QUALITATIVE ANALYSIS

INTRODUCTION AND CLASSIFICATION

 Becausethey
Because theyare
are
Qualitative Inorganic analysis derivedfrom
derived frombases
acids.

Detection of Cations Detection of Anions

(Basic radicals) (Acidic radicals)

Acidic radical
HA + BOH BA + H2O

Basic radical
 Acid Radicals

IA IB II A II B
Species give Species give Species Species
volatile gas volatile gas which which
fumes with fumes with get undergo
dilute acids. conc. acids. precipitate redox
(dil. HCl, (conc. (conc. reaction.
dil. H2SO4) H2SO4) HNO3)
 Gr-IA Acid Radicals

Species give volatile gas fumes with dilute acids.

Example: dil. HCl , dil. H2SO4

Anions included in group I A are :

 CO32- (Carbonate)  S2- (Sulphide)

 HCO3– (Bicarbonate)  NO2– (Nitrite)
 SO32- (Sulphite)  CH3COO– (Acetate)
 HSO3– (Bisulphite)  S2O32- (Thiosulphate)
CLASSIFICATION OF ACID RADICALS
 Gr-IB Acid Radicals

Species give volatile gas fumes with conc. acids.

Example: conc. H2SO4

Anions included in group I B are :-

 F– (Fluoride)  C2O4–2 (Oxalate)
 Cl– (Chloride)  BO3–3 (Borate)
 Br – (Bromide)  NO3– (Nitrate)
 I– (Iodide)
 Gr-IIA Acid Radicals

Species which get precipitated with conc. HNO3.

Anions included in group II A are :-

 SO4–2 (Sulphate)

 PO4–3 (Phosphate)
 Gr-IIB Acid Radicals

Species which undergo redox reaction. Cr2O7 2- + OH– 2CrO4-2 + H+

Orange Yellow
Anions included in group II B are :

 Cr2O7–2 (Dichromate)

 CrO4–2 (Chromate)

 MnO4– (Permanganate)
CARBONATE (CO3–2)
 Gr-IA Acid Radical
 Carbonate (CO3–2)
All carbonates are insoluble in water with the
exception of group IA.
Example : (Na+ , Rb+ , Cs+ , K+ ) and NH4+
 They will hydrolyze to give metal hydroxide.
 Reagent : dil. HCl

Preliminary Test:
CO3–2 + dil. HCl H2CO3 H2O + CO2
(Effervescence of Acidic gas)
 Confirmatory Test for CO32-

CO3–2 + dil. HCl H2CO3 H2O + CO2

(Effervescence of Acidic gas)

CO2
CO2 + Ca(OH)2 CaCO3 excess
Ca(HCO3)2
Lime stone Soluble
(Lime H2O)
insoluble (Milkiness
(milky white) Disappeared)

CO2
CO2 + Ba(OH)2 BaCO3 excess
Ba(HCO3)2
(Baryta H2O) (milky white) Milkiness
disappeared
  Some More Confirmatory Test for CO32-
AgNO3  For cations Ag, Ba,1 Pb
Ag2CO3 Ag2O reactions Ag common.
are + O2
100o C 300 C
o
2
(white) Brown black black
BaCl2
BaCO3
CO32– (white)

(CH3COO)2 Pb
Sugar of Lead
PbCO3
(white)
CaCl2
CaCO3
(white)

Majority CO3-2 are white. They rarely have color

due to impurities.
BICARBONATE (HCO3-)
 Bicarbonate (HCO3–)
 Generally all bicarbonates are soluble (due to H– bonding).
 (KHCO3 – dimeric, NaHCO3 – Polymeric)
2–
O H O
KHCO
HCO 3 +
– O C
HCl(dil)
3 = H2COC3 O CO2 + H2O
 O H–2 O
HCO3 –
CO3 + H2O + CO2

 In group I, exceptOLi2CO3 all otherOcations

NaHCO O Con OH
do not3 =decompose heating.O C OH

Li2CO3 Li2O + CO2
 Q. When Barium chloride solution is added to Carbonate solution under cold
condition barium carbonate is formed Predict what will happen if Barium
chloride solution is added to Bicarbonate solution under same condition.
Solution
BaCl2
CO3 -2
BaCO3
cool
BaCl2
HCO3 – No precipitation
cool

BaCl2
HCO3 –
BaCO3

The reaction of HCO3– at high temperature resembles CO3–2
at low temperature.
SULPHITE (SO32–)
 Sulphite (SO3–2)
Why Lime water and Baryta
All sulphites are insoluble in water with thetest
exception of group
is not confirmation of
IA ( Na , Rb , Cs , K ) and NH4 .
+ + + + +
CO32- in presence of SO32- ?

