt contains which of the
 + SO42– + 2OH– following ion?
Therefore, option (3) is the correct answer. (1) PO43– (2) Mg2+
5. Which of the following gives a precipitate with Pb(NO3)2 (3) Al3+ (4) Zn2+
but not with Ba(NO3)2?
Sol. Mg2+ salt gives white residue in charcoal cavity test but in
(1) Sodium chloride cobalt nitrate test it gives pink mass. In this test, magnesium
(2) Sodium acetate oxide produced in the charcoal cavity test reacts with CoO
(3) Sodium nitrate in cobalt nitrate test to produce a pink mass due to the
(4) Disodium hydrogen phosphate formation of MgO.
Sol. (1) Pb2+ + 2Cl– —→ PbCl2↓ (white) Therefore, option (2) is the correct answer.

Ba2+ + 2Cl– —→ BaCl2 (water soluble) 10. What happens when solution of KCl, KF and KBr are treated
with I2?
(2) (CH 3COO) Pb and (CH 3COO) 2Ba both are water
(1) Cl2 and Br2 are evolved.
soluble salts.
(2) Cl2 is evolved.
(3) Nitrates are mostly soluble in water.
(3) Cl2, F2 and Br2 are evolved.
(4) 3Pb2+ + 2HPO42– —→ Pb3(PO4)2 ↓ (white) + 2H+
(4) None of these.
Ba2+ + HPO42– —→ BaHPO4 ↓ (white)

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 Sol. I2 is weak oxidising agent. It does not oxidise the F–, Cl–, Sol. NO3– ion belongs to conc. H2SO4 group.
Br– ion. 4NO3– + 2H2SO4 —→ 4NO2 + 2SO42– + 2H2O + O2
Therefore, option (4) is the correct answer. (Brown)
Therefore, option (2) is the correct answer.
11. An inorganic lewis acid (X) fumes in moist air, and intensity
of fumes increases when rod dipped in NH4OH is brought 13. An inorganic Lewis acid (X) shows the following reactions:
near to it. An acidic solution of (X) on addition of NH4Cl (i) It fumes in moist air.
and NH4OH gives a precipitate which dissolves in NaOH
solution. An solution of (X) does not give precipitate with (ii) The intensity of fumes increases when a rod dipped in
H2S. Hence, compounds (X) is: NH4OH is brought near it.
(1) FeCl3 (2) AlCl3 (iii) An acidic solution of (X) does not give a precipitate
with H2S. Identify (X) and give chemical equation for
(3) CrCl3 (4) ZnCl2
steps (i) to (iii) gives a precipitate which dissolves in
Sol. The Compound (X) is AlCl3. NaOH solution.
(i) AlCl3 + 3H2O → Al(OH)3 ↓ + 3HCl (1) Al(OH)3 (2) CrCl3 (3) Fe(OH)3 (4) AlCl3
(ii) AlCl3 + 3NH4OH → Al(OH)3 ↓ + 3NH4Cl Sol. X - AlCl3
(iii) Al(OH)3 + NaOH → NaAlO2 + 2H2O Reactions:
(iv) AlCl3 + H2S + H+ → No ppt. (i) AlCl3 + 3H2O —→ Al(OH)3 + 3HCl↑
(fumes)
Therefore, option (2) is the correct answer.
(ii) AlCl3 + 3NH4OH —→ Al(OH)3 + 3NH4Cl
12. An unknown salt (S) when heated with dil. H2SO4 does not (White fumes)
evolve brown vapours but with conc. H2SO4 brown vapours
(iii) AlCl3 + 3NH4OH —→ Al(OH)3 + 3NH4Cl
are obtained. The vapours when brought in contact with
(White ppt)
AgNO3 solution do not give any precipitate. The salt (S)
contains: Al(OH)3 + NaOH —→ NaAlO2 + 2H2O
(Soluble)
(1) NO2– (2) NO3– (3) Ι– (4) Br–
Therefore, option (4) is the correct answer.

PRARAMBH EXERCISE-1 (TOPICWISE)

DETECTION OF EXTRA ELEMENTS OH H
1. In the estimation of sulphur in an organic compound, fuming 4.
nitric acid is used to convert sulphur into: and
(1) SO2 (2) H2S
can be differentiated by:
(3) H2SO3 (4) H2SO4 (1) FeCl3 (2) NaOH
2. An organic compound which produces a bluish green (3) NaNO2 + HCl (4) Fehling’s solution
coloured flame on heating in presence of copper is :
(1) benzaldehyde (2) benzoic acid INORGANIC COMPOUNDS
(3) aniline (4) chlorobenzene
5. How many water of crystallisation are in Mohr's salt?
(1) 3 (2) 2 (3) 1 (4) 6
DETECTION OF THE FUNCTIONAL GROUP
6. What product is formed when aniline is treated with
3.
O CH3COCl?
(1) Acetanilide (2) Hydrazo benzene
(3) Phenol (4) Para acetyl aniline
7. Which of the following is the molecular formula of aniline
yellow?
OH
(1) O N NHCOCH3
Which of the following reagents will not react with above 2
compound?
(1) Na metal (2) AgNO3 + NH4OH (2) N == N — NH
(3) Cu2Cl2+NH4OH (4) NaHCO3

