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Principles Related to
Practical Chemistry

(CHEMISTRY)
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Principles Related to Practical Chemistry

● Qualitative Analysis of Organic Compounds:

This is used to detect nitrogen, halogen and sulphur present in organic compounds.

a) Sodium Extract: Aqueous solution containing soluble sodium salt of the elements i.e NaCl, Na2S and NaCNS
formed by fusion of compound with sodium metal.

b) Formation of Sodium Extract: It is a two step process

Step 1: Organic compounds are fused with dry sodium in a fusion-tube

Step 2: Fused mass after extraction with water is boiled and filtered.

c) Use of Sodium Extract: Sodium extract (S.E.) is used to detect elements (other than C and H) and the tests are
given in the table.

Element Sodium Extract (S.E.) Confirmed Test

Nitrogen S.E.+ FeSO4 +NaOH, boil and cool

Na + C + N +Δ→ NaCl +

FeCl3 + conc. HCl → Blue/ green colour

Reactions Involved:

Sulphur (i) S.E. + sodium nitroprusside → Violet Colour

2Na + S → Na2S (ii) S.E + CH3CO2H + (CH3CO2)2Pb → black ppt.

Reactions Involved:
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Halogen Na +X + Δ→ NaX S.E. + HNO3+AgNO3→

(X = Cl, Br, I) (i) White ppt soluble in aq NH3 confirms Cl.

(ii) Pale yellow ppt partially soluble in aq. NH3 confirms Br.

(iii) Yellow ppt insoluble in aq. NH3 confirms I.

Reactions Involved:

Nitrogen As in a test for nitrogen; instead of green or blue colour, blood

and sulphur red colouration confirms presence of N and S both.
together Na+ C + N + S+ Δ→ NaCNS
Reactions Involved:
with excess Na the
thiocyanate formed
decomposes into cyanide and
sulphide.
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NaCNS + 2Na → NaCN

+Na2S

● Qualitative Analysis of Inorganic Salts:

1. Physical Examination of Salts/Mixture

Observation Inference

1. Substance is coloured

i) Blue Copper salt

ii) Dark green Chromium salt

iii) Green Salts of Fe(II), Ni, Cu or Cr

iv) Light yellow or brown Salts of Fe(III)

v) Dark brown PbO2,Bi2S3

vi) Light pink Salts of Mn

vii) Pink Salts of Co

viii) Red HgO, HgI2,Pb3O4

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ix) Orange red Sb2S3

2. Substance is deliquescent CaCl2,ZnCl2,MgCl2, MnCl2, nitrites, nitrates

3. Substance is heavy Salts of Pb, Hg and Ba

4. Substance is light Carbonates of Bi, Mg, Al, Zn, Ca, Sr

2. Effect of Heating:

Observation Inference

1. Substance melts Salts of alkali metals and salts having water of

crystallisation.

2. Substance decrepitates (crackling noise) NaCl, KI, Pb(NO3)2 and Ba(NO3)2

3. Substance swells (due to loss of water of Alums, borates and phosphates

crystallisation)

4. The substance sublimes and the colour of

sublimate is

i) White HgCl2, Hg2Cl2,NH4X, AlCl 3, As 2O3, Sb2O3

ii) Yellow As2S3 and HgI2 (turns red when rubbed with glass rod).

iii) Blue black and violet vapours Iodides

5. A residue (generally oxide) is left and its

colour is
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i) Yellow (hot) and white (cold) ZnO

ii) Reddish brown (hot); yellow (cold) PbO

iii) Black (hot); Red (cold) HgO, Pb3O4

iv) Black (hot); Red brown (cold) Fe2O3

6. Gas is evolved

(A) Colourless and odourless

i) O2 - rekindles a glowing splinter Alkali nitrates (2KNO3 → 2KNO2 + O2)

ii) CO2 - turns lime water milky Carbonates and oxalates (CaCO3 → CaO + CO2)

iii) N2 Ammonium nitrite (NH4NO2 → N2 + 2H2O)

