d-& f Block elements

• The element in which last electron enters into the d-subshell of

penultimate shell are called d-block elements.
• The elements of d-block of the periodic table are known as
transition elements. The general electronic configuration of
transition elements is (n − 1)d 1−10ns1−2
• Transition elements posses partially filled d-orbitals in their
elementary form or in their ions existing in chemically significant
oxidation states. Hence Zn, Cd, and Hg are not regarded as
transition elements due to absence of partly filled d-orbitals in
their commonly occurring ions.
• Atomic radii and ionic radii
The decrease in atomic radii is small compared to the S and
P block elements. This is due to the screening effect caused by the
electrons of the (n-1)d subshell on the outermost shell. ... Thus,
for ions of a given charge the radius decreases slowly with increase
in atomic number.
Metallic character
almost all transition elements exhibit typical metallic properties like
metallic lustre, malleability, ductility, high tensile strength etc
(Malleability is the quality of something that can be shaped into
something else without breaking)
Ductile-capable of being shaped or bent or drawn out

Malleable (very thin layers we can made)

Sonorous (good sound –Bells)
Ductile (thin rings we can made)
Lustrous (Shining- due to loosely held electrons)
Density:
➢ Density of transition metal is higher than S-block metals.
➢ Down the group density decreases as size increases.
➢ Osmium and Indium has high density in the periodic table.
➢ Zn is having less density than copper. Due to Zn is having
greater size than copper.
 Ionization Enthalpy
• The ionization of transition elements are quite high and lies
between s-block and p-block elements.
• The first ionization energy increases with increase in atomic
number across a given transition series .
• Zn, Cd and Hg have very high IE1 due to the fully filled electronic
configuration.
• IE2 Cr>Mn & Cu>Zn
 Enthalpy of atomization
➢ Heat of atomization: Enthalpy change when a compound s bonds
are broken and the component atoms are reduced to individual
atoms.
➢ Cr has highest heat of atomization among 3d series
➢ Enthalpy of atomization is depends upon number of unpaired
electrons.
➢ Heat of atomization is similar to melting point.
 Melting point
➢ Group – 6 has highest melting point
➢ 3d-Cr
4d-Mo
5d-W
More enthalpy of atomisation, then more melting point
Down the group melting point increases
Highest melting point in periodic table Tungstun(W)
 Oxidation states
• The most common oxidation state of elements of first transition
series is +2, due to loss of two 4s electrons.
• The highest oxidation state shown by transition element is +8.
hence transition metal shows variable valency.
• The bonds formed in +2 and +3 oxidation state are generally ionic,
whereas other are covalent.
 Formation of colored compounds
• The transition metal ions possessing one or more unpaired
electrons, absorbs energy of suitable wavelength, from the light
falling on it and gets promoted from lower energy d-orbitals to
higher energy d-orbital, this is known as d-d transition.
• The transition metal ions having completely filled d-orbitals
(e.g.Zn+2, Cu+) and completely vacant d-orbital are colourless(eg.
Sc+3)
• Most of the compounds of transition metals are coloured both in
solid state and in aqueous solution, due to d-d transitions taking
place between splitted d-orbitals of unpaired electrons.
 Colour’s of Oxideds
➢ Fe2O3→red brown
➢ Cr2O3→Greeen
➢ Al2O3→white (Dirty)
➢ V2O5→Amphoteric

MnO  MnO2  Mn2O7 ( Acidicnature)

➢ When metal ‘Fe’ is reacts with a strong acid then reaction stops
some time. Explain.
Fe ⎯⎯ ⎯⎯→ Fe2O3 (Ferric oxide)
concHNO3

A protective layer of Fe2O3 forms which do not react with acid

prevent the contact of ‘Fe’ with acid. Thus reaction stops.
➢ When ‘Al’ is reacted with some oxidizing agent then reaction stops
after some time. Explain
Al ⎯⎯→
( 0)
Al2O3 (Corrundum)
Very hard
Magnetic properties
• Due to unpaired electrons in d-orbital, many compounds of
transition elements are paramagnetic in nature. As the number of
unpaired electrons increases, paramagnetic character increases.
Where as, the presence of paired electrons causes diamagnetic
character in elements and their compounds .
• Ferromagnetism as in iron is due to maximum number of unpaired
electrons.
• Iron is the much more paramagnetic than rest of the elements due
to more number of unpaired electrons. It is used to prepare
permanent magnets.
 Complex compounds

The tendency to form complex ions or compounds is due to i) small

size ii) high charge on the transition metal ions
iii) Availability of vacant d-orbital’s
Catalytic property
Most of the transition metals and their compounds act as a catalyst
because of the variable oxidation states and the presence of
vacant d orbital's, and large surface area of transition metals also
attributes to their catalytic property.