Salt Analysis 185

 16. A mixture when rubbed with organic acid smells like vinegar.
(3) N=N NH2 It contains:
(1) Sulphate (2) Nitrate
(4) None of these
(3) Nitrite (4) Acetate
TITRATION 17. If addition of conc. H2SO4 is made to an unknown salt, a
colourless and odourless gas is produced then which of the
8. Heat of neutralization will be maximum for: following can be present?
ACID (1 M) Base (1M) (1) CO2– 3 (2) S2– (3) Cl¯ (4) NO–3

1. 30 mL HCl 70 mL NaOH Rotten egg smell

(P)
2. 40 mL HCl 60 mL NaOH
 dil. H2SO4
3. 20 mL HCl 80 mL NaOH CdCO3
suspension Salt with (CH3COO)2Pb
4. 80 mL HCl 20 mL NaOH 18. Yellow ppt↓ 2–
X anion
Black ppt↓
(S) (Q)
(1) 1 (2) 2 (3) 3 (4) 4 Sodium Nitroprusside

9. If 83 mL of 0.45 M NaOH solution neutralizes a 235 mL Violet

HCl solution. Calculate the molarity of the HCl solution. (R)

(1) 0.12 (2) 0.16 (3) 0.1 (4) 0.2 Anion (X2–) is:

(1) CO32– (2) SO2–
3 (3) S2– (4) S2O2–
3
PRELIMINARY/WET TESTS
10. Which of the following can not evolve more than one gas
Concentrated HCl/Conc. H2SO4 Group
(vapour) if heated in dry test tube? 19. Which of the following pair of anions are identified by conc.
H2SO4?
(1) NaNO3(s) (2) MgCO3(s)
(1) NO3–, CO32– (2) Cl–, NO3–
(3) FeSO4(s) (4) (NH4)2Cr2O7(s)
(3) Br–, CO32– (4) CO2–3
11. On heating, a white amorphous inorganic compound 20. Which of the following salts evolved brown fumes on
becomes yellow and on cooling, turns white again.The salt treatment with conc. H2SO4?
may be:
(1) Nitrate (2) Bromide
(1) PbCO3 (2) MgCO3 (3) ZnCO3 (4) K2CO3 (3) Both (4) None of these
12. Which of the following will not react with each other when 21. A solution of a salt in concentrated H 2SO4 produced a
heated together? deep blue colour with starch iodide solution. The salt may
(1) BeO + MgO (2) Li2CO3 + BeO contain:
(3) MgO + CaCO3 (4) MgCO3 + Al2O3 (1) Chloride (2) Carbonate
13. In the Borax bead test of Cu2+, the blue colour of bead is (3) Acetate (4) Bromide
due to the formation of:
Precipitation Reactions
(1) B2O3 (2) Cu3B2
22. When a mixture containing phosphate is heated with conc.
(3) Cu(BO2)2 (4) CuO HNO3 and ammonium molybdate solution, a canary yellow
14. The hottest part of the flame of a Bunsen burner is the precipitate is formed. The formula of the yellow precipitate
(1) Zone of complete combustion. is:
(2) Blue Zone. (1) (NH4)3PO4 (2) (NH4)3PO4.12MoO4
(3) Zone of partial combustion. (3) (NH4)3PO4.12MoO3 (4) (NH4)3PO4.(NH4)2MO4
(4) All parts of the flame are equally hot. 23. A salt which gives CO2 with hot conc. H2SO4 and also
decolourizes acidified KMnO4 on warming is:
Dilute HCl/dil. H2SO4 Group
(1) HCO3– (2) CO32–
15. Tests on an aqueous solution of a sodium salt having anion (3) Oxalate (4) Acetate
Xn– gave the following results
K Cr O /H +
2 2 7
Xn–  → green solution + gas CATIONS RADICALS
Pb(NO )
3 2 → black ppt Group I Radicals
Xn– 

24. A metal nitrate reacts with KI solution to give yellow
Xn– is:
precipitate which on addition of excess of more concentrated
(1) I– (2) NO2– (3) S2– (4) SO42–

