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Salt Analysis

Qualitative analysis involves identification of ions (cations and


anion) of a salt or a mixture of salts through their characteristic
reactions. The process involves.

1. Analysis of anions
2. Analysis of cations.

Group I
Anions which liberate gases with dil. HCl or dil. H2SO4
.CO2−3 , HCO−3 , SO2−3 , S2−, S2O−3 , NO−2
Group II
Gases or acid vapours evolved with conc. H2SO4 (Cl−, Br−, I− ,NO−3)
Group III
Anions which do not liberate any gas with dil HCl or conc.H2SO4.
They are detected by precipitation (SO2−4 , PO3−4)
The detection of cations (basic radicals) and anions (acidic radicals)
in a salt or in a mixture is known as qualitative analysis.

Some Important Observations during


Qualitative Analysis
1. List of different coloured salts

S.No. Salts Colour

1 Copper Salts Bluish Green

2 Nickel Salts Greenish Blue

3 Chromium Salts Dark Green

4 Cobalt Salts Pinkish or purple

5 Manganese salts Light Pink

6 Ferrous Salts Light green

7 Ferric Salts Pale Yellow

2. Action of Heat (Colour of Residue)

S.No. Colour Residue

1 Yellow(hot) and white (cold) ZnO

Reddish brown(hot) and yellow


2 PbO
(cold)

3 Black(hot) and Red(cold) HgO, Pb3O4

4 Black(hot) and Red Brown(cold) Fe2O3

5 Decrepitation Pb(NO3)2, NaCl

6 White sublimate Ammonium salts

3. Gases

S.No. Nature Gases

1 Colourless and odourless O2, CO2, N2


S.No. Nature Gases

gases

2 Colourless and odour NH3, SO2, HCl, H2S

NO2 (brown), Br2 (reddish


3 Coloured gases
brown), I2(violet), Cl2 (greenish yellow)

4. Flame Test

Metals Colour

Li Crimson Red

Na Golden Yellow

K Violet

Ca Brick Red

Sr Crimson

Ba Apple Green

Methods available for the detection of anions are not as systematic as


those used for the detection of cations. Furthermore anions are
classified essentially on the basis of process employed.

Class A: Includes anions that are identified by volatile products


obtained on treatment with acids. It is further divided into two sub
groups:

1. Gases evolved with dil HCl / dil H2SO4.


2. Gases or acid vapours evolved with conc. H2SO4.

Class B: Includes anions that are identified by their reactions in


solution. It is subdivided into two groups:

1. Precipitation reactions
2. Oxidation and reduction in solution

Class A.1
Anions which evolve gases on reaction with dil. HCl/dil. H2SO4. It
includes -CO2−3,SO2−3,S2−,NO−2,CH3COO−,S2O2−3
1. Carbonate (CO2−3)

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


dioxide.

CO2−3+2H+ → CO2↑ +H2O

The gas gives white 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

The following tests performed with then aqueous salts solution.

(ii) Barium chloride or calcium chloride solution : White ppt. of


barium or Calcium carbonate is obtained, which is soluble in mineral
acid.

CO2−3+Ba2+ → BaCO3 ↓

CO2−3+Ca2+ → CaCO3 ↓

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

CO2−3+2Ag+ → Ag2CO3 ↓

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 be happened if the mix is boiled, due to the formation of silver
oxide.

Ag2CO3 ↓ → CO2↓+Ag2O↓

2. Sulphites (SO2−3)

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


sulphur dioxide

SO2−3+2H+ → SO2↑+H2O

The gas has a suffocating odour of burning sulphur.


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

SO2+K2Cr2O7+H2SO4 → K2SO4+Cr2(SO4)3(green)+H2O

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

SO2+Ca(OH)2 → CaSO3(milky) ↑ +H2O

Precipitate dissolves on prolonged passage of the gas, due to the


formation of soluble hydrogensulphite ions

CaSO3 ↓ +SO2+H2O→ +Ca(HSO3)2

(iv) Barium chloride or Strontium chloride solution : Salt solutions


gives white ppt of barium or strontium sulphite.

