handout d & f-block Elements

Course : ARJUN

Target: JEE (Main + Advanced)

Handout of

d & f-block Elements

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handout d & f-block Elements

PREPARATIONS AND PROPERTIES OF SOME IMPORTANT d-BLOCK

METAL COMPOUNDS
[A] COMPOUNDS OF IRON :
 Ferrous Sulphate, FeSO4.7H2O (Green vitriol)
It is commonly known as harakasis
 Preparation
(i) By iron scrap :
Fe + H2SO4  FeSO4 + H2
(ii) From kipp's waste :
3FeS2 + 2H2O + 11O2  FeSO4 + Fe2(SO4)3 + 2H2SO4
Fe2(SO4)3 + Fe  3FeSO4
(iii) FeCO3 + H2SO4  FeSO4 + H2O + CO2
 Properties
(a) Physical : Hydrated ferrous sulphate is a green crystalline compound, effloresces on exposure
to air. Anhydrous FeSO4 is colourless.
(b) Chemical :
(i) On exposure to atmosphere, it turns brownish-yellow due to the formation of basic ferric
sulphate.
4FeSO4 + 2H2O + O2  4Fe(OH) . SO4 (basic ferric sulphate)
(ii) Aqueous solution is acidic due to hydrolysis.
Fe2+ + 2H2O Fe(OH)2 + 2H+

140C High
(iii) FeSO4 . 7H2O   FeSO4. H2O 300
 ºC
 2FeSO4  Fe2O3 + SO2 + SO3
Temp.

(iv) FeSO4 + 6KCN  K4[Fe(CN)6] + K2SO4

(v) It acts as reducing agent.
AuCl3 + 3FeSO4  Au + Fe2(SO4)3 + FeCl3
6HgCl2 + 6FeSO4  3Hg2Cl2 + 2Fe2(SO4)3 + 2FeCl3
MnO4– + 8H+ + 5Fe2+  5Fe3+ + Mn2+ + 4H2O
Cr2O72– + 14H+ + 6Fe2+  6Fe3+ + 2Cr3+ + 7H2O
 Uses : It is used :
(i) for making Blue - Black ink.
(ii) as mordant in dyeing
(iii) as insecticide in agriculture
(iv) for making laboratory reagents like Mohr's salt etc.
FeSO4 + (NH4)2 SO4 + 6H2O)  FeSO4 (NH4)2SO4.6H2O (Mohr's salt)
(v) FeSO4 + H2O2 known as Fenton's reagent is used as catalyst.
 Ferric Oxide, Fe2O3 :
 Preparation :

(i) 2Fe(OH)3   Fe2O3 + 3H2O

(ii) 2FeSO4   Fe2O3 + SO2 + SO3
(iii) 4FeS + 7O2  2Fe2O3 + 4SO2

 Properties :
(a) Physical : It is a deep red powder and is insoluble in water.

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handout d & f-block Elements
(b) Chemical :
(i) Amphoteric nature of iron (III) oxide.
Fe2O3 + 6HCl  2FeCl3 + 3H2O
fusion
Fe2O3 + 2NaOH  H2O + 2NaFeO2
fusion
Fe2O3 + Na2CO3  2NaFeO2 + CO2

NaOCl and chlorine oxidises the NaFeO2 in to Na2FeO4.

NaFeO2 + Cl2 + 4NaOH  2Na2FeO4 + 2NaCl + 2H2

(ii) 6Fe2O3 1300

 ºC
 4Fe3O4 + O2

(iii) Fe2O3 + 3H2  2Fe + 3H2O

 Uses : It is used as (i) a red pigment, (ii) an abrasive polishing powder and (iii) a catalyst.

 Ferric Chloride, FeCl3 :

 Preparation :
(a) Anhydrous FeCl3 :

(i) 12FeCl2 (anhydrous) + 3O2  2Fe2O3 + 8FeCl3

(ii) 2Fe + 3Cl2(dry)  2FeCl3
(iii) FeCl3 . 6H2O + 6SOCl2  FeCl3 + 12HCl + 6SO2
OCH3
|
(iv) FeCl3.6H2O + 6CH3 — C — CH3  FeCl3 + 12CH3OH + 6CH3COCH3
|
OCH3
(b) Hydrated FeCl3 :
(i) Fe(OH)3 + 3HCl  FeCl3 + 3H2O
(ii) Fe2O3 + 6HCl  2FeCl3 + 3H2O
(iii) Fe2(CO3)3 + 6HCl  2FeCl3 + 3H2O + 3CO2
(iv) 2Fe + 4HCl + Cl2  2FeCl3 + 2H2 
All solutions of FeCl3 obtained in above chemical reactions on crystallisation gives hydrated
FeCl3.6H2O.