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 solution (6M) of KI dissolves forming a solution. The cation 30. A metal chloride original solution (i.e. O.S) on mixing
of metal nitrate is: with K2CrO4 solution gives a yellow precipitate soluble in
(1) Hg22+ (2) Ag+ (3) Pb2+ (4) Cu2+ aqueous sodium hydroxide. The metal may be:
(1) Mercury (2) Iron (3) Silver (4) Lead
25. Three separate samples of a solution of a single salt gave
these results. One formed a white precipitate with excess Group III Radicals
ammonia solution, one formed a white precipitate with dilute
NaCl solution and one formed a black precipitate with H2S. 31. To avoid the precipitation of hydroxides of Zn2+, Mn2+ and
The salt could be: Ni2+ along with those of Fe3+, Al3+ and Cr3+, the third group
solution should be:
(1) AgNO3 (2) Pb(NO3)2
(1) Concentrated HNO3 is added.
(3) Hg(NO3)2 (4) Mn(NO3)2
(2) Treated with excess of NH4Cl.
26. A white powder when strongly heated gives off brown fumes. (3) Concentrated H2SO4 is added.
A solution of this powder gives a yellow precipitate with a
solution of KI. When a solution of barium chloride is added (4) Treated with excess of NH4OH.
to a solution of powder, a white precipitate results. This white Group IV Radicals
powder may be:
(1) A soluble sulphate (2) KBr or NaBr 32. To increase significantly the concentration of free Zn2+ ion
in a solution of the complex ion [Zn(NH3)4]2+
(3) Ba(NO3)2 (4) AgNO3
Zn2+ (aq.) + 4NH 3 (aq.)  [Zn(NH3)4]2+ (aq.)
27. Consider the following observation;
add to the solution some:
∆
Mn+ + HCl (dilute) —→ white precipitate → water
(1) H2O (2) HCl (aq.)
CrO 2 −
4 → yellow precipitate.
(3) NH3(aq.) (4) NH4Cl (aq.)
soluble 
33. An aqueous solution of colourless metal sulphate M gives a
The metal ion Mn+ will be:

white ppt, with NH4OH. This is soluble in excess of NH4OH.
(1) Hg2+ (2) Ag+ (3) Pb2+ (4) Sn2+ On passing H2S through this solution a white ppt. is formed.
The metal M in the salt is:
Group II A Radicals
(1) Ni (2) Ba (3) Al (4) Zn
28. H2S in the presence of HCl precipitates ΙΙ group but not
ΙV group because: 34. A metal salt of cobalt form brown solution with excess of
(1) HCl activates H2S. KCN solution. This brown solution turns yellow when boiled
for a longer time in air due to formation of:
(2) HCl increases concentration of Cl–.
(1) Co(CN)2 (2) K4[Co(CN)6]
(3) HCl decreases concentration of S2–.
(3) K3[Co(CN)6] (4) K2[Co(CN)6]
(4) HCl lowers the solubility of H2S in solution.
29. Which diagram correctly represents change for given nitrate Group V, VI and Zero Radicals
solution?
HS 35. The addition of K2CO3 (aq.) to the following solution is
(1) Cd(NO3)2 2 CdS
expected to produce a precipitate in every case but that one
dil. dil.
which does not produce precipitate is:
HNO3 CH3COOH
dil. (1) BaCl2(aq.) (2) CaBr2(aq.)
Cd(OH)2 Cd(CH3COO)2
NaOH (3) Na2SO4(aq.) (4) Pb(NO3)2 (aq.)
HS
(2) Cd(NO3)2 2 CdS 36. An aqueous solution of salt gives white precipitate with
dil. dil. AgNO3 solution as well as with dilute H2SO4. It maybe:
HCl
HNO3 (1) Pb(NO3)2 (2) Ba(NO3)2
dil.
Cd(OH)2
NaOH
CdCl2 (3) BaCl2 (4) CuCl2
(3) Cd(NO3)2 NaCN 37. A metal salt solution form a yellow ppt with potassium
Cd(CN) 2
chromate in acetic acid, a white ppt with dilute sulphuric
dil. NaCN
excess acid but gives no ppt with sodium chloride or iodide it is:
HNO3
2– (1) Lead carbonate (2) Basic lead carbonate
CdS [Cd(CN)4]
(3) Barium Carbonate (4) Strontium nitrate
(4) Cu(NO3)2 NaCN Cu(CN)2 38. The brown precipitate formed by passing ammonia into
dil. NaCN Nessler’s reagent in due to the formation of
HNO3 Excess (1) Hgl42– (2) NH2O–Hg–Hgl
H2S 3–
(3) NH2–Hg–O–Hg–I (4) NH3–Hg–I
Cu2S [Cu(CN)4]

Salt Analysis 187

 PRABAL EXERCISE-2 (LEARNING PLUS)

1. Which of the following will not give positive iodoform test? 9. Which one of the following metal salts produces a blue
(1) CH3 C OH coloured bead in cobalt nitrate charcoal cavity test?