SO2−3+Ba2+ → BaSO3 ↓

SO2−3+Sr2+ → SrSO3 ↓

3. Sulphide (S2−)

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

S2++2H+ → H2S↑

(ii) The gas turns lead acetate paper black

(CH3COO)2Pb+H2S → PbS↓+2CH3COOH

(iii) Salt solution gives yellow ppt. with CdCl2

Na2S+CdCl2 → CdS(yellow)↓ +2NaCl

(iv) Silver nitrate solution : black ppt. of silver sulphide insoluble in


cold but soluble in hot dil nitricacid.

S2++2Ag+ → Ag2S↓

(v) Sodium nitroprusside solution : Turns sodium nitroprusside


solution purple

Na2S+Na2[Fe(CN)5NO]→ Na4[Fe(CN)5NOS]
4. Nitrites (NO−2)

(i) Dil HCl and Dil.H2SO4: Adding to solid nitrite in cold yield 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

NO−2+H+ → HNO22HNO3 → H2O+N2O33HNO2 → HNO3+2NO↑


+H2O2NO↑+O2↑ → 2NO2↑

Following tests performed with an aqueous salt solution.

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

NO−2 + Ag+ → AgNO2↓

(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, due to the formation
of [Fe,NO]SO4at the junction of the two liquids.

NO−2+CH3COOH → HNO2+CH3COO−3HNO2 → HNO3+2NO↑ +H


2OFe2++SO2−4+NO↑→ [Fe,NO]SO4

5. Acetate (CH3COO−)

(i) Dilute Sulphuric Acid: Smell of vinegar

CH3COO−+H+→ CH3COOH↑

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

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

6. Thiosulphates(S2O2−3)

(i) Dil Hydrochloric acid : Gives sulphur & sulphur dioxide

S2O2−3+2H+ → S↓ +SO2↑+H2O

(ii) Iodine Solution : Decolourise due to formation of tetrathionate ion

I2+2S2O2−3→ 2I+S4O2−6

(iii) Barium chloride solution : White ppt. of barium thiosulphate is


formed
S2O2−3+Ba2+→ Ba2S2O3↓

But no ppt. is obtained with CaCl2solution

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


S2O2−3+2Ag+→ Ag2S2O3↓

The ppt. is unstable, turning dark on standing, due to the formation


of silver sulphide.

Ag2S2O3↓+H2O → Ag2S+H2SO4

(v) Lead acetate or Lead nitrate solution : Gives white ppt.

S2O2−3+Pb2+→ PbS2O3↓

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

PbS2O3↓+H2O → PbS↓+2H++SO2−4

Class A.2
Gases or acid vapours evolved with conc. Sulphuric acid, it
includes Cl−,Br−,I−,NO−3

1. Chloride (Cl−)

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

Cl−+H2SO4→HCl+HSO−4

Gas so produced

1. Turns blue litmus paper red


2. Gives white fumes ofNH4Cl when a glass rod moistened with
ammonia solution is brought to the mouth of test tube

(ii) Manganese dioxide and conc. sulphuric acid: When a solid


chloride is treated with MnO2and conc.H2SO4, yellowish green
colour is obtained

MnO2+2H2SO4+2Cl− → Mn2++Cl2↑+2SO2−4+2H2O

The following tests are performed with the salt solution

(iii) Silver nitrate solution: White, curdy ppt. of AgCl insoluble in


water & in dil nitric acid, but soluble in dilute ammonia solution

Cl−+Ag+→ AgCl↓AgCl↓+2NH3→[Ag(NH3)2]ClAg(NH3)2Cl+2H+ →
AgCl+2NH+4
(iv) Lead acetate solution: White ppt. of lead chloride is formed

2Cl−+Pb+2⟶PbCl2 ↓

(v) Chromyl chloride test : When a mix containing chloride ion is


heated with K2Cr2O7 and conc.H2SO4 orange red fumes of chromyl
chloride CrO2Cl2are formed.

K2Cr2O7+4NaCl+6H2SO4 ⟶ 2KHSO4+4NaHSO4+2CrO2Cl2↑+3H2
O

Chlorides of mercury, owing to their slight ionization, do not respond


to this test and only partial conversion to CrO2Cl2occurs with the
chlorides of lead, silver, antimony and tin.