SO3–2 + HCl (dil) SO2 + H2 O

(Poisonous gas)
Suffocating odour,
smell of burning
sulphur
  
 Confirmatory Test for
SOSO –2
3
2-
CO3–2 + S
4 C

S S2O3–2
Sugar of Lead 
(CH3COO)2Pb PbSO3
PbSO4
[O]
(white) (white)
BaCl2
SO3 -2 BaSO3
(white)
AgNO3
Ag2SO3
(white)
KMnO4
H+ SO4–2 + Mn+2
K2Cr2O7
H+
SO4–2 + Cr +3
(Green)
BISULPHITE (HSO3–)
 Bisulphite (HSO3–) What is
SO2 used
What inispreparation
the
Comproportionation
 All bisulphites are soluble in water. of one acidname?
Process i.e. H2SO4
reaction?
 Neutral to litmus paper (very weak acid).
dil. HCl
HSO3 –
H2SO3 H2O + SO2
 SO2 also turns Ca(OH) 2 / Ba(OH)2
milky (CaSO3/BaSO3).
Comproportionation
Milkiness disappears if SO2 is in excessis a
or symproportionation
( chemical
Ca(HSOreaction where two reactants, each containing
3)2 , Ba(HSO3)2 ).
the same element but with a different oxidation number,
SO 2+
will H2Sa product in which
form S the+ elements
H2O involved
reach the same(Comproportionation
oxidation number. reaction)
Points to remember
H2 O ToWhat
get variable
is the
• SO2 + Cl2 SO2 Cl2 SO4 +conc.
–2
HCl ofoleum?
use of H2SO4.
(Free halogenation reaction)

• S + O2 SO2
FeS2 + O2 Fe2O3 + SO2
SO3–2 + HCl SO2
Contact process :
V2O5
SO2(g) + O2(g) SO3
H2SO4 + SO3 H2 S2 O7
Oleum
H2S2O7 + H2O H2SO4
SULPHIDE (S2–)
 Reactions of S-2 :
What
WhyisBaS
the
Cd2+/ Hg+2 / Bi+3
CdS / HgS / Bi2S3 precipitate
structure is
ofnot
dil. HCl
methylene
forming?blue?
H2S (Rotten egg smell)
BaCl2
No precipitation
Na2[Fe(CN)5NO]
Na4[Fe(CN)5NOS] (Violet Purple)
S
-2
Sod. Nitroprusside
AgNO3 (aq)
Ag2S (Black)
N
+ FeCl3
O

NH2
Methylene Blue
(CH3COO)2Pb
PbS (Black)
THIOSULPHATE (S2O3–2)
 Thiosulphate (S2O3–2)
What is the type
 All are water soluble except (BaS2O3) of this reaction ?

+2 0 +4
S2 O3 -2
+ dil. HCl S + H2SO3 (Disproportionate reaction)
Colloidal Sulphur
(Yellow)

H2O + SO2
Disproportionation is a specific type of redox reaction
in which a species is simultaneously reduced and
oxidised to form two different products
 Stand
 Reactions (Black)
AgNO3 of S2O3 : 2- Ag 2 S
Ag2S2O3 S2O3–2
[Ag(S2O3)2]–3
BaCl2 Photography complex
BaS2O3
(white)
Stand PbS (Black)
(CH3COO)2 Pb S2O3–2
PbS2O3 Na2[Pb(S2O3)2]
Br2
SO4–2
S2O3-2 Stand CuS (Black)
Cu+2
Cu2S2O3 S2O3 Na [Cu (S O ) ]
–2

4 6 2 3 5
Cl2 (Colourless)
HSO4– (465 complex)
I2
I– + S4O6–2
[Ni(en)3](NO3)2 [Ni(en)3](S2O3)2 (Violet)
[R] S
NITRITE (NO2–)
 Nitrite (NO2–) Blue color interferes
with yellowish brown.
All are H2O soluble except AgNO2.
dil.  O 
NO –
2 HCl HNO2 HNO3  NO NO2  yellowish brown

N2O3 blue dehydration
 Sulphanalic
Reactions acid
[O] of NO2-: AgNO3
NO3– NH2 AgNO2 (white)
Napthamine
K2Cr2O7 FeSO4 (fresh)
[Fe (H2O)5NO]SO4
or O
NH KMnO4 (aq)
2
Zn/Al Color due to charge transfer,
NH3 O SO O 3H
H2O Also written as [Fe(NO)]2+aq.
(CH3COO)2Pb
No precipitation
 NH4 +
NO2–
N2 NH4NO2
Sulphamic acid
(NH2– SO3H)
Urea N2
N2 BaCl2
No precipitation
Thiourea Sulphanalic acid
HSCN + N2 Diazonium
Napthamine