(B) Colourless gas with odour

i) NH3 - Turns red litmus blue and Ammonium salts (NH4)2SO4 → NH4HSO4 + NH3
mercurous nitrate paper black

ii) SO2 - Smell of burning sulphur, Sulphites and thiosulphates

turns acidified K2Cr2O7 paper green
CaSO3 →CaO + SO2

iii) HCl - Pungent smell, white fumes with Hydrated chlorides

ammonia
CaCl2.6H2O → Ca(OH)2 + 4H2O + 2HCl
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iv) H2S - smell of rotten eggs, turns lead Sulphides

acetate paper black
Na2S + 2H2O → 2NaOH + H2S

(C) Coloured gas

i) NO2 - Brown, turns starch iodide Nitrites and nitrates of heavy metals
paper blue
2Cu(NO3)2 → 2CuO + 4NO2 + O2

ii) Br2 - Reddish brown Bromides

2CdBr2 + O2 → 2CdO + 2Br2

(A) Turns starch paper yellow

(B) turns starch iodide paper blue

iii) I2 - Violet, turns starch paper blue Iodides

2CdI2 + O2 → 2CdO + 2I2

iv) Cl2 - Greenish yellow Chlorides

(A) bleaches moist litmus paper CuCl2 + H2O → CuO + 2HCl

CuO + 2HCl → Cu + H2O + Cl2

(B) bleaches indigo solution

(C) turns starch iodide paper blue

3. Flame test:
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Metals Colour

Li crimson red

Na golden yellow

K Violet

Ca Brick red

Sr Crimson

Ba apple green

● Test for Anions:

1. Carbonate (CO32- )

i) Dilute HCl : gives effervescence, due to the evolution of carbon dioxide.

CO32- + 2H+ → CO2­ + H2O

The gas gives turbidity with lime water and baryta water.

CO2 + Ca2+ + 2OH- → CaCO3 ¯ + H2O

CO2 + Ba2+ + 2OH-→ BaCO3 ¯ + H2O

On prolonged passage of carbon dioxide in lime water, the turbidity slowly disappears due to the formation of
soluble hydrogen carbonate.

CaCO3 ¯→ + CO2 + H2O → Ca(HCO3)2

ii) Barium chloride or Calcium chloride solution: White ppt of barium or calcium carbonate is obtained, which
is soluble in mineral acid.

CO32- + Ba2+ → BaCO3 ¯

CO32- + Ca2+ → CaCO3 ¯

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iii) Silver nitrate solution: White ppt of silver carbonate is obtained.

CO32- + 2Ag+ → Ag 2CO3¯

The ppt so obtained is soluble in nitric acid and in ammonia. The ppt becomes yellow or brown on addition of
excess reagent and same may also happen if the mix is boiled, due to the formation of silver oxide

Ag2CO3¯ → Ag 2O ¯ + CO2 ­

2. Sulphites (SO32-)

i) Dilute HCl or Dilute H2SO4 : decomposes with the evolution of sulphur dioxide

SO32- + 2H+ → SO2 + H2O

The gas has a suffocating odour of burning sulphur.

ii) Acidified potassium dichromate solution: Turns filter paper moistened with acidified potassium dichromate
solution, green due to the formation of Cr3+ions.

iii) Lime water : On passing the gas through lime water, a milky ppt is formed.

Precipitate dissolves on prolonged passage of the gas, due to the formation of hydrogen sulphite ions.

iv) Barium chloride or Strontium chloride solution: Gives white ppt. of barium or strontium sulphite.

3. Sulphide (S-2)

i) Dil. HCl or Dil. H2SO4: A colourless gas smelling of rotten eggs (H2S) is evolved.

S2- + 2H+ → H2S­

ii) The gas turns lead acetate paper black

iii) Gives yellow ppt. with CdCO3

Na2S + CdCO3 → CdS¯ + Na­2CO3

iv) Silver nitrate solution: black ppt. of silver sulphide insoluble in cold but soluble in hot dil nitric acid.

S2- + 2Ag+ → Ag 2S ¯

v) Sodium nitroprusside solution : Turns sodium nitroprusside solution purple

Na2S + Na2[Fe(CN)5NO] → Na4[Fe(CN)5NOS]

4. Nitrites (NO2-)

i) Dil HCl and Dil. H2SO4 : Adding to solid nitrite in cold yields pale blue liquid (due to the presence of free
nitrous acid HNO2 or its anhydride N­2O3) & the evolution of brown fumes of nitrogen dioxide, the latter being largely
produced by combination of nitric oxide with the oxygen of the air

ii) Silver nitrate solution : White crystalline ppt. is obtained

NO2- + Ag + → AgNO 2¯
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iii) Turns acidified KI - starch paper blue

2KI + 2NO2 → 2KNO2 + I2 ­

Starch + I2 → Blue colour

iv) Brown ring test: When the nitrite solution is added carefully to a conc. solution of Iron(II) sulphate acidified
with dil acetic acid or with dilute sulphuric acid, a brown ring is formed, due to the formation of [FeNO]SO4 at the
junction of the two liquids.