When chromyl chloride vapours are passed into sodium hydroxide a


yellow solution of sodium chromateis formed which when treated
with lead acetate gives yellow ppt. of lead chromate.

CrO2Cl2+2NaOH→Na2CrO4(Yellow solution)+2HClNa2CrO4+(CH3
COO)2Pb→2CH3COONa+PbCrO4↓ (yellow ppt.)

2. Bromide (Br−)

(i) Conc. H2SO4: Gives reddish brown vapours of bromine

2KBr+H2SO4→ K2SO4+2HBr2HBr+H2SO4→2H2SO4+SO2↑+Br2↑

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

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

The following tests are performed with the salt solution

(iii) Silver nitrate solution: A pale yellow ppt. of silver bromide is


obtained. This ppt. is sparingly soluble in dilute but readily soluble in
concentrated ammonia solution and insoluble in dil. HNO3.

Br−+Ag+ ⟶AgBr

(iv) Lead acetate solution: White crystalline ppt. of lead bromide


which is soluble in boiling water

2Br−+pb+2 ⟶PbBr2↓

(v) Chlorine water: When this solution is added to a solution of


bromide and chloroform free bromine is liberated, which colours the
organic layer orange – red
2KBr+Cl2(water)→2KCl+Br2Br2+chloroform→ orange red colour

(vi) Potassium dichromate & conc. H2SO4 is heated and passing the
evolved vapours into water, a yellowish brown solution is obtained.

2kBr+K2Cr2O7+7H2SO4 → 3Br2↑+Cr2(SO4)3+4K2SO4+7H2O

3. Iodide (I−)

(i) Conc. H2SO4 : Gives violet vapours of iodine

2I−+2H2SO4 → I2+SO2−4+2H2O+SO2↑

The following tests are performed with the salt solution.

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

I−+Ag+ → AgI

(iii) Lead acetate solution: Yellow, curdy ppt. of lead iodide soluble in
much hot water forming a colour less solution & yielding golden
yellow plates (spangles) on cooling

2I−+Pb2+ → PbI2↓

(iv) Potassium dichromate & conc. sulphuric acid: Iodine is liberated

6I−+Cr2O2−7+2H2SO4 → 3I2↑+2cr3++7SO2−4+7H2O

(v) Chlorine water: Iodine is liberated, by the drop wise addition of


chlorine water to iodide, and on addition of CHCl3violet coloured
organic layer is obtained.

2I−+Cl2→ I2+2Cl−I2+chloroform → violet coloured layer

(vi) Copper sulphate solution: Gives brown ppt. consisting of a


mixture of copper (I) iodide & iodine and on addition of hypo solution
brown ppt changes to white ppt.

4I−+2Cu2+ → 2CuI+I2I2+2S2O2−3 → 2I−+S4O2−6

(vii) Mercury (II) chloride solution: Forms scarlet ppt. of HgI2

2I−+HgCl2→ HgI2↓+2Cl−

This ppt. dissolves in excess of KI, forming tetraiodo mercurate (II)


complex.
4. Nitrate (NO−3)

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

4NO−3+2H2SO4 → 4NO2↑+2SO2−4+2H2O+O2↑

The following tests are performed with the salt solution.

(ii) Brown ring test : When a freshly prepared solution of iron (II)
sulphate is added to nitrate solution & conc. H2SO4is poured slowly
down the side of the test - tube, a brown ring is obtained.

2NO−3+4H2SO4+6Fe2+→ 6Fe3++2NO+4SO−4+4H2OFe2++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.

Action of heat : The result varies with the metal

1. Nitrates of sodium and potassium evolve oxygen (test with glowing


splint) & leave solid nitrites (brown fumes with dilute acid)

2NaNO3→ 2NaNO2+O2↑

2. Ammonium nitrate yields dinitrogen oxide & steam

NH4NO3→ N2O ↑+2H2O

3. Nitrates of the noble metals leave a residue of the metal and a mix
of nitrogen dioxide and oxygen is evolved.

2AgNO3→2Ag+2NO2↑+O2↑

4. Nitrates of other metals, such as those of lead and copper, evolve


oxygen and nitrogen dioxide and leave a residue of the oxide

2Pb(NO3)2 → 2PbO+4NO2↑+O2↑

Class B.1
1. Sulphate (SO2−4)

All sulphates except those of Ba, Pb, Sr are soluble in water.