 Properties
(a) Physical :
Anhydrous ferric chloride is dark black solid while hydrated salt, FeCl3 . 6H2O is yellowish-brown
deliquescent crystalline solid. Both are soluble in water as well as in ether forming solvated species,

[Fe(H2O)4Cl2]Cl . 2H2O and O  FeCl3 respectively..

It is sublimed at 300°C giving a dimeric gas, .

(b) Chemical :
(i) Action of heat :

(a) 2FeCl3 (anhydrous)  2FeCl2 + Cl2

(b) 2[FeCl3. 6H2O]  Fe2O3 + 6HCl + 9H2O
(ii) Aqueous solution is acidic due to hydrolysis.
[Fe(H2O)6]3+ + H2O [Fe(H2O)5(OH)]2+ + H3O+
acid base base acid
(iii) As oxidising agent : 2FeCl3 + SnCl2  2FeCl2 + SnCl4
2FeCl3 + H2S  2FeCl2 + 2HCl + S
2FeCl3 + SO2 + 2H2O  2FeCl2 + H2SO4+ 2HCl
2FeCl3 + 2KI  2FeCl2 + 2KCl + 2

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handout d & f-block Elements

(iv) Formation of addition compounds :

FeCl3 + 6NH3  FeCl3. 6NH3 ; FeCl3 + NOCl  [Link]
(v) 2FeCl3 + 3Na2CO3 + 3H2O  2Fe(OH)3 + 6NaCl + 3CO2
 Uses :
It is used :
(i) as a medicine (its alcoholic solution named as tincture is ferri perchloride).
(ii) for detection of acetates and phenols.
(iii) for making prussian blue dye.
(iv) as an oxidising agent.
[B] COMPOUNDS OF ZINC :

 Zinc oxide, ZnO (Chinese white or philosopher's wool)

It is found in nature as zincite or red zinc ore.
 Preparation :

(i) 2Zn + O2  2ZnO (ii) ZnCO3  ZnO + CO2
 
(iii) 2Zn(NO3)2  2ZnO + 4NO2 + O2 (iv) Zn(OH)2  ZnO + H2O
 Properties

(a) Physical :
It is a white powder which becomes yellow on heating due to change in the structure of lattice
but again turns white on cooling. it is insoluble in water and sublimes at 400°C.
(b) Chemical :
(i) It is amphoteric in nature.
ZnO + H2SO4  ZnSO4 + H2O
ZnO + 2NaOH  Na2ZnO2 + H2O

(ii) ZnO + H2   Zn + H2O
400 º C

 Uses :
It is used :
(i) as a white paint. It does not get tarnished even in presence of H2S because ZnS is also
white.
(ii) for preparing Rinmann's green (Green paint - ZnCoO2)
(iii) as catalyst for preparation of methyl alcohol
(iv) for making soft rubber
(v) for making cosmetic powders, creams and in medicine

 Zinc Sulphate, ZnSO4 . 7H2O (White vitriol)

 Preparation :

(i) Zn + H2SO4  ZnSO4 + H2

(ii) ZnO + H2SO4  ZnSO4 + H2O
(iii) ZnCO3 + H2SO4  ZnSO4 + H2O + CO2
 Properties :

(a) Physical : It is a colourless, crystalline solid soluble in water. It slowly effloresces when exposed
to air.
It is isomorphous with Epsom salt (MgSO4 . 7H2O)
(b) Chemical :
(i) ZnSO4 + 2NaOH  Zn(OH)2 (white) + Na2SO4
Zn(OH)2 + 2NaOH  Na2ZnO2 (soluble complex) + 2H2O
(ii) ZnSO4 + 2NaHCO3  ZnCO3 + Na2SO4 + H2O + CO2
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handout d & f-block Elements

(iii) ZnSO4.7H2O 100

 ºC
 ZnSO4 . 6H2O 280
 ºC
 ZnSO4 800
 ºC
 ZnO + SO3

 Uses :
It is used :
(i) as eye lotion, (ii) for making lithophone - mixture of BaS + ZnSO4 (white paint) and (iii) as
mordant in dyeing
 Zinc Chloride ZnCl2.2H2O
 Preparation :
It is prepared by dissolving zinc oxide, carbonate or hydroxide in dilute hydrochloric acid
ZnO + 2HCl  ZnCl2 + H2O
The solution so obtained on concentration and cooling gives the crystals of ZnCl2 . 2H2O.
Anhydrous zinc chloride cannot be prepared merely by heating the crystals of ZnCl2 . 2H2O
b e c a u s e
a basic chloride Zn(OH)Cl is formed during decomposition which on further heating gives ZnO.
ZnCl2 . 2H2O  Zn(OH)Cl + HCl + H2O
Zn(OH)Cl  ZnO + HCl
Hence anhydrous zinc chloride is obtained either by heating zinc in a current of chlorine gas or by
distilling a mixture of zinc powder and mercuric chloride

