Salt Analysis

Quantitataive Qualitative
Analysis Analysis

Salt

Cation Anion
Basic Radical Acidic Radical
Cations – Pb2+, Cu2+, Al3+, Anions – CO32–, S2–, SO42–,
Fe3+, Zn2+, Ca2+, Ba2+, NO2–, NO3–, Cl–, Br–, I–
Mg2+, NH4+
 Identification of Anion
Identification of Anion wet test
 Test carried out in solution phase
 Identification carriedout by colour change, gas evolved, smell or ppt formation
etc.
If salt is water insoluble then soda extract is prepared.
 Sodium carbonate extract (SCE), (soda extract) is prepared by replacement of
cation by Na+, because almost all sodium salt are water soluble.

Insoluble salt + Na2CO3 — Soluble salt. (double displacement / ppt

exchange reaction)
The basic nature of soda extract is neutralized by small amount of acid.
Anions
Class 1A - CO32–, S2–, NO2–,
Class 1B - NO3–, Cl–, Br–, I–,
Class 2 - SO42–
Preliminary test with dilute sulphuric acid
∆
Soluble salt + dilute H2SO4 Gas evolved (then Class 1A anion)
If gas not evolved then Class 1B or
Class 2 anion

Inference
Observations
Gas Evolved Possible Anion
A colourless, odourless gas is evolved with brisk effervescence,
CO2 Carbonate (CO32–)
which turns lime water milky.
Colourless gas with the smell of rotten eggs is evolved which
H2S Sulphide (S2–)
turns lead acetate paper black.
Brown fumes which turn acidified potassium iodide solution
NO2 Nitrite (NO2–)
containing starch solution blue.
 Test for carbonate ion (CO32–)

Solubility – All carbonates except Group 1 metals and NH4+ are water insoluble.
Li2CO3 is sparingly soluble in water.

Preliminary test with dilute sulphuric acid

∆
Na2CO3 + dilute H2SO4 NaCl + H2O + CO2
brisk effervescence
Confirmatory test
(i) Lime water test

Co2 turns lime water milky and when excess of CO2 is passed, milkiness disappeared.
∆
CO2 + Ca(OH)2 CaCO3 + H2O
Milkiness

(ii) Test by AgNO3

∆ ∆ 1
2AgNO3 + Na2CO3 2NaNO3 + Ag2CO3 2Ag + O2 + CO2
2
 Test for sulphide ion (S2–)

Solubility – All sulphide except Group 1 metals and NH4+ are water insoluble.

Preliminary test with dilute sulphuric acid

∆
Na2S + dilute H2SO4 Na2SO4 + H2S
rotten egg like smell
Confirmatory test
∆
(i) Na2S + few drop of dilute H2SO4 H2S (pass through lead acetate black
precipitate formed)
 CH3COO 2 Pb  H 2S 
 PbS  CH 3COOH
Lead sulphide
Black precipitate
(ii) Test by sodium nitroprusside
Na2S + Na2[Fe(CN)5 (NO)] — Na4[Fe(CN)5 NOS]
Purple color

NO+ + S2– — NOS

 Test for nitrite ion (NO2–)

Preliminary test with dilute sulphuric acid

∆
NaNO2 + dilute H2SO4 Na2SO4 + HNO2 (double displacement
reaction)

∆
3HNO2 HNO3 + 2NO + H2O (Ostwald
method)

1
NO + O — NO2
2 2

immediately brown colour gas

Confirmatory test
(i) NO2– + CH3COOH — HNO2 + CH3COO–
2HNO2 + 2KI + 2CH3COOH — 2CH3COOK + 2 H2O + 2NO + I2
I2 + Starch — Blue complex

(ii) Sulphanilic acid – 1-naphthylamine reagent test (Griss-Ilosvay test)

NO2– + CH3COOH — HNO2 + CH3COO–

Test solution should be very dilute.