5. Acetate (CH 3COO-)

i) Dilute Sulphuric Acid : Smell of vinegar is observed.

CH3COO- + H+ → CH3COOH ­

The following test is performed with the aqueous salt solution.

ii) Iron (III) Chloride Solution: Gives deep - red colouration

CH3COONa + FeCl3 → (CH3COO)3Fe + 3NaCl

Brown colour

6. Thiosulphates

i) Dil Hydrochloric acid: Gives sulphur & sulphur di oxide

ii) Silver nitrate solution: Gives white ppt. of silver thiosulphate.

S2O32-+ 2Ag+ → Ag 2S2O3 ¯

The ppt. is unstable, turning dark on standing, when silver sulphide is formed.

Ag2S2O3¯ + H2O → Ag 2S + H2SO4

iii) Lead acetate or Lead nitrate solution: Gives white ppt.

S2O32-+ Pb2+ → PbS2O3 ¯

On boiling it turns black due to the formation of PbS.

PbS2O3 ¯ + H2O →PbS ¯ + 2H+ + SO42

7. Chloride (Cl-)

i) Conc. H2SO4 : decomposes with the evolution of HCl.

Cl- + H2SO4 → HCl + HSO

Gas so produced

(1) Turns blue litmus paper red

(2) Gives white fumes of NH4Cl when a glass rod moistened with an ammonia solution is brought near the mouth of
the test tube.
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ii) Silver nitrate solution: White, curdy ppt. of AgCl insoluble in water & in dil .nitric acid, but soluble in dilute
ammonia solution.

v) Chromyl chloride test: When a salt containing chloride ion is heated with K2Cr2O7 and conc. H2SO4 orange red
fumes of chromyl chloride (CrO2Cl2) are formed.

K2Cr2O7 + 4NaCl + 6H2SO4 → 2KHSO4 + 4NaHSO4 + 2CrO2Cl2 ­+ 3H2O

orange – red fumes

Chlorides of mercury, owing to their slight ionization, do not respond to this test and only partial conversion to
CrO2Cl2 occurs with the chlorides of lead, silver, antimony and tin.

When chromyl chloride vapours are passed into sodium hydroxide a yellow solution of sodium chromate is formed
which when treated with lead acetate gives yellow ppt. of lead chromate.

CrO2Cl2 + 2NaOH → Na2CrO4 + 2HCl

Yellow solution

Na2CrO4 + (CH3COO)2 Pb → 2CH3COONa + PbCrO4 ¯ (yellow ppt.)

8. Bromide (Br-)

i) Conc. H2SO4 : Gives reddish brown vapours of bromine accompanying the hydrogen bromide.

ii) Manganese dioxide and conc. sulphuric acid : When a mix of solid bromide, MnO2 and conc. H2SO4 is
heated reddish brown vapours of bromine.

2KBr + MnO2 + 2H2SO4 → Br2 ­+ K2SO4 + MnSO4 + 2H2O

The following tests are performed with the aqueous salt solution.

iii) Silver nitrate solution: Pale yellow ppt. of silver bromide is obtained. This ppt. is sparingly soluble in dil but
readily soluble in conc. ammonia solution and insoluble in dil. HNO3.

iv) Lead acetate solution: White crystalline ppt. of lead bromide which is soluble in

boiling water.

9. Iodide (I-)

i) Conc. H2SO4 : Gives violet vapours of iodine

ii) Silver nitrate solution: Yellow ppt. of silver iodide AgI, very slightly soluble in conc. ammonia solution and
insoluble in dil nitric acid.

10. Nitrate (NO3- )

i) Conc H2SO4 : Gives reddish - brown vapours of nitrogen dioxide

4NO3- + 2H2SO4 → 4NO2­+ 2SO42- + 2H2O + O2­

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ii) Brown ring test: When freshly saturated solution of iron (II) sulphate is added to nitrate solution and conc.
H2SO4 is poured slowly down the side of the test - tube, a brown ring is obtained.