Zn + Cl2  ZnCl2 ; Zn + HgCl2  ZnCl2 + Hg
 Properties :
It is a white crystalline solid, deliquescent and soluble in water. On heating it forms the oxychloride
and finally the oxide. Its concentrated solution sets to a hard mass when mixed with zinc oxide and
the product is used as a dental filling.

[C] COMPOUNDS OF COPPER

 Copper Sulphate, CuSO4 . 5H2O (Blue Vitriol)
It is also called 'Nilathotha'.
 Preparation :
(i) CuO + H2SO4  CuSO4 + H2O
(ii) Cu(OH)2 + H2SO4  CuSO4 + 2H2O
1
(iii) Cu + H2SO4 + O  CuSO4 + H2O
2 2
(iv) [Link](OH)2 (malachite ore) + 2H2SO4  2CuSO4 + 3H2O + CO2 

 Properties
(a) Physical : It is a blue crystalline compound and is soluble in water.
(b) Chemical :
(i) CuSO4 + 2NaOH  Cu(OH)2  (blue) + Na2SO4
2CuSO4 + Na2CO3 + H2O  Cu(OH)2  (blue) + Na2SO4 + CO2  .
(ii) 2CuSO4 + SO2 + 2H2O + 2KI  CuI2 + 2H2SO4 + K2SO4
2CuSO4 + 2FeSO4 + 2KI  Cu2 I2 + Fe2(SO4)3 + K2SO4
(iii) CuSO4 + Fe  Cu + FeSO4
CuSO4 + Zn  Cu + ZnSO4
(iv) 2CuSO4 + 2KSCN + SO2 + 2H2O  2CuSCN  (white) + K2SO4 + 2H2SO4

100 º C
(v) CuSO4.5H2O air CuSO4.4H2O   250 º C
 CuSO4 . H2O  750 º C
 CuSO4    CuO + SO2
effloresce s

+ O2

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handout d & f-block Elements

 Uses :
It is used :
(i) for making other copper compounds.
(ii) for electroplating, electrotyping, as mordant in dyeing.
(iii) in making Bordeaux mixture which is used in agriculture as fungicide and germicide.
(iv) in making Fehling's solution.
(v) in medicine as antiseptic.
(vi) in electric batteries.

 Cupric Oxide, CuO

It is called black oxide of copper and is found in nature as tenorite.
 Preparation : It is prepared

(i) By heating Cu2O in air or by heating copper for a long time in air (the temperature should
n o t
exceed above 1100°C)
2Cu2O + O2  4CuO
2Cu + O2  2CuO

(ii) Cu(OH)2  CuO + H2O

(iii) 2Cu(NO3)2  2CuO + 4NO2 + O2
(iv) On a commercial scale, it is obtained by heating/calcination of malachite which is found in
nature.
CuCO3 . Cu(OH)2  2CuO + CO2 + H2O
 Properties

(a) Physical :
It is black powder insoluble in water and stable to moderate heating.
(b) Chemical :
(i) The oxide dissolves in acids HCl, H2SO4 of HNO3 forming corresponding salts.
CuO + 2H+  Cu2+ + H2O
(ii) When heated to 1100 – 1200°C, it is converted into cuprous oxide with evolution of oxygen.
4CuO  2Cu2O + O2
(iii) It is reduced to metallic copper by reducing agents like hydrogen, carbon and carbon
monoxide.
CuO + H2  Cu + H2O
 Cupric Chloride, CuCl2 . 2H2O
 Preparation :
(i) The metal or cupric oxide or cupric hydroxide or copper carbonate is dissolved in
concentrated HCl. The resulting solution on crystallisation gives green crystals of
hydrated cupric chloride.
2Cu + 4HCl + O2  2CuCl2 + 2H2O
CuO + 2HCl  CuCl2 + H2O
Cu(OH)2CuCO3 + 4HCl  2CuCl2 + 3H2O + CO2

(ii) Anhydrous cupric chloride is obtained as a dark brown mass when copper metal is heated
in excess of chlorine gas or by heating hydrated cupric chloride in HCl gas at 150°C.
Cu + Cl2  CuCl2