Preliminary examination with concentrated sulphuric acid (Class 1B anions)
Inference
Observations Gas / Vapours Possible Anion
Evolved
A colourless gas with pungent smell, which gives dense white
fumes when a rod dipped in ammonium hydroxide is brought HCl Chloride, (Cl–)
near the mouth of the test tube.
Reddish brown gas with a pungent odour is evolved. Intensity
of reddish gas increases on heating the reaction mixture after
Br2 vapours Bromide, (Br–)
addition of solid MnO2 to the reaction mixture. Solution also
acquires red colour.
Violet vapours, which turn starch paper blue and a layer of
violet sublimate is formed on the sides of the tube. Fumes I2 vapours Iodide, (I–)
become dense on adding MnO2 to the reaction mixture.
Brown fumes evolve which become dense upon heating the
reaction mixture after addition of copper turnings and the NO2 Nitrate, (NO3–)
solution acquires blue colour.
 Test for chloride ion (Cl–)
Solubility – All chlorides except AgCl, Hg2Cl2, PbCl2 and Cu2Cl2 are water soluble.

Preliminary test with dilute sulphuric acid

NaCl + H2SO4 — NaHSO4 + HCl
warm conc. colorless gas (pungent smell)

Confirmatory test
(i) Litmus paper test (moist)-blue litmus turns into red.
(ii) Glass rod dipped in NH4OH – white cloudy appearance due to formation of NH4Cl
(iii) Test by AgNO3
NaCl + AgNO3 — AgCl + NaNO3
white precipitate
(iv) Test by MnO2 (redox reaction)
𝐻+
Cl– + MnO2 Cl2 + Mn2+
yellowish green
(v) Chromyl chloride test
∆ 
H2O
NaOH

for NaCl + K2Cr2O7 + conc. 6H2SO4 2KHSO4 + 4 NaHSO4 + 3H2O + 2CrO2Cl2
Na2CrO4
chromium chloride
 Test for bromide ion (Br–)

Solubility – All bromides except AgBr, Hg2Br2, PbBr2 and Cu2Br2 are water soluble.

Preliminary test with dilute sulphuric acid

2NaBr + 2H2SO4 — Br2 + SO2 + Na2SO4 + 2H2O

warm conc. reddish brown
fume

𝐻+
Br– + MnO2 Br2 + Mn2+
intense
reddish brown
Confirmatory test
(i) AgNO3 + NaBr — AgBr + NaNO3
pale yellow
precipitate
(ii) NaBr + Cl2 — NaCl + Br2 (Br2 soluble in CCl4 while NaBr insoluble in CCl4)
 Test for iodide ion (I–)

Solubility – All iodide except AgI, PbI2, HgI2 and BiI3 are water soluble.

Preliminary test with dilute sulphuric acid

2NaI + 2H2SO4 — I2 + SO2 + Na2SO4 + 2H2O

warm conc. violet vapour

Confirmatory test
(i) 2NaI + 2H2SO4 — I2 + SO2 + Na2SO4 + 2H2O
warm conc. violet vapour
I2 + starch solution — blue color solution

𝐻+
(ii) I– + MnO2 I2 + Mn2+
intense
violet vapour

(iii) AgNO3 + NaI — AgI + NaNO3

yellow
 Test for nitrate ion (NO3–)

Solubility – All nitrates are water soluble.

Preliminary test with dilute sulphuric acid

2NaNO3 + H2SO4 — 2HNO3 + Na2SO4

warm conc.
∆
4HNO3 H2O + 4NO2 + O2
brown
Confirmatory test
(i) 2NaNO3 + H2SO4 — 2HNO3 + Na2SO4
warm conc.
∆
4HNO3 H2O + 4NO2 + O2

2NaNO3 + 4H2SO4 + 3Cu — 3CuSO4 + SO2 + Na2SO4 + 4H2O + 2NO

copper sulphate (blue)
2NO + O2 — 2NO2
(Brown fumes)
(ii) Brown ring test
NaNO3 + conc. H2SO4 + freshly prepare FeSO4 — brown ring on liquid junction
(mixed through wall of test tube)

NaNO3 + H2SO4 — NaHSO4 + HNO3

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

FeSO4 + NO — [Fe(NO)]SO4
Nitroso ferrous sulphate (Brown ring)
 Test for sulphate ion (SO42–)

Solubility – All sulphates except Hg2SO4, PbSO4, Li2SO4, BaSO4, SrSO4 and CaSO4 are
water soluble.