2NO3- + 4H2SO4 + 6Fe2+ → 6Fe3+ +2NO + 4SO4–2 + 4H2O

Fe2+ + NO­→ [Fe(NO)]2+

On shaking and warming the mix, the brown colour disappears, nitric oxide is evolved and a yellow solution of
Iron(III) ions remains.

11. Sulphate (SO42-)

i) Barium chloride solution: White ppt. of barium sulphate BaSO4 insoluble in warm dil. hydrochloric acid and
in dilute nitric acid, but moderately soluble in boiling, conc. hydrochloric acid.

ii) Mercury (II) nitrate solution: Gives yellow ppt. of basic mercury (II) sulphate

12. Chromate CrO42 -and Dichromate (Cr2O)

i) Barium chloride solution: Pale - yellow ppt. of barium chromate soluble in dilute mineral acids but insoluble
in water and acetic acid.

CrO + Ba2+ → BaCrO4 ¯

Dichromate ion also gives the same ppt. but due to the formation of strong acid precipitation is partial.

Cr2O+ 2Ba2+ + H2O 2 BaCrO4 ¯ + 2H+

If sodium hydroxide or sodium acetate is added, precipitation becomes quantitative.

ii) Silver Nitrate Solution: Brownish - red ppt. of silver chromate Ag2CrO4 which is soluble in dil. nitric acid & in
ammonia solution, but insoluble in acetic acid.

A reddish brown ppt. of silver dichromate Ag 2Cr2O7 is formed with a conc. solution of a dichromate.

13. Permanganate MnO

i) Hydrogen peroxide : It decolourises acidified potassium permanganate solution

2MnO4- + 5H2O2 + 6H+ ¾¾® 5O2 ­+ 2Mn2+ + 8H2O.

ii) Iron (II) sulphate, in the presence of sulphuric acid, reduces permanganate to manganese (II). The solution
becomes yellow because of the formation of iron (III) ions

MnO4- + 5Fe2+ + 8H+ → 5Fe3+ + Mn2+ + 4H2O

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● Test For Cations:

Group Group reagent Ions Colour & ppt.

Group I dil HCl Pb2+, Hg+, Ag + PbCl2, Hg2Cl2, AgCl -

white

Group II Yellow-CdS,As2S3,

Group II A H2S in dil HCl Hg2+, Cu2+, Bi3+, Cd2+ As2S5 , SnS2

Black - HgS, CuS, PbS

Group II B As3+, As 5+, Sb3+, Sb5+, Orange - Sb2S3, Sb2S5

Sn2+, Sn4+
Brown - Bi2S3 ,SnS

Group III A NH4OH in presence of NH4Cl Fe3+, Al 3+, Cr3+ Fe(OH)3, Al(OH) 3,Cr(OH)3
Brown White
Green

GroupIII B H2S in presence of NH3 & NH4Cl or Ni2+, Co+2, Mn+2, Zn2+ ZnS - white or grey,
(NH4)2S.
Black - CoS, NiS

MnS - Buff (light pink)

Group IV (NH4)2CO3 in presence of NH4Cl & Ba+2, Sr2+, Ca+2 BaCO3, SrCO3, CaCO3 -
NH4OH. white

Group V No common group reagent. Mg+2, Na+, K+, NH4+ ¾

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Group I (Pb2+, Ag +, Hg+)

(A) PbCl2 gives a yellow ppt. with K2CrO4. The ppt. is insoluble in acetic acid but soluble in NaO

(B) PbCl2 + 2KI → PbI2 + 2KCl

(Yellow)

PbCl2 + 2KI (excess) → K2[PbI4]

AgCl is soluble in NH4OH forming a complex while Hg2Cl2 forms a black ppt. with NH4OH.

AgCl + 2NH4­OH → Ag(NH 3)2Cl + 2H2O

Hg2Cl2 + 2NH4OH → H2NHgCl + Hg + NH4Cl + 2H2O

Amino mercuric Chloride

2. Group II A (Hg 2+, Cu2+, Bi3+, Cd2+)

i) Hg+2ions in solution, in addition to SnCl2, give a white precipitate turning black.

2Hg+2 + SnCl2 → Sn+4 + Hg2Cl2

White

Hg2Cl2 + SnCl2 → SnCl4 + 2Hg

Black

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

Cu+2 + 4NH4OH → [Cu(NH3)4 ]+2 + 4H2O

Deep blue in colour

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

2Cu+2 + K4Fe(CN)6 → Cu2[Fe(CN)6] + 4K+

iii) Bi+3 ions in solution of HCl on addition of water give white cloudy precipitate.