Sulphates of calcium and mercury(II) ares lightly soluble. The
following tests are performed with the salt solution.

(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.
SO2−4+Ba2+→BaSO4↓

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

SO2−4+3Hg2+ +2H2O → HgSO4.2HgO↓+4H+

Class B.2
1. Chromate (CrO2−4) and Dichromate(Cr2O2−7)

Metallic chromates gives yellow solution when dissolved in water. In


the presence of H+ chromates are converted into dichromates
(orange-red solution).

2CrO2−4+2H+⇌ Cr2O2−7+H2OCrO2−4+2OH−⇌ 2CrO2−4+H2O

It may also be expressed as :

2CrO2−4+2H+⇌2HCrO−4⇌ Cr2O2−7+H2O

(i) Barium chloride solution: Pale - yellow ppt. of barium chromate


soluble in dilute mineral acids but insoluble in water and acetic acid.

CrO2−4+Ba2+ → BaCrO4↓

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

Cr2O2−7+2Ba2++H2O ⇌2BaCrO4↓+2H+

If sodium hydroxide or sodium acetate is added, precipitation


becomes quantitative.

(ii) Silver nitrate solution: Brownish - red ppt. of silver


chromate Ag2CrO4which is soluble in dil. nitric acid & in ammonia
solution, but is insoluble in acetic acid.

CrO2−4+2Ag+ →Ag2CrO4↓2Ag2CrO4+2H+→4Ag++Cr2O2−7+H2OA
g2CrO4↓+4NH3→2[Ag(NH3)2]+ +CrO2−4Ag2CrO4↓+2Cl−→2AgCl+
CrO2−4

A reddish brown ppt. of silver dichromate Ag2Cr2O7 is formed with a


conc. solution of a dichromate

Cr2O2−7+2Ag+→ Ag2Cr2O7

(iii) Lead acetate solution: Yellow ppt. of lead


chromate PbCrO4 insoluble in acetic acid, but soluble in dil nitric
acid

CrO2−4+Pb2+→PbCrO4↓2PbCrO4↓+2H+⇌2Pb2++Cr2O2−7+H2O
**(iv) H2O2 a deep blue solution of chromiumpenta oxide is obtained

CrO2−4+2H+ +2H2O2→CrO5+3H2O

Cr+3 Salt.

2. Permanganate (MnO−4)

(i) Hydrogen peroxide : It decolourises acidified potassium


permanganate solution

2MnO−4+5H2O2+6H+→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

MnO−4+5Fe2++8H+→5Fe3++Mn2++4H2O

(iii) Action of heat : On heating, a residue of potassium


manganate K2MnO4 and black manganesedioxide remains behind.
Upon extracting with water and filtering, a green solution of potassium
manganateis obtained

2KMnO4 → K2MnO4+MnO2+O2↑

For the purpose of systematic qualitative analysis, cations are


classified into five groups on the basis of their behaviour with some
reagents and classification is based on whether a cation reacts with
these reagents by the formation of precipitate or not (solubility
difference)

Group
Group Ions Colour & Precipitate
Reagent
Group I dil. HCl Pb2+,Hg+,Ag+ PbCl2,HgCl2,AgCl- white
Hg2+,Cu2+,Bi3+,Cd2+, A
Group II & H2S in
s3+,As5+,Sb3+,Sb5+,Sn5 Yellow CdS,As2S3,As2S6,SnS2
Group II A dil HCl
+
Black−HgS,CuS,PbS,Orange−
Group II B – Sn4+
Sb2S3,Sb2S6,Brown−Bi2S3,SnS
NH4OH
In Fe(OH)3 (brown),Al(OH)3(white
Group III A Fe3+,Al3+,Cr3+
presence ),Cr(OH)3 (green)
of NH4Cl
H2S in ZnS white or grey, Black -
Group III B presence Ni2+,Co2+,Mn2+,Zn2+ CoS,NiS, MnS - Buff (light
of NH3 & pink)
Group
Group Ions Colour & Precipitate
Reagent
NH4Cl or
NH4S
(NH4)2CO
3in
Group IV presence Ba2+,Sr2+,Ca2+ BaCO3,SrCO3,CaCO3- white
of NH4Cl
& NH4OH
No
common Mg^{2+},Na^+,K^+,NH_4
Group V –
group ^+
reagent