It does not give test with conc. / dil. H2SO4

Confirmatory test
𝑎𝑐𝑒𝑑𝑖𝑓𝑖𝑒𝑑 (𝐶𝐻3𝐶𝑂𝑂𝐻)
(i) Na2SO4 + BaCl2 BaSO4 + 2NaCl
barium sulphate white precipitate
(insoluble in conc. HCl or conc.
HNO3)

(ii) Na2SO4 + BaCl2 — BaSO4 + 2NaCl

Neutralised by Barium sulphate
CH3COOH (White precipitate)
 DETECTION OF CATION

Cations - Pb2+, Cu2+, Al3+, Fe3+, Ni2+, Zn2+ ,Ca2+, Ba2+, Mg2+, NH4+

PRELIMINARY EXAMINATION
1. Colour Test

Colour Cations indicated

Light green, Yellow, Brown Fe2+, Fe3+
Blue Cu2+
Bright green Ni2+
 2. DRY HEATING TEST

Colour when hot Colour when cold inference

Blue White Cu2+

White Yellow Zn2+

 3. Flame Test
• The chlorides of several metals impart characteristic colour to the flame
because they are volatile in non-luminous flame.
• This test is performed with the help of a platinum wire
• Make a tiny loop at one end of a platinum wire.
• To clean the loop dip it into concentrated hydrochloric acid and hold it in a
non-luminous flame

Colour of the flame Colour of the flame Inference

observed by naked eye observed through blue
glass

Green flame with blue Same colour as Cu2+

centre observed without glass
Apple green Bluish green Ba2+ Zn2+
Brick red Green Ca2+ Ba2+
 4. BORAX BEAD TEST
• This test is employed only for coloured salts because borax reacts with
metal salts to form metal borates or metals, which have characteristic
colours.
• Red hot platinum wire dipped into borax powder and heat it again until
borax forms a colourless transparent bead on the loop.
• Dipped the loop in small quantity of salt and hold it in flame.
• To remove bead from loop heat is to red hot and tap it.

Na2B4O7 .10H2O → Na2B4O7 + 10H2O

Borax
Na2B4O7 → 2NaBO2 + B2O3
Sodium metaborate Boric anhydride
 4. BORAX BEAD TEST
• On treatment with metal salt, boric anhydride forms metaborate of the
metal which gives different colours in oxidising and reducing flame.

• In Case of copper sulphate reactions:

Reaction :
CuSO4 + B2O3 Cu(BO2)2 + SO3
Cupric metaborate
(Blue-green)
Reaction (ii):
Blue Cu(BO2)2 is reduced to colorless cuprous metaborate
2Cu(BO2)2 + 2NaBO2 + C 2CuBO + NaB2O4 + CO2
Reaction (ii): Cupric metaborate is reduced to metallic copper, and the bead
appears red and opaque
2Cu(BO2)2 + 2NaBO2 + 2C 2Cu + 2NaB2O4+ 2CO2
 Heating in oxidizing Heating in reducing
(non-luminous ) flame (luminous) flame
Inference
Colour of the salt bead Colour of the salt bead

In cold In hot In cold In hot

Blue Green Red opaque colourless Cu2+

Reddish brown Violet Grey Grey Ni2+

Yellowish
Yellow Green Green Fe3+
brown
 5. CHARCOAL CAVITY TEST
• Metallic carbonate ( In charcoal cavity ) oxides ( cloured residue )

• Sometimes oxide may be reduced to metal by the carbon of the charcoal

cavity.
• A charcoal block with the help of a charcoal borer.