CuCl2 . 2H2O 150

 ºC
 CuCl2 + 2H2O
HCl gas

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handout d & f-block Elements

 Properties

(a) Physical :
It is deliquescent compound and is readily soluble in water. The dilute solution is blue but concentrated
solution is, however, green. It changes to yellow when concentrated HCl is added. The blue colour
is due to complex cation [Cu(H2O)4]2+ and yellow colour due to complex anion [CuCl4]2– and green
when both are present.
(b) Chemical :
(i) The aqueous solution is acidic due to its hydrolysis
CuCl2 + 2H2O Cu(OH)2 + 2HCl
(ii) The anhydrous salt on heating forms Cu2Cl2 and Cl2
2CuCl2  Cu2Cl2 + Cl2

3CuCl2 . 2H2O  CuO + Cu2Cl2 + 2HCl + Cl2 + 5H2O
Strong

(iii) It is readily reduced to Cu2Cl2 by copper turnings or sulphur dioxide gas or nascent
hydrogen (obtained by the action of HCl on Zn) or SnCl2.
CuCl2 + Cu  Cu2Cl2
2CuCl2 + SO2 + 2H2O  Cu2Cl2 + 2HCl + H2SO4
2CuCl2 + 2H  Cu2Cl2 + 2HCl
2CuCl2 + SnCl2  Cu2Cl2 + SnCl4

(iv) A pale blue precipitate of basic cupric chloride CuCl2 . 3Cu(OH)2 is obtained when NaOH is
added.
CuCl2 + 2NaOH  Cu(OH)2 + 2NaCl
CuCl2 + 3Cu(OH)2  CuCl2 . 3Cu(OH)2 
It dissolves in ammonium hydroxide forming a deep blue solution. On evaporation of this
solution deep blue crystals of tetraammine cupric chloride are obtained.
CuCl2 + 4NH4OH  [Cu(NH3)4]Cl2 . H2O + 3H2O

[D] COMPOUNDS OF SILVER :

 Silver Nitrate, AgNO3 (Lunar caustic) :
 Preparation :
It is prepared by heating silver with dilute nitric acid. The solution is concentrated and cooled when
the crystals of silver nitrate separate out.
heat
3Ag + 4HNO3 (dilute)  
 3AgNO3 + NO + 2H2O
 Properties
(a) Physical :
It is a colourless crystalline compound, soluble in water and alcohol. It melts at 212°C.
(b) Chemical :
(i) It possesses powerful corrosive action on organic tissues, which it turns black especially in
presence of light. The blackening is due to finely divided metallic silver, reduced by organic
tissue. It is, therefore, stored in coloured bottles.
(ii) On heating above its melting point, it decomposes to silver nitrite and oxygen.
2AgNO3  2AgNO2 + O2
When heated red hot, it gives metallic silver
2AgNO3  2Ag + 2NO2 + O2
(iii) Solutions of halides, phosphates, sulphides, chromates, thiocyanates, sulphates and
thiosulphates, all give a precipitate of the corresponding silver salt with silver nitrate solution
(for reactions refer qualitative analysis sheet).

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handout d & f-block Elements
(iv) Solid AgNO3 absorbs ammonia gas with the formation of an addition compound, AgNO3.
3NH3.
When NH4OH is added to silver nitrate solution, a brown precipitate of silver oxide appears
which dissolves in excess of ammonia forming a complex salt.
2AgNO3 + 2NH4OH  Ag2O + 2NH4NO3 + H2O
Ag2O + 2NH4NO3 + 2NH4OH  2[Ag(NH3)2]NO3 + 3H2O
(v) The ammonical solution of AgNO3 react with acetylene to form a white precipitate.
2AgNO3 + 2NH4OH + C2H2  Ag2C2 (silver acetylide) + 2NH4NO3 + 2H2O
(vi) Ammonical silver nitrate is called Tollen’s reagent and is used to identify reducing sugars
and aldehydes.

RCHO + 2Ag+ + 3OH–  RCOO– + 2Ag + 2H2O
It is known as “silver mirror” test of aldehydes and reducing sugars.
Ag2O + HCHO  2Ag + HCOOH
Ag2O + C6H12O6  2Ag + C6H12O7
(vii) Reaction with iodine :
(a) 6AgNO3 (excess) + 3I2 + 3H2O  AgIO3 + 5AgI + 6HNO3
(b) 5AgNO3 + 3I2 (excess) + 3H2O  HIO3 + 5AgI+ 5HNO3
(viii) Silver is readily displaced from an aqueous silver nitrate solution by the base metals,
particularly, if the solution is some what acidic.
2AgNO3 + Cu  2Ag + Cu(NO3)2
2AgNO3 + Zn  2Ag + Zn(NO3)2
(ix) Phosphine, arsine and stibine all precipitate silver from silver nitrate solution
PH3 + 6AgNO3 + 3H2O  6Ag + 6HNO3 + H3PO3
AsH3 + 6AgNO3 + 3H2O  6Ag + 6HNO3 + H3AsO3
 Uses :