Points to Remember:-

1. Group I radicals (AgCl,PbCl2,Hg2Cl2) is less than the solubility


products of all other chlorides which remain in solution.
2. Group II radicals are precipitated as sulphides because
sulphides of other metals remain in solution because of their
high solubility products, HCl acts as a source ofS2−- is only
sufficient to precipitate the Group II radicals only.
3. Group III A radicals are precipitated as hydroxides and
the NH4OH so that only the group III A radicals are
precipitated because of their low solubility product. Note:

1. Excess of of NH4Cl should be added otherwise manganese


will be ppt. as MnO2.H2O.
2. (NH4)2SO4 can’t be used in place of NH4Clbecause
the SO2−4 will ppt. barium as BaSO4.
3. NH4NO3 can’t be used in place
of NH4Clbecause NO−3 ions will
oxidise Mn2+ to Mn3+ and thus Mn(OH)3 will be
precipitated in III A group.
4. Only Al(OH)3 is soluble in excess of NaOHfollowed by
boiling to form sodium metaluminate
while Fe(OH)3 and Cr(OH)3 are insoluble.
4. Ammonium hydroxide increases the ionisation of H2Sas
unionised water by removing H+ from H2S in unionised water
H2S ⇌2H++S2−, H+ +OH−→H2O
Now excess of H2S is passed through a neutral solution,
incomplete precipitation will take place due to the formation of
HCl which decreases the ionization of H2S.
MnCl2+H2S→MnS+2HCl
Identification of Basic Radicals
All confirmatory tests for basic radicals are performed with the salt
solution.

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

(a) K2CrO4. The ppt. is insoluble in acetic acid but soluble in NaOH

Pb(NO3)2+K2CrO4→PbCrO4↓+2KNO3
PbCrO4+4NaOH→Na2[PbO2]+Na2CrO4+2H2O

(b) Pb(NO3)2+2KI→PbI2↓+2KNO3(Yellow)
PbCl2+2KI(excess)→K2[PbI4]

AgCl is soluble in NH4OH

AgCl+2NH4OH→Ag(NH2)2Cl+2H2O

Hg2Cl2+2NH4OH⟶H2N−Hg−Cl + Hg↓ + NH4Cl + 2H2O


Amino mercuric chloride.

2. Group II A (Hg2+,Cu2+,Bi3+,Cd2+)

(i) SnCl2, give white precipitate turning black.

2Hg+2+SnCl→Sn+4+Hg2Cl2↓(white)

Hg2Cl2+SnCl2→SnCl4+2Hg↓(black)

(ii) Cu+2 ions in solution gives a pale blue precipitate which gives a
deep blue colour with excess of NH4OH

Cu+2+4NH4OH→[Cu(NH3)4]+2 (Deep blue in colour)+4H2O

Cu2+ 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↓(white ppt.)+2HCl

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

2BiCl3+3Na2SnO2→2Bi↓(black)+3Na2SnO3+6NaCl+3H2O

(iv) Cd+2 ions in solution, with ammonium hydroxide gives a white


precipitate which dissolves.
Cd+2+2NH4OH→Cd(OH)2↓+2NH+4(yellow)

Cd(OH)2+4NH4OH→[Cd(NH3)4](OH)2

3. Group II B (As3+,As5+,Sb3+,Sb5+,Sn3+,Sn4+)

(i)HNO3

As+3−→−−−−−OxidationHNO3 As+5(as H3AsO4)

H3AsO4+12(NH4)+21HNO3→(NH4)3AsMo12O40↓+21NH4NO3(yell
owppt.)+12H2O

(ii)HgCl2 , which turns black on standing.

SnCl2+2HgCl2→SnCl4+Hg2Cl2↓(white)

Hg2Cl2+SnCl2→SnCl4+2Hg↓(black)

(iii)SbCl3 , on addition of water give white precipitate.