• For CuSO4
CuSO4 + Na2CO3 CuCO3 + Na2SO4

CuCO3 CuO+CO2

CuO + C Cu + CO
red color
 5. CHARCOAL CAVITY TEST
• Metallic carbonate ( In charcoal cavity ) oxides ( cloured residue )
• Sometimes oxide may be reduced to metal by the carbon of the charcoal
cavity.
• A charcoal block with the help of a charcoal borer.
• For CuSO4
CuSO4 + Na2CO3 CuCO3 + Na2SO4
CuCO3 CuO+CO2
CuO + C Cu + CO
red color
In case of ZnSO4
ZnSO4 + Na2CO3 ZnCO3 + Na2SO4
ZnCO3 ZnO + CO2
Yellow when hot,
White when cold
 5. CHARCOAL CAVITY TEST

Observation Inference

Yellow residue when hot and grey metal

Pb2+
when cold

Yellow residue when hot white when

Zn2+
cold
 6. COBALT NITRATE TEST
• If the residue in the charcoal cavity is white, cobalt nitrate test is performed.
(i) Treat the residue with two or three drops of cobalt nitrate solution.
(ii) Heat it strongly in non-luminous flame with the help of a blow pipe and
cobalt nitrate cobalt (II) oxide
cobalt (II) oxide + Metal ion → characteristic colour
2Co(NO3)2 → 2CoO + 4NO + O2
CoO + ZnO → CoO·ZnO (Green)
CoO + MgO → CoO·MgO (Pink)
CoO + Al2O3 → CoO·Al2O3 (Blue)
 WET TESTS FOR IDENTIFICATION OF CATION
• The first essential step is to prepare a clear and transparent solution of the
• salt. This is called original solution.
little amount of the salt + distilled water(a few ml) → Solution
( heat if salt is insoluble)
• If the salt is insoluble in water
Salt + dil HCl (a few ml ) → Solution
( heat if salt is insoluble)
• If the salt does not dissolve either in water or in dilute HCl then add some drop
conc.HCl if salt is still insoluble than use nitric acid.
• If still insoluble then use mixture of conc.HCl + conc.HNO3 (3:1)
• A salt not soluble in aqua regia is considered to be an insoluble salt.
GROUP ANALYSIS
 GROUP ANALYSIS
1. Analysis of Zero group cation (NH4+ ion)

(a) Salt + NaOH(1-2ml) smell of ammonia ( with HCl dipped rod it

it gives white fumes (NH4Cl)
(NH₄)₂SO₄ + 2NaOH → Na₂SO₄ + 2NH₃ + 2H₂O

NH₃ + HCl → NH₄Cl (white fumes)

(b) Pass the gas through Nessler’s reagent. Brown precipitate is obtained.

2K₂HgI₄ + 3KOH + NH₃ → HgO·Hg(NH₂)I + 7KI + 2H₂O

Nessler’s reagent Basic mercury (II) amido-iodine
(Brown precipitate)
 GROUP ANALYSIS
2.Analysis of Group-I Cation
The Confirmatory Tests of Pb2+ ions
• Lead is precipitated as lead chloride in the first group
-
Pb2+ + 2Cl → PbCl2

1. PbCl₂ + 2KI → PbI₂ + 2KCl

(hot solution) ( yellow ppt)
• This yellow precipitate (PbI2) is soluble in boiling water and reappears
on cooling as shining crystals
2. PbCl₂ + 2K₂CrO₄ → PbCrO₄ + 2KCl
(hot solution) lead chromate
( yellow ppt) ( soluble in NaOH)

PbCrO₄ + 4NaOH → Na₂[Pb(OH)₄] + Na₂CrO₄

(Sodium tetra hydroxoplumbate (II))
 GROUP ANALYSIS
2.Analysis of Group-I Cation
The Confirmatory Tests of Pb2+ ions
3. PbCl₂ + H₂SO₄ → PbSO₄ + 2HCl
(Lead sulphate)
(White precipitate) ( soluble in acetic acid)

PbSO₄ + 4CH₃COONH₄ → (NH₄)₂[Pb(CH₃COO)₄] + (NH₄)₂SO₄

(Ammonium tetraacetoplumbate(II))
 GROUP ANALYSIS
3. Analysis of Group–II Cations
Pb2+/ Cu2+ + S2- → PbS / CuS ( black PPT)

precipitate + Ammonium sulphide → Insoluble ( then Pb2+/ Cu2+ Group II A)