O (1) Zn2+ (2) Mg2+ (3) Sn2+ (4) Al3+

(2) Ph C CH3 10. BaCl2 solution gives a white precipitate with a solution of
a salt, which dissolves in dilute hydrochloric acid with the
O
evolution of colourless, pungent smelling gas. The gas as
(3) CH3 C CH2CH2OH well as the salt both are used as bleaching agent in the textile
O industries. The salt contains:
(1) Sulphite (2) Sulphide
(4) CH3 C
(3) Acetate (4) Carbonate
OH 11. When KI is added to acidified solution of sodium nitrite:
2. Which one is soluble in dilute HCl?
(1) NO gas is liberated and I2 is set free.
(1) AgNO3 (2) Pb(NO3)2
(2) N2 gas is liberated and HI is produced.
(3) Hg2(NO3)2 (4) Cu(NO3)2
(3) N2O gas is liberated and I2 is set free.
3. Which will not give colour with FeCl3? (4) N2 gas is liberated and HOI is produced.
(1) OH 12. Zinc pieces are added to acidified solution of SO32–. Gas
liberated can:
OH O
(1) Turn lead acetate paper black.
(2) CH3 C== CH C OC2H3 (2) Turn lime water milky.
(3) OH (3) Give white precipitate with AgNO3 solution.
(4) None of these.
(4) NH2 13. A substance on treatment with dilute H2SO4 liberates a
colourless gas which produces (i) turbidity with baryta
4. Which of the following compounds decolourise Br2—H2O water and (ii) turns acidified dichromate solution green. The
and also given positive test with neutral FeCl3? reaction indicates the presence of:
OH
(1) (2) (1) CO32– (2) S2– (3) SO32– (4) NO2–
14. A colourless gas is dissolved in water and the resulting
(3) OH (4) OH solution turns red litmus blue ; the gas may have been which
one of the following?
5. Solution of a salt in dilute H2SO4 or acetic acid produces deep
(1) HCl (2) H2S (3) SO2 (4) NH3
blue colour with starch iodide solution. The salt contains:
(1) Br– (2) I– (3) NO3– (4) NO2– 15. In the test for iodine, I2 is treated with sodium thiosulphate
(Na2S2O3):
6. A test tube containing a nitrate and another containing a
bromide and MnO2 are treated with concentrated H2SO4. Na2S2O3 + I2 → NaI + _____
The reddish brown fumes evolved are passed through water. (1) Na2S4O6 (2) Na2SO4
The water will be coloured by:
(1) The nitrate (2) The bromide (3) Na2S (4) Na3ISO4
(3) Both (1) and (2) (4) None of these 16. Which metal gives violet colour in oxidising flame when
heated with borax?
7. Colourless salt (a) + dil. H2SO4 or CH3COOH + KI —→
(1) Fe (2) Pb (3) Co (4) Mn
blue colour with starch, (a) can be:
(1) K2SO3 (2) Na2CO3 (3) NH4NO2 (4) NH4Cl 17. Which of the following halide is soluble in water?
8. There are four test tubes containing dilute HCl, BaCl2, CdCl2 (1) AgF (2) AgCl (3) AgBr (4) AgI
and KNO3 solutions. Which of the following reagents will 18. Which of the following radical can not be confirmed by
help in the identification of BaCl2? using dil.HCl?
(1) NaOH (2) K2CrO4 (1) S2– (2) S2O32– (3) CO32– (4) NO–2
(3) AgNO3 (4) Both (2) and (3)

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 19. A white solid imparts a violet colour to a Bunsen flame. On 24. A coloured solution of an inorganic salt reacts with potassium
being heated with concentrated H2SO4, the solid gives violet thiocyanate to give first a black precipitate, which slowly
vapours that turn starch paper blue. The salt may be: turns white. The salt solution also gives black precipitate
(1) KI (2) NaI (3) MgI2 (4) CaBr2 with H2S gas in slightly acidic medium. The black precipitate
20. NaCl, NaBr, NaI mixture on adding conc. H2SO4 gives gases, dissolves in potassium cyanide forming a colourless solution.
respectively: The basic radical present in the inorganic salt is:
(1) HCl, HBr, HI (2) HCl, Br2, I2 (1) Bi3+ (2) Cu2+
(3) Hg 2+ (4) None of these
(3) Cl2, Br2, I2 (4) None of these
21. What are the products formed when an aqueous solution of 25. An inorganic salt when heated with concentrated H2SO4
magnesium bicarbonate is boiled? evolves a colourless pungent smelling gas but with
(1) MgCO3, H2O, CO2 (2) Mg(HCO3)2, H2O concentrated H2SO4 and MnO2, evolves a coloured pungent
(3) Mg(OH)2, H2O, CO2 (4) Mg, CO, H2O smelling gas which bleaches moist litmus paper. The
coloured gas is:
22. A mixture is known to contain NO3– and NO2–. Before
performing ring test for NO3–, the aqueous solution should (1) NO2 (2) Cl2 (3) Br2 (4) I2
be made free of NO2–. This is done by heating aqueous 26. When CS2 layer containing both Br2 and I2 is shaken with
extract with: excess of chlorine (Cl2) water, the violet colour due to I2
(1) Conc. HNO3 (2) dil. HNO3 disappears and a pale yellow colour appears in the solution.
(3) Urea (4) Zinc dust The disappearance of violet colour and appearance of pale
yellow colour is due to the formation of:
Cations –
(1) I3 and Br2 respectively.
23. A blue colouration (in solution or precipitate) is not obtained (2) HIO3 and BrCl respectively.
when: (3) ICl and BrCl respectively.
(1) Ammonium hydroxide dissolves in copper sulphate. (4) I– and Br– respectively.
(2) Cobalt chloride reacts with NH4SCN in presence of 27. A white sodium salt dissolves in water to give a solution
amyl alcohol. which is neutral to litmus. When silver nitrate solution is
(3) Ferric chloride reacts with sodium ferrocyanide. added to the solution, a white precipitate is obtained which
(4) Aqueous ammonia reacts with white precipitate of silver does not dissolve in dilute HNO3. The anion is:
(I) chloride. (1) CO32– (2) Cl– (3) SO32– (4) S2–