SbCl3+H2O→SbOCl↓(white)+2HCI

4. Group III A (Al3+,Fe3+,Cr3+)

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

Al(OH)3+NaOH→NaAlO2+2H2O

(ii) Precipitate of BaCl2 to this solution gives yellow precipitate

Br2+H2O→2HBr+(O)2Cr(OH)3+4NaOH+3(O)→2Na2CrO4+5H2ONa
2CrO4+BaCl2→BaCrO4↓(yellow ppt.)+2NaClFe(OH)3 is insoluble in
NaOH

(iii) Brown precipitate of Fe(OH)3 is dissolved in HCl and addition


of KCNS to this solution gives blood red colour

Fe(OH)3+3HCl→ FeCl3+3H2OFeCl3+3KCNS→Fe(CNS)3(blood red)


+3KClAlso on addition of K4Fe(CN)6 to this solution,a prussian blue
colour is obtained.FeCl3+3K4Fe(CN)6→Fe4[Fe(CN)6]3(prussia blue c
olour)+12KCl

5. Group III B (Ni2+,Co2+,Mn2+,Zn2+)

(i)Ni+2 is present.

CoCl2+6KHCO3→K4[Co(CO3)3]+2KCl+3CO2↑+3H2O2K4[Co(CO3)3]
+2KHCO3+[O]→2K3[Co(CO3)3](Apple green colour)+2K2CO3+H2O
NiCl2+2KHCO3→NiCO3+2KCl+H2O+CO2↑2NiCO3+4NaOH+[O]→
Ni2O3↓(black ppt.)+2Na2CO3+2H2O

(ii)Zn+2 ions in solution give a white precipitate with NaOH, which


dissolves in excess of NaOH

Zn+2+2NaOH→Zn(OH)2↓(white)+2Na+

Zn(OH)2+2NaOH→Na2ZnO2+2H2O

(iii)Mn+2ions in solution give pink precipitate with NaOHturning


black or brown on heating.

Mn+2+2NaOH→Mn(OH)2(pink)+2Na+

Mn(OH)2+[O]−→Δ MnO2(brown or black)+H2O

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

(i) Ba+2 ions in solution give

(a) Yellow precipitate with K2CrO4

Ba+2+K2CrO4→BaCrO4↓(yellow)+2K+

(b) White precipitate with (NH4)2SO4

Ba+2+(NH4)2SO4→BaSO4↓(white)+2NH+4

(c) White precipitate with (NH4)2C2O4

Ba+2+(NH4)2C2O4→BaC2O4↓(white)+2NH+4

(ii) Sr+2 ions give white precipitate


with (NH4)2SO4 and (NH4)2C2O4

Sr+2+(NH4)2SO4→SrSO4↓(white)+2NH+4Sr+2+(NH4)2C2O4→SrC2
O4↓(white)+2NH+4

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


Ca+2+(NH4)2C2O4→CaC2O4↓(white)+2NH+4

7. Group V (NH+4,Na+,K+,Mg+2)

(i) All ammonium salts on heating with alkali say NaOH give a
colourless, pungent smelling gas (NH3).

NH4Cl+NaOH→NaCl+NH3↑+H2O

(a) Gas evolved gives white fumes with a rod dipped in conc. HCl
NH3+HCl→NH4Cl↑(white fumes)

(b) Paper soaked in NH3

CuSO4+4NH3→[Cu(NH3)4]SO4(deep blue)

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

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

(d) An aqueous solution of an ammonium gives a brown ppt. with


Nessler’s reagent (alkaline solution of potassium
tetraiodomercurate(II) ).

(ii) Potassium salts give a yellow ppt. with sodium cobaltinitrite

Na3[Co(NO2)6]+3KCl→K3[Co(NO2)6](yellow)+3NaCl

(iii) Sodium salts give a heavy white ppt. with potassium dihydrogen
antimonate

KH2SbO4+NaCl→NaH2SbO4↓(white ppt.)+KCl

(iv) Mg2+ gives white ppt. of magnesium hydroxide with sodium


hydroxide

Mg2++2NH3+2H2O→Mg(OH)2↓+2NH+4

The ppt. obtained is sparingly soluble in water but readily soluble in


ammonium salt.