RED DYE
ACETATE (CH3COO–)
 Reactions of CH3COO-
Vinegar contains 5-10%
What is theacetic acid,
H+ one of the weak Vinegar?
acids. Most of the
CH3COOH (Vinegar)
remainder of the liquid is water.
R’OH
CH3COOR’(Ester)
H +

(Fruity smell)
AgNO3
CH3COO -
CH3COOAg
(white)

CH3COCH3 (Acetone)
(Ca salt)
BaCl2
No precipitation
Fe+3
Fe3 [(OH)2(CH3COO)6]+
(Red, on standing brown)
FLOURIDE (F–)
 Gr-IB Acid Radicals H
H F
F F
Reagent : conc. H2SO4 Why HF forms
H
FdimerHand trimer?
H
F
 Fluoride (F–)
Dimer Trimer

 BeF2 is highly soluble in H2O

 HF exists in two form i.e. Dimer and Trimer

F– + Conc. H2SO4 H2 F2

H F2 –
(acidic conjugate base)
 Confirmatory Tests

H2 O
HF + SiO2 SiF4 H2SiF6 + H2SiO3
(moisture)
(glass rod) (Etching of glass)
(Cracks on surface of glass)

 F– can also be checked by using CaCl2 :

F– + CaCl2 CaF2
(White)
CHLORIDE (Cl–)
  Reactions
Conc. H2SO4 of Cl
NH-
3:
HCl NH4Cl (Dense fumes) CrOPbCl
2Cl2 is is
also involved
soluble in hot
How do2 you solubilize
NH3 in Etard process
HAgCl tocold
convert
[Ag(NH3)2]+ 2O but innot
water? H 2O
AgNO3 Toluene to Benzaldehyde
AgCl KCN
(white)
[Ag(CN)2]–
S2O3 –2
[Ag(S2O3)2]–3
(CH 3COO)
Metal 2Pb
chromates
•Disproportionation is (MCrO
a Cl– ) are
specific typegenerally
of
4 [PbCl –2 redox reaction in which
PbCl2 4]
Cl–a species
yellowis with
simultaneously reduced
the exceptions
(white) and oxidised
of Ag+ and to form two
different
Hg+ products
K2Cr 2O7
H2SO
which are
4 red. NaOH
CrO2Cl2 Na2CrO4
BaCl2
No precipitations (CH3COO)2Pb
MnO2 H2O PbCrO4
Cl2 HCl + HOCl (Disproportion)
BROMIDE (Br-) AND IODIDE (I–)
 Reactions of Br-:
conc. H2SO4 [O] Oxidizing agents can be
Cl2 HBr Br2 HNO3, KMnO4, K2Cr2O7.
Cl– + Br2 (Brown)
[O] AgNO3 
Br2 AgBr Ag + Br2
Starch paper (photo sensitive)
(Yellow orange)
Br–

MnO2 BaCl2
Mn+2 + Br2 No Precipitation
Conc. H3PO4 Sugar of Pb
HBr PbBr2
(White)
  Reactions of I-:
AgNO3 conc. H2SO4 NH 4OH
[O] I–
AgI K2[HgIHI
4] IHgO.HgI.NH
I3 – 2
2
(Yellow) Nessler’s (Violet)Iodide of
Reagent
Cu+2 Million’s base
[O] [O]
HIO3 I2 CuI2 Cu2I2 + I2
H2O
(Yellow) (White) (Violet)

I–
Excess
KI HgCl2 BaCl2
K2[HgI4] HgI2 No Precipitation
(Red) Sugar of Pb
KI3 form dark Starch / I2 PbI2
blue colored
complex with starch (Yellow)
NITRATE (NO3-), BORATE (BO3–3) AND
OXALATE (C2O4-2)
 Nitrate (NO3–):
Reaction should be
All Nitrates are H2O Soluble. Rarely found in earth’sOxalates
crust. areby
performed mostly
very
whiteslowly
in color
NaNO3 + H2SO4 NaHSO4 + HNO3
6FeSO4 + 2HNO3 + 3H2SO4 3Fe2(SO4)3 + NO + 4H2O
On standing
FeSO4 + NO + 5H2O [Fe(H2O)5NO]SO4 NO + FeSO4 (aq)
 Oxalate (C2O4–2 ):
AgNO3 H+ H2O
Ag2C2O4 H2 C 2 O4 H2C2O4 .2H2O

C2O4–2 H2O + CO + CO2
Neutral Acidic
  Borate (BO3–3) On heating,
Ba Apple green
ROH BF3 Green edged flame
BO3–3 +Conc. H2SO4 H3BO3 B(OR)3 (Green color to flame)

O O
H2O Vicinal diols
H3BO3 B
O O
(Complex)
GROUP II A AND FLAME TESTS
 Gr-IIA Acid Radical
 SO4–2 : Sulphates of Pb+2, Ba+2, Sr+2 are insoluble

PbCl2
PbSO4 (White)

BaCl2
BaSO4 (White)
SO4–2
SrCl2
SrSO4 (White)

HgCl2
HgO. HgSO4 (Yellow)

PbSO4 +CH3COONH4 Soluble complex

 Detection of Phosphate (PO4 )–3 :

 Phosphates are yellow.