PARIKSHIT EXERCISE-3 (MULTICONCEPT)

MATCH THE COLUMN MCQS 2. Match the column:
1. Match the following: Detection of
Test
functinal group
Property to be Method used for A. Schiff’s Test P. Carboxylic acid
determined determination
B. Litmus Test Q. Phenol
A. Estimation of carbon and P. Lassaigne’s test
hydrogen in an organic C. Liebermann nitroso test R. Halogen
compound D. Beilstein Test S. Aldehyde
B. Estimation of nitrogen Q. Carius method (1) A-(Q), B-(R), C-(S), D-(P)
in aniline
(2) A-(Q), B-(S), C-(R), D-(P)
C. Estimation of chlorine R. Liebig’s method
in carbon tetrachloride (3) A-(R), B-(P), C-(S), D-(Q)
(4) A-(S), B-(P), C-(Q), D-(R)
D. Detection of nitrogen, S. Kjeldahl’s
sulphur and halogens method 3. Match the items given in Column-I and Column-II.
(1) A-(P), B-(Q), C-(R), D-(S) Column-I Column-II
A. Protective colloid P. FeCl3 + NaOH
(2) A-(S), B-(R), C-(P), D-(Q)
(3) A-(Q), B-(P), C-(S), D-(R) B. Liquid-liquid colloid Q. Lyophilic colloids
(4) A-(R), B-(S), C-(Q), D-(P) C. Positively charged colloid R. Emulsion
D. Negatively charged colloid S. FeCl3 + hot water

Salt Analysis 189

 (1) A-(R), B-(R, S), (C)-(Q), (D)-(P) (1) A–(P,R); B–(T); C–(Q); D–(R,S); E–(P)
(2) A-(Q, S), (B)-(Q), (C)-(R), (D)-(P) (2) A–(P,R); B–(T); C–(Q); D–(S); E–(P)
(3) A-(Q), B-(R), C-(S), D-(P) (3) A–(R); B–(Q,S); C–(S); D–(S,T); E–(P)
(4) A-(S), B-(R), C-(P), D-(Q) (4) A–(Q); B–(S); C–(T); D–(R); E–(Q)
4. Match the Column-I with Column-II. 7. Match Column-I with Column-II and select the correct
answer using the codes given below the lists:
Column-I Column-II
Cation Group Number Column-I Column-II
Colour Ppt.
A. Co2+ and Ni2+ P. Group-II
A. White turbidity P. –
IO3 + SO2 + Starch →
B. Al3+ Q. Group-I
B. Rotten egg smell Q. SO2 + MnO4– →
C. Pb2+ R. Group-III
C. Colourless solution R. Zn + NaOH + SO2 →
D. Cu2+ S. Group-V
D. Blue colour S. CO2 + Ca(OH)2 →
E. Ba2+ T. Group-IV
(1) A–(R); B–(S); C–(Q); D–(P)
(1) A–(T); B–(R); C–(Q); D–(P); E–(S)
(2) A–(P); B–(R); C–(Q); D–(S)
(2) A–(T); B–(R); C–(Q); D–(S); E–(P)
(3) A–(R); B–(Q); C–(S); D–(P)
(3) A–(R); B–(Q); C–(S); D–(T); E–(P)
(4) A–(S); B–(R); C–(Q); D–(P)
(4) A–(Q); B–(S); C–(T); D–(R); E–(Q)
8. Match the reactions/reaction conditions listed in Column-I
5. CuCO3 was strongly heated to obtain a residue (A) and gas with the characteristics/precipitate colour of the reaction
(B). The residue obtained was treated with a salt of sodium products listed in Column-II.
(X) and oxide (Y), which produced a blue colored glassy
Column-I Column-II
compound (C) on heating in oxidizing flame. The same
Colour Ppt.
combination of (X) and (Y) gave a green colored glassy
compound (D) when Cr2(SO4)3 was heated with them in A. 2NiS + 2HNO3 + 6HCl P. Black precipitate and
oxidizing flame. Match the following accordingly: ∆ its chloride imparts
  →
extract with water greenish blue flame.
Column-I Column-II B. CoCl2 + 4NH4 CNS Q. Blue colour in organic
Colour Ppt. amyl alcohol layer.
→
A. (A) P. Cu(BO2)2 C. R. White precipitate soluble
∆
B. (B) Q. Na2CO3 CuCl2 + NaOH  →
in ammonium acetate.
C. (C) R. CuO D. H2SO4 + PbCl2 → S. Green colour solution.
D. (X) S. CO E. HgCl2 + KI (Not in T. Scarlet / red precipitate.
T. Cu2O excess) →
U. CO2 (1) A–(S); B–(Q); C–(P); D–(R); E–(T)
V. NaBO2 (2) A–(S); B–(Q); C–(P); D–(T); E–(P)
W. Cr(BO2)2 (3) A–(R); B–(T); C–(P); D–(S); E–(T)
(1) A–(V); B–(U); C–(T); D–(R) (4) A–(R); B–(V); C–(P); D–(S); E–(T)
(2) A–(R); B–(U); C–(P); D–(W) 9. Match the Column-I with Column-II.

