Chapter 32

Salt Analysis
DEFINITION
The branch of chemical analysis which aims to find out the constituents of a
mixture of compound is known as Qualitative Analysis.
The Identification of a substances usually involves its conversion into a new
substance possessing characteristic properties with the help of one or more
substance of known composition. The Substance which is used to bring about
such change is called a Reagent.
Analysis of Cation

• by Wet Test
• by Dry Test
(B)
SALT ANALYSIS

Analysis of Anion
• by Wet Test
(A)
ANALYSIS OF ACIDIC RADICAL
Classification of Acidic Radical
Class - A Class - B
(Form volatile product with acid) (Does not form volatile product with acid)
Sub group-I Sub group-I

(Form volatile product with dil. HCl/ (Detected by precipitation reaction)

dil. H2SO4)
2– – 2– – 2–
SO4 , PO4 , AsO3 , AsO4
2– 3– 3– 3–

CO3 , HCO3 , SO3 , HSO3 , S2O3 ,

2– – 2–
S , CH3COO , NO2
Sub group-II Sub group-II
(Form volatile product with conc. (Detected by redox reaction)
H2SO4) CrO42–, Cr2O72–, MnO4–, MnO4–2
F–, Cl–, Br–, I–, NO3–, BO33–, C2O42–
+ sub group-I

● CO2 is colourless, odourless gas evolved with brisk effevescence,

Detected by lime water test.
● So2 is colourless, Suffocating gas with burning sulphur odour.
Detected by lime water test or by passing in Cr2O72–/H+ solution.
● H2S is a colourless gas having rotten egg odour.
● CH3COOH has colourless fumes having vinegar odour.
● NO2/Br2 is brown gas.
● I2 is violet gas.

LIME WATER / BARYTA WATER TEST

When CO2 is passed in lime water or baryta water then white turbidity (milky
appearance) is formed due to the formation of soluble carbonate but when
excess of CO2 is passed then white turbidity disappeared due to formation of
soluble bicarbonate.
CO2 ↑ + Ca2+ + 2OH– → CaCO3 ↓ + H2O
White turbidity
CaCO3 ↓ + CO2 ↑ + H2O → Ca(HCO3)2
Soluble

NOTES

SO2 also gives similar observation.

 ACIDIC RADICAL TABLE
dil. H2SO4 Conc. H2SO4 Cacl2 BaCl2 HgCl2 AgNO3 Pb(OAc)2 MnO4– /H+

CaCO3↓ BaCO3↓ HgCO3. 3HgO↓ PbCO3.

CO32– CO2↑ CO2↑ Ag2CO3↓ –
white white Reddish brown 2Pb(OH)2↓

HgCO3. 3HgO↓ PbCO3.

HCO3– + D CO2↑ CO2↑ CaCO3↓ BaCO3↓ Ag2CO3↓ –
Reddish brown 2Pb(OH)2↓

CaSO3↓ BaSO3↓ Ag2SO3↓ PbSO3↓

SO32– SO2↑ SO2↑ – SO42–
white white white white

BaS2O3↓ HgS2O2↓ Ag2S2O3↓ PbS2O3↓

S2O32– SO2↑ + S↓ SO2↑ – SO42– + S↓
white white white white

BaS↓ HgS↓ Ag2S↓ PbS↓

S2– H2S↑ S↓ + SO2↑ – S↓
black black black black
– –
NO2 NO2↑ NO2↑ – – – AgNO2↓ – NO3

CH3COOH +
CH3COO– CH3COOH↑ – – – – – –
SO2↑

I2↑ HgI2↓ AgI↓ PbCl2↓

I– – – I2↑
violet scarlet red yellow dark yellow
 dil. H2SO4 Conc. H2SO4 Cacl2 BaCl2 HgCl2 AgNO3 Pb(OAc)2 MnO4– /H+

AgCl↓ PbCl2↓
Cl– HCl↑ – – – Cl2↑
white white

Br2↑ AgBr↓ PbBr2↓

Br– – – – Br2↑
brown pale yellow white

CaC2O4↓ BaC2O4↓ Ag2C2O4↓

C2O42– – CO2↑ + CO↑ – – CO2↑
white white white

Ca(BO2)↓ Ba(BO2)↓ AgBO2↓

BO2– – H3BO3↑ – – –
white white white

NO3– – NO2↑ – – – – – –

BaSO4↓
2– CaSO4↓ HgSO4.2HgO↓ PbSO4↓
SO 4 – – curdy – –
white yellow white
white ppt

CaHPO4↓ BaHPO4↓ Ag3PO4↓

PO43– – – – – –
white white yellow

2– BaCrO4↓ Ag2CrO4↓ PbCrO4↓

CrO4 – – – – –
yellow brick red yellow
 SPECIFIC REACTION OF ACIDIC RADICAL
Anion Reaction Nmae /with Reagent Product Observation
Sodium Nitro
S2– Na2[Fe(CN)5NO] Na4[Fe(CN)5NOS] Purple Complex
Prusside
+
NH2 N(Me)2 S N(Me)2
+ FeCl3
S2– Methylene blue Test + Conc. Methylene Blue
(Me)2N HCl (y) N
+Fe + Cl