PO4–3 + H+ (conc. H2SO4 / HNO3) H3PO4

PO4–3 + (NH4)2MoO4 (NH4)3PO4. 12MoO3

Ammonium molybdate (Canary yellow)

PO43- + NH4Cl + NH4OH + MgSO4 Mg(NH4)PO4

(White)
 Cu Blue Green
Ba Apple green
Sr Crimso Red
Ca Brick red
Cs Blue
 Flame tests :

Rb Lilac
K Lilac/Violet
Na Golden yellow
Li Crimson Red
 Colours of compounds:

• HgO Yellow

• PbO PbO (Litharge)
Yellow (Red)
(Massicot)

• ZnO ZnO
(White) (Yellow)


• HgI2 HgI2
(Red) (Yellow)
BORAX BEAD TEST
 Borax Bead test :
 On heating borax forms a colorless glassy bead of NaBO 2
and B2O3.
 
Na2B4O7 . 10 H2O Na2B4O7 2NaBO2 + B2O3
 On heating with the colored salt, the
glassy bead forms a colored metaborate
in oxidising flame.
 Example,

In oxidising flame copper salt give blue

bead.
 CuSO4 CuO + SO3 ;
CuO + B2O3 Cu(BO2)2 (blue bead)
 In reducing flame the colors may be different due
to different reactions.
2Cu(BO2)2 + C 2CuBO2 + B2O3 + CO

2Cu(BO2)2 + 2C 2Cu + 2B2O3 + 2CO

(brown red/red and opaque bead)
 Microcosmic Salt Bead Test

A test similar to Borax Bead test in used for identification of coloured

cations if microcosmic salt, Na(NH4)HPO4 . 4H2O is used.


Na(NH4)HPO4 NaPO3 + B2O3 + NH3
transparent
bead

NaPO3 + CoO  NaCoPO4

(blue bead)
 Example

Which forms coloured bead in qualitative cation analysis

(a) Borax (b) Microcosmic salt

(c) Both (a) & (b) (d) None of the above

Option (c)
CLASSIFICATION OF CATIONS
List of Reagents and species detected and precipitate found in each group

Species to
Reagent Products
detect

Ag+, Hg2+2,
I dil. HCl AgCl, Hg2Cl2, PbCl2
Pb+2
dil. HCl + Hg+2, Pb+2,
II A H2S Cu+2, Cd+2, HgS, PbS, CuS, Bi2S3,
Bi+3
CdS
II B dil. HCl + As+3, Sb+, Sb2S3, As2S3, SnS2,
H2S Sn+3, Sn+4
SnS

III NH4Cl + Fe+3 Cr+3, Cr(OH)3, Fe(OH)3,

NH4OH Al+3 Al(OH)3
 Species to
Reagent Products
detect

IV NH4OH + Co+2, Ni+2, MnS, ZnS,

H2S Mn+2, Zn+2
CoS, NiS

V NH4Cl + Ba+2, Ca+2, BaCO3, CaCO3,

(NH4)2CO3 Sr+2 SrCO3

VI Na2HPO4 Mg+2 Mg(NH4)HPO4

0 NH4OH/ NH4+ Ammonia gas

KOH is evolved
INTERFERING ACID RADICALS
  Properties of Interfering acid radicals
2– 3– –
 Certain anions oxalate (C2O4 ), borate (BO4 ), Fluoride(F ) Phosphate which
make systematic analysis of basic radical difficult.
 Interfere after second group as in their presence the basic radicals of IV, V,
VI groups are prematurely precipitated in the third group.
 Further the presence of oxalate anion hinders
the complete precipitation or no precipitation
of Fe, Al and Cr even if they are present due to
the formation of soluble complexes with
NH4OH.
 Properties of Interfering acid radicals

 The salt of these acid radicals are soluble in acidic solution and
insoluble in neutral or alkaline medium.
 Upto second group the solution remain acidic so no interference
but beyond that problem arises as solution become alkaline.

 Example

 Precipitate of BaC2O4 in acidic medium form

Corresponding acid.
BaC2O4 + 2HCl BaCl2 + H2C2O4
 This interfering acids are weak acids so they dont dissociate completely
and remain in their unionized form. Equilibrium is developed
between dissociated and undissociated acid.
H2 C 2 O4 2H+ + C2O2–
4

 So this resulting the dissolution of BaC2O4 precipitate.