(3) A–(R); B–(U); C–(P); D–(V) Column-I Column-II

(Compound) (Colour)
(4) A–(Q); B–(S); C–(T); D–(R)
A. HgO P. Purple solution
6. Match the Column-I with Column-II.
B. BaCO3 Q. Yellow ppt
Column-I Column-II
Test C. Na4[Fe(CN)5NOS] R. Dark brown
Anions
A. Brown ring test P. NO2– D. KI3 S. White ppt
B. Chromyl chloride test Q. CO32– (1) A–(R); B–(S); C–(P); D–(Q)
C. Baryta water (Ba(OH)2) test R. NO3– (2) A–(Q); B–(S); C–(P); D–(R)
D. Sodium nitroprusside solution S. S2– (3) A–(Q); B–(S); C–(R); D–(P)
E. Starch iodide paper test T. Cl– (4) A–(Q); B–(S); C–(R); D–(P)

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 10. Match the Column-I with Column-II. (3) A–(R); B–(P); C–(Q); D–(S)
Column-I Column-II (4) A–(Q); B–(S); C–(P); D–(R)
(Basic Radical) (Group) 14. Match the Column-I with Column-II.
A. Fe+3 P. II group Column-I Column-II
(Colour) (Gas)
B. Ni+2 Q. V group
A. Violet color gas P. SO2
C. Ba2+ R. IV group
B. Rotten egg smell Q. NO2
D. Pb2+ S. III group
C. Brown color R. I2
(1) A–(S); B–(Q); C–(P); D–(R) D. Suffocating smell S. H2S
(2) A–(Q); B–(S); C–(P); D–(R) T. Br2
(3) A–(R); B–(P); C–(Q); D–(S)
(1) A–(R); B–(S); C–(Q, T); D–(P)
(4) A–(S); B–(R); C–(Q); D–(P) (2) A–(P); B–(Q); C–(S); D–(R)
11. Match the Column-I with Column-II. (3) A–(R); B–(Q); C–(P); D–(S)
Column-I Column-II (4) A–(S); B–(Q); C–(P); D–(R)
(Cations) (Group reagent) 15. Match the Column-I with Column-II.
A. Co2+ P. Na2HPO4 in presence of NH4OH Column-II
Column-I
B. Fe3+ Q. H2S gas in acidic medium (Reaction) (Precipitate obtained
as one of the products)
C. Cu2+ R. H2S in presence of NH4OH
A. Hg2+(aq) + I–(aq) → P. Yellow precipitate
D. Mg2+ S. NH4OH in presence of NH4CI
B. Cu2+(aq) + [Fe(CN)6]4– Q. Brown precipitate
(1) A–(S); B–(Q); C–(P); D–(R) (aq) →
(2) A–(R); B–(P); C–(S); D–(Q)
C. Mg2+(aq) + NH3(aq) R. White precipitate
(3) A–(P); B–(Q); C–(R); D–(S)
+ HPO42– (aq) →
(4) A–(R); B–(S); C–(Q); D–(P)
D. Pb2+(aq) + CrO42– (aq) → S. Red precipitate
12. Match the Column-I with Column-II.
Column-I Column-II (1) A–(P); B–(Q); C–(R); D–(S)
(Reaction) (Product) (2) A–(Q); B–(P); C–(S); D–(R)
A. P. H2S (3) A–(S); B–(Q); C–(R); D–(P)
dil H SO
CO32– →
2 4
(4) A–(R); B–(S); C–(Q); D–(P)
B. dil H SO Q. SO2 16. Match the Column-I with Column-II.
S2– →
2 4