NH2

(i) Sulphanilic acid

NO2– Gries Illosavay Test Red Azo dye
(ii) 1, Methyl Amine
N=N SO3H

–
NO2 Brown Ring Test FeSO4 + dil.H2SO4 [Fe(H2O)5NO]SO4 Brown Ring
H3C O CH3
CH3COO– Cacodyl Test As2O3 AS AS Nauseating odour
H3C CH3

Blood Red solution

– n boil +
CH3COO FeCl3 Sol FeCl3 + H2O → [Fe3(HO)2(CH3OO)6] ↓ Boiling
Reddish Brown ppt.
 Anion Reaction Nmae /with Reagent Product Observation
–
NO 3 Brown Ring test FeSO4 + Conc. H2SO4 [Fe(H2O)5NO]SO4 Brown Ring
C2O42– Mn+2 + NaOH ∆ [Mn(C2O4)3]3– Red Complex
NaOH + Mn+2  →
Br– Layer Test Cl2 Water + CCl4 Br2 + CCl4 Red layer
I– Layer Test Cl2 Water + CCl4 I2 + CCl4 Violet Layer
–
I HgCl2 HgCl2 HgI2 Red/yellow
–
Cl Chromyl Chloride Test

(i) K2Cr2O7(s) + conc. Reddish brown Vapour
H2SO4 CrO2Cl2
↓
CrO42–
(ii) NaOH Yellow Solution
↓
↓
(
iii) Pb(CH3COO)2 + PbCrO4
CH3COOH Yellow PPt.

Conc. H2SO4 + ROH +

BO33– Green Flame Test B(OR)3 Green edge flame
D(Flame)
Modified Green Flame
BO33– CaF2 + Conc. H2SO4 BF3 ↑+ Ca(HSO4)2 + D Green flame
Test
3– (NH4)2MoO4 + dil HNO3
PO4 Ammonium molybdate Na3MoO4.12MoO3 Canary yellow ppt.
+ 30 – 40º C

2–
Cr O4 / Acidic Solution of H2O2
+ CrO5 Blue Solution
Cr2O7 + pyridine H2O2 + H +
N
BASIC RADICAL ANALYSIS
Dry Text of Cation
+2 +2
Flame test : used for s-block cation (except Be , Mg )

Cation: Li+ Na+ K+ Ca+2 Sr+2 Ba+2 Cu+2

Observation: Caramine G o l d e n Lilac B r i c k Crimosn A p p l e Green

(Naked eye) red yellow Red Red green flame

Cobalt glass: flame crimson Green Purple Bluish Green

disappear red green flame

Borax Bead Text

● Used for cloured cation (d-block cation)
● Given salt heated on borax bead than metal metaborate are form.
● Metal metaborate on heating show characteristic bead colour.

Oxidizing flame Reducing flame

Hot Cold Hot Cold

Mn Violet Amethyst Colourless Colourless

Cr Yellow Yellow Green Green

Fe Yellowish brown Green Green Green

Co Blue Blue Blue Blue

Ni Violet Brown Grey Grey

Cu Green Blue Colourless Opaque red

Charcol Cavity Text

Heat salt with Na2CO3 in charcoal cavity
Zn+2 In hot yellow and in cold white residue.
Pb+2 Yellow residue in hot and grey metal in cold.
As+3 White residue with garlic odour.
Cd+2 Brown residue.
If white residue is obtain then add. Co(No3)2 and heat.

Zn+2 ZnO.CoO Rinmann’s Green

Al+3 Al2O3 Thenard Blue

+2
Mg MgO.CoO Pink residue

+2
Sn SnO.CoO Bluish residue

CLASSIFICATION OF BASIC RADICAL

Group Basic Radical Reagent used Precipitate form

Group-I Pb+2, Hg2+2 dil HCl AgCl PbCl2 Hg2Cl2

white ppt.

+2 +2 +2
Group-II Cu , Pb , Hg , H2S+dil. HCl Cu2S, PbS, HgS, CdS, Bi2S3
Cd+2, Bi+3 yellow black
Black

Sn+2, Sn+4, As+3, SnS SnS2 As2S3As2S5 Sb2S3Sb2S5

As+5, Sb+3, Sb+5 Brown Brown yellow Gray

Group-III Cr+3, Al+3, Fe+3 NH4OH + Al(OH)3+ Fe(OH)3, Cr(OH)3

NH4Cl gelatinous reddish green
white brown

Group-IV Zn+2, Mn+2, Ni+2, H2S + NH4OH ZnS MnS NiS CoS
Co+2 white buff black

Group-V Ca+2, Sr+2, Ba+2 (NH4)2CO3 + CaCO3, SrCO3, BaCO3

NH4OH white
 TEST OF BASIC RADICAL
Ag+ Hg22+ Pb2+ Cu+2 Hg+2 Cd+2 Al+3

AgI Hg2I2 PbI2 CuI + I3– HgI2

KI — —
Yellow Green Yellow White solution Scarlet Red

Hg + [HgI4]2– [PbI4]2– [HgI4]2–

ex KI — — — —
Black soluble complex Red solution

AgCN Pb(CN)2 Cd(CN)2

KCN Hg + Hg(CN)2 White CuCN + [CN]2↑ — —
White White

K3[Cu(CN)4]
ex KCN [Ag(CN)2]– — — — [Cd(CN)4]2 —
soluble complex

Al(OH)3
Ag2O Hg2O Pb(OH)2 Cu(OH)2 HgO Cd(OH)2
NaOH Gelatinous
Brown Black White Pale Blue yellow White
white