(i) It is used as a laboratory reagent for the identification of various acidic radicals especially
for chloride, bromide and iodide. The ammonical silver nitrate solution i.e., Tollen's reagent
is used in organic chemistry for testing aldehydes, reducing sugars, etc.
(ii) Silver nitrate is used for making silver bromide which is used in photography.
(iii) It is used in the preparation of making inks and hair dyes.
(iv) It is used extensively for the preparation of silver mirrors. The process of depositing a thin
and uniform layer of silver on a clean glass surface is known as silvering of mirrors. It is
employed for making looking glasses, concave mirrors and reflecting surfaces. The process
is based on the reduction of ammonical silver nitrate solution by some reducing agent like
HCHO. The silver film deposited on the glass is first coated with a varnish and finally
painted with red lead to prevent its being scraped off.
 Silver oxide (Ag2O) :
 Preparation :
It is prepared as brown solid by adding sodium hydroxide solution to silver nitrate solution.
2AgNO3 + 2NaOH  Ag2O + 2NaNO3 + H2O
 Properties :
It is a brown solid sparingly soluble in water.
(i) On heating, it is decomposed to black metallic silver with evolution of oxygen at 160°C.

2Ag2O  4Ag + O2 
(ii) It is reduced to the metal by hydrogen on heating

Ag2O + H2  2Ag + H2O

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handout d & f-block Elements
(iii) The aqueous solution is strongly basic, solution behaving as AgOH. Moist silver oxide
hydrolyses the alkyl halide to alcohol.
C2H5Br + AgOH  C2H5OH + AgBr
(iv) Dry distillation of a mixture of alkyl halide with silver oxide produces ether.

2C2H5Br + Ag2O  C2H5 – O – C2H5 + 2AgBr
 Uses :
It is used :
 As Tollen’s reagent for the detection of aldehydes, formic acid and terminal alkynes.
 In the manufacture of mirrors.
Photography :
A photographic film consists of a light sensitive emulsion of fine particles (grains) of silver salts in
gelatine spread on a clear celluloid strip or a glass plate. The grain size is very important to
photographers, as this affects the quality of the pictures produced. AgBr is mainly used as the light
sensitive material. Some AgI is used in ‘fast’ emulsions.
The film is placed in a camera. When the photograph is exposed, light from the subject enters the
camera and is focussed by the lens to give a sharp image on the film. The light starts a photochemical
reaction by exciting a halide ion, which loses an electron. The electron moves in a conduction band
to the surface of the grain, where it reduces a Ag+ ion to metallic silver.
light
2AgBr(s)   2Ag + Br2
In modern photography only a short exposure of perhaps 1/100th of a second is used. In this short
time, only a few atoms of silver (perhaps 10–50) are produced in each grain exposed to light. Parts
of the film which have been exposed to the bright parts of the subject contain a lot of grains with
some silver. Parts exposed to paler parts of the subject contains a few grains with some silver,
whilst parts not exposed contain none. Thus the film contains a latent image of the subject. However,
the number of silver atoms produced is so small that the image is not visible to the eye.
Next the film is placed a developer solution. This is a mild reducing agent, usually containing
quinol. Its purpose is to reduce more silver halide to Ag metal. Ag is deposited mainly where there
are already some Ag atoms. Thus the developing process intensifies the latent image on the film so
it becomes visible. The correct conditions for processing must be used to obtain an image of the
required blackness.

2AgBr(s) + 2OH–(aq) + HO OH (aq)  2Ag(s) + 2H2O() + O O+

2Br–(aq)
hydroquinol hydroquinone
If the film was brought out into daylight at this stage, the unexposed parts of the emulsion would
turn black and thus destroy the picture. To prevent this happening any unchanged silver halides are
removed by placing the film in a fixer solution. A solution of sodium thiosulphate is used as fixer. It
forms a soluble complex with silver halides.
AgBr + 2Na2S2O3  Na3[Ag(S2O3)2] + NaBr
After fixing, the film can safely be brought out into daylight. Parts blackened by silver represent the
light parts of the original picture. This is therefore a negative.
To obtain an image with light and dark the right way round, a print must be made. Light is passed
through the negative onto a piece of paper coated with AgBr emulsion. This is then developed and
fixed in the same way as before.