C. dil H SO R. CO2 Column-I (Colour) Column-II (Reaction)

SO32– →
2 4

D. dil H SO S. S + SO2 A. White ppt. P. CO32– + BaCl2 →

S2O32– →
2 4

(1) A–(R); B–(S); C–(P); D–(Q) B. Brown ppt. Q. CO32– + Pb(NO3)2 →

(2) A–(Q); B–(P); C–(S); D–(R)
Reddish-
(3) A–(R); B–(P); C–(Q); D–(S) C. R. Ag2CO3 Δ→ Ag2O
brown ppt.
(4) A–(Q); B–(S); C–(P); D–(R)
S. CO32– + 4Hg2+ + 3H2O →
13. Match the Column-I with Column-II.
(1) A–(S); B–(P); C–(R,Q)
Column-I Column-II
(Molecule) (Characteristic Odour) (2) A–(P,Q); B–(R); C–(S)
A. CO2 P. Rotten egg smell (3) A–(R); B–(Q); C–(R,S)
(4) A–(R,P); B–(Q); C–(S)
B. SO2 Q. Suffocating smell of burning
sulphur 17. Match the Column-I with Column-II.
C. H2S R. Vineger like smell Column-I Column-II
D. CH2COOH S. Odour less (Ppt Colour) (Reaction)
(1) A–(S); B–(Q); C–(P); D–(R) A. Pale green P. Na2S + Hg(NO3)2 →
(2) A–(Q); B–(S); C–(P); D–(R) solution

Salt Analysis 191

 B. Black ppt. Q. Na2S + Na2[Fe(CN)5NO] → 23. Identify (A):
(1) ZnCO3 (2) BaCl3 (3) BeCO3 (4) BaCO3
C. Finally purple R. Pb2+ + SO42− →
color 24. Identify (C):
D. White ppt. S. [Ag(NH3)2]Cl + 2H+ → (1) ZnO (2) ZnS (3) NH3 (4) ZnCO3
T. Fe3+ + S2O32– → 25. Identify (D):
(1) ZnCO3 (2) ZnS (3) NH3 (4) CO2
(1) A–(T); B–(P); C–(Q); D–(R,S)
(2) A–(P); B–(Q); C–(S); D–(R,T) STATEMENT BASED MCQS
(3) A–(T,S); B–(R); C–(Q); D–(P) (1) Both Statement-I and Statement-II are correct.
(4) A–(P); B–(R); C–(S,T); D–(Q) (2) Both Statement-I and Statement-II are incorrect.
(3) Statement-I is correct and Statement-II is incorrect.
COMPREHENSION BASED QUESTIONS
(4) Statement-I is incorrect and Statement-II is correct.
Comprehension (Q. 18 to 20): Read the following passage
carefully and answer the questions. 26. Statement-I: Copper sulphate with potassium ferrocyanide
forms chocolate coloured ppt. and
When compound (A) is treated with conc. H2SO4, a reddish brown
Statement-II: Oxidation state of Fe changes from +2 to +3
colour gas (B) is evolved. To this solution, a solution of (C) is
from potassium ferrocyanide to form chocolate coloured ppt.
added slowly from the side of the test tube, a blue ring is obtained
at the junction of two layers due to formation of (D). (1) Both Statement-I and Statement-II are correct.
(2) Both Statement-I and Statement-II are incorrect.
18. Gas (B) may be:
(3) Statement-I is correct and Statement-II is incorrect.
(1) Cl2 (2) Br2 (3) I2 (4) NO2
(4) Statement-I is incorrect and Statement-II is correct.
19. Compound (D) has formula:
27. Statement-I: On passing CO2 gas through lime water, the
(1) C6H5NH–C6H5 solution turns milky. because
(2) (C6H5)2N–N(C6H5)2 Statement-II: Acid-Base (neutralisation) reaction takes
(3) C6H5–NH–NH–C6H5 place.
(4) C6H5—NH—N—C6H5 (1) Both Statement-I and Statement-II are correct.
(2) Both Statement-I and Statement-II are incorrect.
O (3) Statement-I is correct and Statement-II is incorrect.
20. Which compound gives same test as compound (A)? (4) Statement-I is incorrect and Statement-II is correct.
(1) NaCl (2) NaBr (3) Na2CrO4 (4) Na2S
ASSERTION & REASON MCQs
Comprehension (Q. 21 to 22):
2 + Directions: These questions consist of two statements each, printed
(A) dil. HCl Cr O – / H
(B) + (C) 2 7 (D) as Assertion and Reason. While answering these questions, you
(Mixture of two salts) (yellow turbidity)
(Gas) (Gas) are required to choose any one of the following four responses.
(1) If both Assertion (A) and Reason (R) are True and the
NO 3
l. H Reason (R) is a correct explanation of the Assertion (A).
– +
MnO4 /H d di
an
Hot
(2) If both Assertion (A) and Reason (R) are True but Reason (R)
(E)
HgCl2 (F) is not a correct explanation of the Assertion (A).
(yellow ppt.)
(3) If Assertion (A) is True but the Reason (R) is False.
21. Find the anion(s):
(4) Assertion (A) is False but Reason (R) is True.
(1) SO32– (2) SO32–, S2–
28. Assertion (A): Phenols having free para position respond
(3) SO32–, CO32– (4) S2O32–
positively to Liebermann’s nitroso test.
22. Find out (E): Reason (R): Secondary amines give positive Liebermann’s
(1) S2– (2) CO32– (3) S2O32– (4) SO42– test.
Comprehension (Q. 23 to 25): A white amorphous powder (A)
29. Assertion (A): During test for nitrogen with Lassaigne
on strongly heating gives a colourless non-combustible gas (B)
extract on adding FeCl3 solution, sometimes a red precipitate
and solid (C). The gas (B) turns lime water milky and turbidity
disappears with a the passage of excess of gas. The solution of is formed.
(C) in dilute HCl gives a white ppt. with an aqueous solution of Reason (R): This indicates that sulphur is also present.
K4[Fe(CN)6]. The solution of (A) in dilute HCl gives a white ppt. 30. Assertion (A): A mixture of o-nitrophenol and p-nitrophenol
(D) on passing H2S in presence of excess of NH4OH. can be separated by steam distillation.