Na[Al(OH)4]
Na2[Pb(OH)4]
ex NaOH — — — — — soluble
soluble complex
complex
 Ag+ Hg22+ Pb2+ Cu+2 Hg+2 Cd+2 Al+3

HgO. Al(OH)3
Ag2O Hg + HgO. Pb(OH)2 Cu(OH)2 Cd(OH)2
NH4OH HgNH2Cl Gelatinous
Brown HgNH+2NO3 White Pale Blue White
White white

+ [Cu(NH3)4]2+ 2+
ex NH4OH [Ag(NH3)2] — — — [Cd(NH3)4] —
Deep blue

Al(OH)3
Ag2S Hg + HgS PbS CuS HgS CdS
H2S/*(NH4)2S Gelatinous
Black black Back Black Black Yellow
white

Ag,CrO4 Hg2CrO4 PbCrO4

K2CrO4 — — — —
Red Red Yellow

Ag2S2O3 PbS2O3 Cu2S2O3 HgS2O3

Na2S2O3 — White — —
White White White

Ag4[Fe(CN)6] Cu2[Fe(CN)6]
K4[Fe(CN)6] — — — — —
White Brown

Cu3[Fe(CN)6]
K3[Fe(CN)6] — — — — — —
Green
 TEST OF BASIC RADICAL
Cr+3 Fe+3 Fe+2 Zn+2 Mn+2 Ni+2 Co+2

FeI2+ I3–
KI — yellowish brown — — — — —
sol.

Zn(CN)2
ex KI — — — — — —
White

Fe(CN)3 Fe(CN)2 Mn(CN)2 . Mn(OH)2 Ni(CN)2 Co(CN)2

KCN — —
Brown yellowish brown Pink green Reddish Brown

K2[Ni(CN)4]
K3[Fe(CN)6] K4[Fe(CN)6] [Co(CN)6]–4
ex KCN — — — Soluble
Yellow Pale yellow Brown Solution
Complex

Zn(OH)2 Mn(OH)2
Cr(OH)3 Fe(OH)3 Fe(OH)2 Ni(OH)2 Co(OH)Cl
NaOH White Pink
Green Reddish Brown ppt Dirty Green Green Blue

Na[(AlOH)4] (CoOH)2
ex NaOH — — Na2[Zn(OH)4] — —
Yellow pink

Cr(OH)3 Fe(OH)3 Fe(OH)2 Ni(OH)2

NH4OH Zn(OH)2 — Co(OH)Cl
Green Reddish Brown ppt Dirty Green Green
 Cr+3 Fe+3 Fe+2 Zn+2 Mn+2 Ni+2 Co+2

[Cr(NH3)6]3+ Ni[(NH3)6]2+ [Co(NH3)6]2+

ex NH4OH — — [Zn(NH3)4]2+ —
Pink/vollet Deep blue Yellow

Cr(OH)3 FeS + S FeS ZnS MnS NiS CoS

H2S/*(NH4)2S
Green Black yellow Black White Pink Black Black

K2CrO4 — — — — — — —

Fe+2
Na2S2O3 —
Green solution

Fe4[Fe(CN6)]3 K2Zn3[Fe(CN)6] Mn2[Fe(CN)6] Ni2[Fe(CN)6] Co2[Fe(CN)6]

K4[Fe(CN)6] — K2Fe[Fe(CN)6]
Prussian blue White White Light green Green

Fe[Fe(CN6)] Fe3[Fe(CN6)]2
K3[Fe(CN)6] — — — — —
Brown Turnbull’s blue
 OTHER IMPORTANT REACTION OF BASIC RADICAL

Basic radical Reagent Product Observation

Fe+3 SCN– Fe(SCN)3 Blood red colcuration

Ni+2 dmg / NH4+ [Ni(dmg)2] Rosy red complex

Co+2 KNO2 K3[Co(NO2)6] Yellow ppt

+2
Hg SnCl2(ex) Hg Grey / black

K+ HClO4 KClO4 White ppt

(NH4)2[PtCl6] H2[PtCl6] K2[Hgl4] + KOH +

HgO, HgNH2I–
yellow
brown
K2[Co(NO2)6] KOH/NaOH CuSO4
(NH4)2[Co(NO2)6] NH
+
4 → NH3 [Cu(NH3)4]SO4
yellow Colourless deep blue
NaHC4H4O6 Gas NiCl2
(NH4HC4H4O6 [Ni(NH3)6]2+
white crystal deep blue

qqq