(Yellow)
1. Test for Lead ion (Pb2+)
3PbS + 8HNO₃ → 3Pb(NO₃)₂ + 2NO + 4H₂O + 3S
Pb(NO₃)₂ + H₂SO₄ → PbSO₄ + 2HNO₃
(White) ( dissolved in ammonium acetate )
PbSO₄ + 4CH₃COONH₄ → (NH₄)₂[Pb(CH₃COO)₄] + (NH₄)₂SO₄
(Ammonium tetraacetoplumbate(II))
Pb²⁺ + CrO₄²⁻ → PbCrO₄
(Lead chromate) (Yellow precipitate)
Pb²⁺ + 2I⁻ → PbI₂
Lead iodide(Yellow precipitate)
 2. Test for Copper ion (Cu2+)
(a) Copper Sulphide Dissolution: Copper sulphide dissolves in nitric acid due to the
formation of copper nitrate.
3CuS + 8HNO₃ → 3Cu(NO₃)₂ + 2NO + 3S + 4H₂O
On heating long time blue colour solution :-
S + 2HNO₃ → H₂SO₄ + 2NO
2Cu²⁺ + 4SO₄²⁻ + 2NH₃ + 2H₂O → Cu(OH)₂ ⋅ CuSO₄ + 4NH₄⁺
Cu(OH)₂ ⋅ CuSO₄ + 8NH₃ → 2[Cu(NH₃)₄]SO₄ + 2OH⁻ + 2SO₄²⁻
Tetraamminecopper(II) sulphate
(Deep blue)
(b) Formation of Copper Ferrocyanide:
[Cu(NH₃)₄]SO₄ + 4CH₃COOH → CuSO₄ + 4CH₃COONH₄
2CuSO₄ + K₄[Fe(CN)₆] → Cu₂[Fe(CN)₆] + 2K₂SO₄
Copper Hexacyanoferrate (II)
(Chocolate brown precipitate)
3. Analysis of Group–III Cations
 1. Test for Aluminium ions (A13+)
(a) Copper Sulphide Dissolution: Copper sulphide dissolves in nitric acid due to the
formation of copper nitrate.
3CuS + 8HNO₃ → 3Cu(NO₃)₂ + 2NO + 3S + 4H₂O
On heating long time blue colour solution :-
S + 2HNO₃ → H₂SO₄ + 2NO
2Cu²⁺ + 4SO₄²⁻ + 2NH₃ + 2H₂O → Cu(OH)₂ ⋅ CuSO₄ + 4NH₄⁺
Cu(OH)₂ ⋅ CuSO₄ + 8NH₃ → 2[Cu(NH₃)₄]SO₄ + 2OH⁻ + 2SO₄²⁻
Tetraamminecopper(II) sulphate
(Deep blue)
(b) Formation of Copper Ferrocyanide:
[Cu(NH₃)₄]SO₄ + 4CH₃COOH → CuSO₄ + 4CH₃COONH₄
2CuSO₄ + K₄[Fe(CN)₆] → Cu₂[Fe(CN)₆] + 2K₂SO₄
Copper Hexacyanoferrate (II)
(Chocolate brown precipitate)
 Test for Group –III Cations
2. Test for ferric ions (Fe3+ )
Fe(OH)₃ + 3HCl → FeCl₃ + 3H₂O
(Reddish brown)

(a) 4FeCl₃ + 3K₄[Fe(CN)₆] → Fe₄[Fe(CN)₆]₃ + 12KCl

Potassium Prussian blue
Ferrocyanide precipitate

FeCl₃ + K₄[Fe(CN)₆] → KFe[Fe(CN)₆] + 3KCl

(in excess) (Soluble Prussian blue)

(b) Fe³⁺ + SCN⁻ → [Fe(SCN)]²⁺

potassium thiocyanate Blood red colour
 (V) Analysis of group-IV cations
White precipitate (Zn2+) Black precipitate (Ni2+, Co2+)