 BaC2O4 Precipitate is not coming with other metal precipitate in

acidic medium
 These radicals do not give any gas with
conc as well as dilute acid in cold.
  Detection of phosphate (PO–3
4 )

 Ammonium molydate test

Na2HPO4(aq) + 12 (NH4)2MoO4 + 23 HNO3 (NH4)3PMo12O40 + 2 Na NO3
Canary 21 NH+
4NO3 + 12 H2O
(NH4)3 PO4. 12MoO3 (Canary yellow) Yellow
 Magnetia mixture test

Na2 HPO4 (aq) + Mg (NO3)2 (aq) + NH4 OH (aq) Mg(NH4)PO4 (White) + 2NaNO3
+
 Magnetia mixture : H2 O

MgCl2, NH4Cl, and little aqueous NH3

DETECTION OF Pb+2 AND Ag+
 ReactionI– of Pb2+ NH3 NH3
PbI2 Pb(OH)2 No soluble complex
(aq.)
(Yellow) (White)
NaOH NaOH
HCl Pb(OH)2 [Pb(OH)4]–2
PbCl2
(White) Plumbosolvancy
CO3–2 CrO4–2
PbCO3 Pb+2 PbCrO4
(White) (Yellow)

H2S SO4–2
PbS PbSO4
(Black) (White)
SO3–2
CN– PbSO3
Pb(CN)2
(White) (White)
  Reaction of Ag +
NH3
–
I NH3
AgI Ag2O [Ag(NH3)2]+
(aq.)
(Yellow) (Brown)

NaOH NaOH
Ag2O No precipitations
HCl
AgCl
(White)
CrO4–2
Ag + Ag2CrO4
(Red)

Br– PO4–3
AgBr Ag3(PO4)
(Pale yellow) (Yellow)

Cl– KCN
AgCl AgCN
(White) (White)
DETECTION OF Bi+3 AND Hg+2
 Reactions of Bi3+: H2O
BiOI
(Brick red)
KI KI
BiI3 KBiI4
(Black) (Orange)
Cl– H2O
BiCl3 BiOCl
(White) (Pearl white)
NaOH
Bi+3 Bi(OH)3 NaOH No reaction

Dil. HCl + H2S Bi S

2 3
(Black)
NH3(aq.)
Bi(OH)2NO3
(White)
It is not soluble in NH3 excess and in NaOH excess
 Reactions of Hg2+:
Co(SCN)2 Co[Hg (SCN)2]
(Blue)
SnCl2 SnCl2
Hg2Cl2 Hg
(Grey)
NaOH NaOH
Hg +2 HgO No reaction
(Yellow)
Dil. HCl + H2S
HgS
(Black)
NH3(aq.)
HgO.Hg(NH2)NO3
(White)
It is not soluble in NH3 excess and in NaOH excess
DETECTION OF Cu+2 AND ITS COMPOUNDS
  Reaction of Cu
K3[Fe(CN) ]
+2
NH3 NH3
6
Cu(OH)2 [Cu(NH3)4]+2
Cu3[Fe(CN)6]2 (aq.)
(Blue) (Deep blue)
(Green)
NaOH Cu(OH)2 NaOH
SCN – No precipitations
Cu(SCN)2
(Black)
H2S
Cu +2 CuS
(Black)

Cu2(SCN)2 + (SCN)2 KCN Cu(CN)2

(White) (Thiocyanogen) (Yellow)
(Yellow)
K4[Fe(CN)6]
Cu2(CN)2 + (CN)2
Cu2[Fe(CN)6]
(White) (Cyanogen)
(Chocolate Brown)
 Colors of Cu Compounds

Cu(OH)2 Blue
Cu(NO3)2 Blue
Cu(CO3) Green
Cu(SCN)2 Black
Cu2(SCN)2 White
Cu2[Fe(CN)6] Brown

Cu3[Fe(CN)6]2 Green
[Cu(NH3)4]+2 Deep blue

Cu2O Red
CuO Black
GROUP III CATIONS
Group III :
1) Detection of Al+3 :
It is not soluble in excess NH3 but it is soluble in excess NaOH
NH4OH
Al(OH)3 (Gelatinous white)

NaOH NaOH
Al+3 Al(OH)3 Na[Al(OH)4]
(CH3COO–)
(CH3COO)3Al (white)
2) Detection of Cr+3 :