BiCl3 + H2O → BiOCl + 2HCl

White ppt.

When treated with sodium stannite a black ppt. is obtained.

2BiCl3 + 3Na2SnO2 → 2Bi ¯ + 3Na2SnO3 + 6NaCl + 3H2O

black

iv) Cd+2 ions in solution, with NaOH give a white precipitate.

Cd+2 + 2NaOH → Cd(OH)2 + 2Na+

white
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With ammonium hydroxide, Cd2+ ions give a white precipitate which dissolves in excess.

Cd2+ + 4NH4OH → [Cd(NH3)4](OH)2 + 2H2O

3. Group II B (As3+, As 5+, Sb3+, Sb5+, Sn3+, Sn4+)

v) As+3 ions in solution give yellow precipitate with ammonium molybdate and HNO3 on heating.

H3AsO4 +12(NH4)2MoO4 +21HNO3 → (NH4)3 AsMo12O40+ 21NH4NO3 + 12H2O

Yellow ppt.

vi) Sn2+ ions in solution as SnCl2 give white ppt. with HgCl2 ,which turns black on standing.

vii) Sb+3 ions in solution as SbCl3 , in addition to water give white precipitate.

SbCl3 + H2O → SbOCl + 2HCI

White

4. Group III A (Al 3+, Fe3+, Cr3+)

1. White precipitate of Al(OH) 3 is soluble in NaOH

Al(OH)3 + NaOH → NaAlO2 + 2H2O

2. Precipitate of Cr(OH)3 is soluble in NaOH + Br2 water and addition of BaCl2 to this solution gives yellow
precipitate.

Fe(OH)3 is insoluble in NaOH

3. Brown precipitate of Fe(OH)3 is dissolved in HCl and addition of KCNS to this solution gives blood red colour.

Also in addition to K4Fe(CN)6 to this solution, a prussian blue colour is obtained.

FeCl3 + 3K4Fe(CN)6 → Fe4[Fe(CN)6]3 + 12KCl

prussian blue colour

5. Group III B (Ni2+, Co2+, Mn2+, Zn+2)

1. Ni+2 and Co+2 ions in solution, in addition to KHCO3 and Br2 water give apple green colour if Co+2 is present and
black precipitate if Ni+2 is present.

CoCl2 + 6KHCO3 →K4[Co(CO3)3] + 2KCl + 3CO2­+ 3H2O

2K4[Co(CO3)3] + 2KHCO3 + [O] → 2K3[Co(CO3)3] + 2K2CO3 + H2O

Apple green colour

NiCl2 + 2KHCO3 → NiCO3 + 2KCl + H2O + CO2­

2NiCO3 + 4NaOH + [O] → Ni2O3 + 2Na2CO3 + 2H2O

Black ppt.
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2. Zn+2 ions in solution give white precipitate with NaOH, which dissolve in excess of NaOH.

3. Mn+2 ions in solution give pink precipitate with NaOH turning black or brown on heating.

6. Group IV (Ba2+, Sr2+, Ca2+)

Ba+2 ions in solution give

(A) Yellow precipitate with K2CrO4

Ba+2 + K2CrO4 → BaCrO4 + 2K+

Yellow

(B) White precipitate with (NH4)2SO4

Sr+2 ions give white precipitate with (NH4)2SO4 and (NH4)2C2O4

Ca+2 ions give white precipitate with (NH4)2 C2O4 only.

7. Group V (NH4+, Na+, K+, Mg+2)

All ammonium salts on heating with alkali say NaOH give a colourless gas with a pungent smell (NH3)

(A) Gas evolved gives white fumes with HCl

(B) Paper soaked in CuSO4 solution, is turned deep blue by NH3 due to complex formation

(C) With Hg2 (NO3)2 , a black colour is obtained

Hg2(NO3)2 + 2NH3 → Hg + Hg(NH2)NO3 ¯ + NH4NO3

black

(D) With Nessler's reagent (alkaline solution of potassium tetraiodomercurate(II) ), a brown ppt. is obtained

1. Potassium salts give yellow ppt. with sodium cobaltinitrite

2. Sodium salts give a heavy white ppt. with potassium dihydrogen antimonate
3. Mg2+ gives white ppt. of magnesium hydroxide with sodium hydroxide