Dissolve the precipitate in dilute HCl by Dissolve the precipitate in aqua regia.
boiling. Divide the solution into two Heat the solution to dryness and cool.
parts. (a) To the first part add sodium Dissolve the residue in water and divide
hydroxide solution. A white precipitate the solution into two parts.
soluble in excess of sodium hydroxide (a) To the first part of the solution add
solution confirms the presence of Zn2+ ammonium hydroxide solution till it
ions. becomes alkaline. Add a few drops of
(b) Neutralise the second part with dimethyl glyoxime and shake the test
ammonium hydroxide solution and add tube. Formation of a bright red
potassium ferrocyanide solution. A bluish precipitate confirms the presence of
white precipitate appears. Ni2+ ions.
(b) (b) Neutralise the second part with
ammonium hydroxide solution.
Acidify it with dilute acetic acid and
add solid potassium nitrite. A yellow
precipitate confirms the presence of
Co2+ ions.
 Tests of Group–IV cations

Test for Zinc ion (Zn²⁺):

Zinc sulphide dissolves in hydrochloric acid to form zinc chloride.
ZnS + 2HCl → ZnCl₂ + H₂S
ZnCl₂ + 2NaOH → Zn(OH)₂ + 2NaCl
White PPT

Zn(OH)₂ + 2NaOH → Na₂ZnO₂ + 2H₂O

Sodium zincate

(b) 2 ZnCl₂ + K₄[Fe(CN)₆] → Zn₂[Fe(CN)₆] + 4 KCl

Zinc ferrocyanide
 Tests of Group–IV cations

Test for Nickel ion (Ni²⁺):

3NiS + 2HNO3 + 6HCI → 3NiCl2 + 2NO + 3S + 4H2O

Black PPT ( soluble in water )
 Tests of Group–V cations
Ba2+ ions Ca2+ ions

(a) To the first part add potassium (a) If both barium and strontium are
chromate solution. A yellow absent, take the third part of the
precipitate appears. solution. Add ammonium oxalate
(b) Perform the flame test with the solution and shake well. A white
preserved precipitate. A grassy precipitate of calcium oxalate is
green flame is obtained obtained.
(b) Perform the flame test with the
preserved precipitate. A brick red
flame, which looks greenish-
yellow through blue glass,
confirms the presence of Ca2+
ions.
 Tests of Group–V cations
Test for Barium ion (Ba²⁺)
BaCO₃ + 2CH₃COOH → (CH₃COO)₂Ba + H₂O + CO₂
(CH₃COO)₂Ba + K₂CrO₄ → BaCrO₄ + 2CH₃COOK
Barium chromate
(yellow precipitate)

(b) Flame test: A grassy green color of the flame confirms the presence of Ba²⁺ ions
 Test for Calcium ion (Ca²⁺)
(a) Solution of the fifth group precipitate in acetic acid gives a white precipitate with
ammonium oxalate solution.
CaCO₃ + 2CH₃COOH → (CH₃COO)₂Ca + H₂O + CO₂
(CH₃COO)₂Ca + (NH₄)₂C₂O₄ → (COO)₂Ca + 2CH₃COONH₄
Ammonium Calcium oxalate
oxalate (White precipitate)

(b) Flame test: Perform the flame test as mentioned above. Calcium imparts
brick-red color to the flame, which looks greenish-yellow through a blue glass.
 Tests of Group–VI cations
Test for Magnesium ion (Mg²⁺)
(a) If group–V is absent the solution may contain magnesium carbonate, which is
soluble in water in the presence of ammonium salts because the equilibrium is shifted
towards the right hand side.
NH₄⁺ + CO₃²⁻ NH₃ + HCO₃⁻
The concentration of carbonate ions required to produce a precipitate is not attained. When
disodium hydrogenphosphate solution is added and the inner walls of the test tube are
scratched with a glass rod, a white crystalline precipitate of magnesium ammonium
phosphate is formed which indicates the presence of Mg2+ ions.
Mg²⁺ + Na₂HPO₄ → Mg(NH₄)PO₄ + NH₄OH + 2Na⁺ + H₂O
Magnesium ammonium
phosphate (White precipitate)