It is soluble in NH3 excess and in excess NaOH

NH4Cl NH3
Cr(OH)3 [Cr(NH3)6]+3
NH4OH
(Green)
NaOH NaOH
Cr+3 Cr(OH)3 [Cr(OH)4]–
(Green)
H2O2
OH– CrO4–2
(Yellow)
 3) Detection of Fe+3 :
NH4Cl NH3
Fe(OH)3 No Precipitation
NH4OH excess
(Brown)
NaOH NaOH
Fe(OH)3 excess
No Precipitation
S–2
FeS
(Black)
K4[Fe(CN)6]
Fe+3 Fe4[Fe(CN)6]3
(Prussian blue)
KCN
Fe(CN)3
(Brown)
K3[Fe(CN)6]
Fe[Fe(CN)6]
(Brown)
SCN –

Fe(SCN)3 (Red)
 Distinction of Fe3+ and Fe2+:

Fe3+ + K3[Fe(CN)6] Fe[Fe(CN)6]

Brown
3Fe2+ + 2K3[Fe(CN)6] Fe3[Fe(CN)6]2 + 6K+
Ferous ferric cyanide
Turnbull’s blue

Fe+2 + SCN– No Blood colouration

GROUP IV CATIONS
Group IV : (NH4OH + H2S)
1) Mn+2 : It is not soluble in NH3 excess and in NaOH excess

NH4OH NH3
H2S
MnS excess No soluble complex
(Pink)
H2O NaOH
Mn+2 Mn(OH)2 excess No soluble complex
NaOH
(White)
[O]
MnO4–
(Purple)
NH3 +

HPO4– Mn (NH4)PO4
(Pink salt)
 NH3 NH3
Zn(OH)2 excess
Na2[Zn(OH)4]
(aq.)
(White)
NaOH NaOH
Zn(OH)2 excess
[Zn(NH3)4]+2
CuSO4 + Hg(SCN)4–2
Zn[Hg(SCN)4] + Cu[Hg(SCN)4] (Violet)
K4[Fe(CN)6]
Zn +2 K2Zn3[Fe(CN)6]2
(Bluish white)
ZnO + CoO
CoZnO2
(Riemann green)
PO4 –3

Zn3(PO4)2
(White)
S–2
ZnS (White)
GROUP V AND VI CATIONS
 Detection of Ba2+ :

 Precipitation with (NH4)2CO3 in presence of NH4OH + NH4Cl

BaCl2 + (NH4)2CO3 BaCO3 + 2NH4Cl

BaCO3 + 2CH3COOH Ba(CH3COO)2 + H2O + CO2

 Potassium chromate test :

Ba(CH3COO)2 + K2CrO4 BaCrO4 + 2CH3COOK

Note: Precipitate is soluble in Acetic acid (distinction

from Sr2+ and Ca2+) but readily soluble in mineral acid.
 Detection of Sr2+ :

 Precipitation with (NH4)2CO3 in presence of NH4OH + NH4Cl

SrCl2 + (NH4)2CO3 SrCO3 + 2NH4Cl

SrCO3 + 2CH3COOH Sr(CH3COO)2 + H2O + CO2

 Ammonium sulphate test:

Sr(CH3COO)2 + (NH4)2SO4 SrSO4 + 2CH3COONH4

 Detection of Ca2+ :

Note: CaCO3 is soluble

 Precipitation in water
with (NH which contains excess carbonic acid
4)2CO3 in presence of NH4OH + NH4Cl
(freshly prepared soda water) because of the formation of soluble
hydrogen carbonate.
CaCl2 + (NH 4)2CO3
CaCO
On boiling 3 + 2NHreappears.
precipitate 4Cl

CaCO3 + 2CH3COOH Ca(CH3COO)2 + H2O + CO2

 Ammonium oxalate test:

Ca(CH3COO)2 + (NH4)2C2O4 CaC2O4 + 2CH3COONH4

 Potassium hexacyanido ferrate (II):

Ca2+ + 2K+ + [Fe(CN)6]4- K2Ca[Fe(CN)6]

 Detection of Mg2+ :
 Disodium hydrogen phosphate test:
 Precipitation in presence of NH4Cl (prevent precipitation of Mg(OH)2)
and ammonia solution.

Mg2+ + NH3 + HPO42- Mg(NH4)PO4

 Ammonia solution:

Mg2+ + 2NH4OH Mg(OH)2 + 2NH4+

 It also respond to the Titan yellow test
forming a deep red color solution.
SOLUBILITY PRODUCT CONSTANT

COMMON ION EFFECT

PREDICT FORMATION OF PRECIPITATE

 Solubility Product Constant
• General Expression
MmXn(s) mMn + (aq) + nXm – (aq)

• Solubility Product, Ksp = [Mn+]m [Xm–]n

Examples:
AgCl(s) Ag+(aq) + Cl–(aq)
Ksp = [Ag+][Cl–]
[Ag+] = s and [Cl–] = s (s is the solubility of AgCl)

s = 1.3  10–5 mol/L

Ksp = [Ag+][Cl–] = 1.6  10–10
  Common Ion Effect

Consider the following solubility equilibrium :