192 P NEET Dropper Module-6 CHEMISTRY

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 Reason (R): o-nitrophenol is steam volatile but p-nitrophenol
34. Assertion (A): In acidic medium, Zn2+ is not precipitated
is not though both are water soluble. by S2– ions.
31. Assertion (A): During digestion with conc. H2SO4 nitrogen Reason (R): Common ion effect reduces the concentration
of the compound is converted to (NH4)2SO4. of S2– ions to the minimum level.
Reason (R): (NH4)2SO4 on heating with alkali given NH3 gas. 35. Assertion (A): Iodine is liberated when KI is added to Cu2+
32. Assertion (A): A solution of AgCl in NH4OH gives a white ions but Cl2 is not liberated when KCI is added to Cu2+ ions.
precipitate with HNO3. Reason (R): The reducing power of I is more than Cl.
Reason (R): [Ag(NH3)2] decomposes in the presence of 36. Assertion (A): PbS can be separated from ZnS by
HNO3. electrostatic separation method.
33. Assertion (A): The solubility of Zn(OH)2 is enhanced in Reason (R): PbS is a good conductor and ZnS is a poor
acidic as well as in basic medium as compared to water. conductor of electricity.
Reason (R): Zn(OH)2 is an amphoteric hydroxide.

Salt Analysis 193

 Answer Key

CONCEPT APPLICATION
1. (4) 2. (1) 3. (4) 4. (2) 5. (3) 6. (3) 7. (2) 8. (3) 9. (1) 10. (3)
11. (4) 12. (1) 13. (3) 14. (1) 15. (4) 16. (3) 17. (4) 18. (1) 19. (1) 20. (2)
21. (4) 22. (1) 23. (4) 24. (2) 25. (1)

PRARAMBH EXERCISE-1 (TOPICWISE)

1. (4) 2. (4) 3. (4) 4. (1) 5. (4) 6. (1) 7. (3) 8. (2) 9. (2) 10. (2)
11. (3) 12. (3) 13. (3) 14. (1) 15. (3) 16. (4) 17. (1) 18. (3) 19. (2) 20. (3)
21. (4) 22. (3) 23. (3) 24. (3) 25. (2) 26. (4) 27. (3) 28. (3) 29. (3) 30. (4)
31. (2) 32. (2) 33. (4) 34. (3) 35. (3) 36. (3) 37. (3) 38. (3)

PRABAL EXERCISE-2 (LEARNING PLUS)

1. (1) 2. (4) 3. (4) 4. (3) 5. (4) 6. (2) 7. (3) 8. (2) 9. (4) 10. (1)
11. (1) 12. (1) 13. (3) 14. (4) 15. (1) 16. (4) 17. (1) 18. (2) 19. (1) 20. (2)
21. (3) 22. (3) 23. (4) 24. (2) 25. (2) 26. (2) 27. (2)

PARIKSHIT EXERCISE-3 (MULTICONCEPT)

1. (4) 2. (4) 3. (3) 4. (1) 5. (3) 6. (2) 7. (4) 8. (1) 9. (2) 10. (4)
11. (4) 12. (3) 13. (1) 14. (1) 15. (3) 16. (2) 17. (1) 18. (4) 19. (2) 20. (3)
21. (2) 22. (4) 23. (1) 24. (1) 25. (2) 26. (3) 27. (2) 28. (2) 29. (2) 30. (1)
31. (2) 32. (1) 33. (1) 34. (1) 35. (1) 36. (1)

194 P NEET Dropper Module-6 CHEMISTRY

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