AgCl(s) Ag+(aq) + Cl–(aq) ; Ksp = 1.6  10–10
• The solubility of AgCl is 1.3  10–5 mol/L at 250C.
• If NaCl is added, equilibrium shifts left due to
increase in [Cl–] and some AgCl will precipitate out.
• For Example, if [Cl–] = 1.0  10–2 M,

• Solubility of AgCl = (1.6  10–10) / (1.0  10–2 )

= 1.6  10–8 mol/L
 Predict formation of Precipitate
• Qsp = Ksp  Saturated solution, but no precipitate

• Qsp > Ksp  Saturated solution, with precipitate

• Qsp < Ksp  Unsaturated solution,

• Qsp is ion product expressed in the same way as

Ksp for a particular syatem.
 Predicting Precipitation
Q. 20.0 mL of 0.025 M Pb(NO3)2 is added to 30.0 mL of 0.10 M NaCl.
Predict if precipitate of PbCl2 will form.
(Ksp for PbCl2 = 1.6  10–5 )
Calculation :
[Pb2+] = (20.0 mL  0.025 M)/ (50.0 mL) = 0.010 M
[Cl–] = (30.0 mL  0.10 M) / (50.0 mL) = 0.060M
Qsp = [Pb2+][Cl–] = (0.010 M)(0.060 M2)
= 3.6  10–5
 Qsp > Ksp  Precipitate of PbCl2 will form
SPECIAL CASES OF THE GROUP ANALYSIS OF METAL CATIONS-I
SPECIAL CASES OF THE GROUP ANALYSIS OF METAL CATIONS
Case I: Both the group – II and Group IV cations precipitates as sulphides
but why they are not precipitating together in Group – II.
[Ksp]IV >> [Ksp]II
[Solubility]IV >> [Solubility]II
To prevent the precipitation of Group–IV sulphides
with Group – II the solution is acidified with dil HCl
before passing H2S(g).
H2 S 2H+ + S2–
HCl H+ + Cl–
 H2 S 2H+ + S2–
HCl H+ + Cl–
 Common ion effect suffers the above equilibrium. Hence lower the
concentration of S2– .
 This concentration is not sufficient for precipitation
for Group – IV but sufficient for Group – II.
 Concentrated HCl is not used as concentrated
HCl greatly suppress the H2S ionisation. Hence
[S2–] not sufficient for precipitation of CdS.
Whose Ksp is moderately high.
 conc H2SO4 or conc. HNO3 cannot be used
as they oxidise H2S to S
Case II: Group IV, V and Mg2+ Cations can also be precipitate as
hydroxide. But they do not precipitate with Group – III hydroxide
[Ksp]IV, V >> [Ksp]III
[Ksp]Mg(OH)2 >> [Ksp]III
NH4Cl NH4+ + Cl–
NH4OH NH4+ + OH–
 Common ion effect suppress the ionisation
–
of NH4OH and lower [OH].
–
 Low [OH] not sufficient for group IV, V and
Mg2+ hydroxide precipitation. As
[Q]sp < Ksp
SPECIAL CASES OF THE GROUP ANALYSIS OF METAL CATIONS-II
Case III: When excess NH4OH is added to a solution containing both AlCl3
and ZnCl2, Only [Al(OH)3] is precipitate.
AlCl3 + 3NH4OH Al(OH)3 + 3NH4Cl
 The NH4Cl suppress ionisation of NH4OH
–
and resultant [OH] is not sufficient for
precipitation of Zn(OH)2 for high Ksp.
Case IV: In the analysis of Group–III , iron is detected as Fe 3+ but not as
Fe2+. –
In Group–III [OH] is reduced by adding NH4Cl in order to prevent
precipitation of other group hydroxide.
[Ksp]Fe(OH)2 >> [Ksp] Fe(OH)3
 So this Unprecipitate Fe2+ appears in
Group IV as black precipitate of FeS.
Fe2+ + S2 FeS (Black)
 This disturbs the Group – IV Cation detection.
HNO3
Fe2+ + S2 Fe3+
–
 Low [OH] sufficient to precipitation of Fe(OH) 3
for low Ksp of Fe(OH)3
Case V : ZnS can be precipitated by passing H2S from a solution
(H3CCOO)2Zn but not ZnCl2.
ZnCl2 + H2S ZnS + HCl

(H3C COO)2 Zn + H2S ZnS + 2 CH3 COOH

 Strong acid removes S2– as H2S.

For such [Zn2+][S2–] < Ksp

 Weak acid (CH3COOH) cannot produce

sufficient H+ to remove sulphide ions.
Hence, [Zn2+][S2–] > Ksp
SPECIAL CASES OF THE GROUP ANALYSIS OF METAL CATIONS-III
Case VI: Group–IV Sulphides are precipitated by passing H 2S
in alkaline medium
 In group IV anions will interfere and produces strong acids.

 Acid suppress ionisation of H2S and

prevent precipitation of metal sulphides.
 NH4OH is added in order to increase
ionisation of H2S.
 NH4Cl is added to control the ionisation of
NH4OH that the resultant [-OH] is not
sufficient for Mg(OH)2 precipitation.
Case VII: In the analysis of Group V, Ba2+ is detected first followed by
Sr2+ and Ca2+.
Ba2+ + K2CrO4 BaCrO4
 Sr2+ and Ca2+ will not precipitated for their high Ksp)
Sr2+ + H2SO4 SrSO4
 CaCrO4 cannot precipitated due to high Ksp
Ca2+ + (NH4)2 C2O4 CaC2O4
Note: If Ba2+ is not removed at first as Oxalate,
BaSO4 is also precipitated along SrSO4
whose Ksp are very similer.
Case VIII: Calcium oxalated is soluble in dil HCl but insoluble
in acetic acid (aq).
HCl H+ + Cl–
2–
C2O4 + 2H+ H2 C 2 O4
 As HCl is strong acid, remove oxalate as weak axalic
acid. 2–
So [Ca2+] [C2O4 ] < Ksp
 CH3 COOH being a weak acid cannot provide
2–
sufficient H+ to remove C2O4
2–
Hence, [Ca2+] [C2O4 ] > Ksp
So salt is insoluble.
PROBLEM-I
 Qualitative Analysis
(1) Colourless salt, (A) (insoluble in water) + dil H 2SO4 (B) + (C )(g)

NaOH NaOH
(B) (D) white ppt (E) (soluble)
(excess)
NH4Cl + NH4OH (C)
no ppt
(A)

(C) + (F) (yellow coloured solution) light green (G)

K4[Fe(CN6)]
+O2 blue (H)
AgNO3
 white ppt (I) (soluble in NH3)
(+C)
H2O + (J) Colloidal white turbidity
Cr2O7 /H+
2–
green
Ca(OH)2
milky
 ZnS + dil H2SO4 ZnSO4 + H2S
Colourless salt (A) (B) (C)

NaOH NaOH
ZnSO4 Zn(OH)2 [Zn(OH)4]2-
(B) (excess) Soluble
White ppt
H2S (C)
(D) (E)
NH4Cl + NH4OH ZnS (A)
(Precipitating reagent
for group III)
No precipitation
 H2S + FeCl3 FeCl2 + S + HCl
(C) (Yellow Light green
colored
(G)
solution)
(F)
K4[Fe(CN)6]
Fe4[Fe(CN)6]3
(Prussium blue) (H)
+ O2
 AgNO3 NH3
AgCl (White) ppt [Ag(NH3)2]Cl
(I)
+ H2S (C)
H2O + SO2 S + H2O
(J) (Colloidal white turbid)
Comproportionation reaction
 H2S (C)
H2O + SO2 S + H 2O Comproportionation reaction
(J) (Colloidal white turbid)

Cr2O7–2/H+ Cr3+
Green
Ca(OH)2
CaSO3
Milky
PROBLEM-II
 (2) K2Cr2O7 NaOH Yellow
Yellow coloured solution Red vapour solution
(A) H2SO4 (F) (G)
Excess CH3 AcOH
K4[Fe(CN)6] Pb(OAC)2
NH4SCN (D)
O Yellow
ppt
Red coloured Blue (I) (H)
(B) Light green (C)
K3[Fe(CN)6] (E)
K2Cr2O7/H+

(J) (A)
Blue
NH3 Red residue KI (D) Greenish (D)
Brown ppt K white Black residue (L)
(Excess) (Excess)
(N) (M)
 (2) K2Cr2O7 NaOH Na2CrO4
Yellow coloured solution CrO2Cl2
Yellow solution
(FeCl3) H2SO4 Red vapour
AcOH (G)
Excess (A) (F) Pb(OAC)2
NH4SCN K4[Fe(CN)6] CH3
PbCrO4
SnCl2(D)
O Yellow ppt
Fe(SCN)3 Fe4[Fe(CN)6]3 (H)
Red coloured Blue CHO
(B) Light green (C)
FeCl2 O
K3[Fe(CN)6] (E)
K2Cr2O7/H+ (I)

Fe3[Fe(CN)6]2 FeCl3
(A)
(J)
 (D)
Hg2Cl2
NH3 KI (D)
HgO.HgNH2I K2[HgI4] K Greenish Hg
(Excess) (Excess) Black residue
Brown ppt Red residue
white
(N) (M) (L)