Alloy formation
A large number of alloys are formed due to their similar atomic size.
Alloys so formed are very hard with high melting points.
Eg: brass(Cu+Zn),
bronze (Cu+Sn),
Gunmetal/Bell metal (Cu+Zn+Sn)
stainless steel (Fe+Cr+Ni+C)
 Lanthanide contraction
➢ On moving from Ce to Lu in lanthanide series, the size of the atoms
and ions decreases regularly. The 4f orbital's containing electrons
are too diffused to screen the nucleus for the as effectively as the
more localized inner shell. Hence the attraction of the nucleus for
the outermost electrons increases steadily with increase in atomic
number. 4f orbitals having poor shielding effect.
➢ Thus, due to imperfect shielding of 4f electrons, a contraction in
the electron cloud of 4f-subshell increases.
 Metallurgy
Metallurgy : The large scale processes involved in the extraction of
pure metals from their respective ores is called Metallurgy.
Mineral : The compounds of various metals found in nature
associated with their earthly impurities are called minerals.
Ore : The naturally occurring minerals from which metals can be
extracted profitably and conveniently are called ores.
Matrix: The rocky impurities including silica (Sio2), mud etc
associated with the ore is called matrix or gangue.
Flux: flux is a substance added to the ore to remove the
impurities(gangue). It combines with gangue to form slag.
FeO + SiO2 → FeSiO3
gangue Flux slag
 Metallurgy of Aluminium (Al)
Aluminium is mainly extracted from its ore bauxite, Al2O3.2H 2O
1. Refining of oxide:
i) Bayer’s process:
• This process is used when bauxite contains a higher percentage of
iron oxide.
• The finely powdered ore is first roasted at low temperature to
convert any ferrous oxide in to ferric oxide.
• It is digested with hot concentrated solution of caustic soda at
423K under pressure when Aluminium oxide passes into the
solution as NaAlO2, ferric remains undissolved.
• some silica present as an impurity also dissolves in sodium
hydroxide to form sodium silicate (NaSiO3). The solution is then
filtered and ignited to get pure alumina.
 Al2O3 .2 H 2O + 2 NaOH → 2 NaAlO2 + 3H 2O
SiO2 + 2 NaOH → Na2 SiO3 + H 2O
The complete process can be represented as

Bauxite ore → to convert FeO into Fe2O3

1500 C hydrolysis
80atm in. presence.of .H 2O
Roasted .ore + NaOH → NaAlO2 → Al (OH ) 3 + NaOH
1473K
2 Al (OH ) 3 → Al2O3 + 3H 2O
 Hall’s process
• In this process, bauxite is fused with Na CO to give sodium meta
2 3

aluminate. The fused mass is then extracted with water in which

Fe2O3 and SiO2 remains insoluble as impurity.
Extracted.with.water warmed
fused
Al2O3 .2 H 2O + Na2CO3 → 2 NaAlO2 → NaAlO2 + Fe2O3 →
ppt
CO2 .is.circulated → Al (OH )3 → Al2O3 + 3H 2O
ppt pure

Reaction would be
2 NaAlO2 + CO2 + 3H 2O → Na2CO3 + 2 Al (OH )3 
1473k
2 Al (OH )3 → Al2O3 + 3H 2O
Serpeck’s process: this process is used when the bauxite ore contains
a higher percentage of silica as impurity. This process can be
represented as
18000 C 3H 2O
Bauxite.ore + nitrogen( N 2 ) + coke(C ) → AlN → Al (OH ) 3  + NH 3 
ppt

Silica (SiO2) as an impurity gets reduced to silicon which being volatile

escapes as vapour while Al (OH ) decomposes on ignition to give
3

pure alumina.
1473k
2 Al (OH )3 → Al2O3 + 3H 2O
Electrolytic reduction
Electrolyte Al2O3 dissolved in cryolite ( Na3 AlF6 ) and fluorspar (CaF2)
in the ratio of 1:2:1. this fused mixture lowers the melting point of
alumina and increases the electrical conductivity.

The electrolysis is carried out in an iron tank lined with carbon which
acts as cathode while the carbon rods act as anode and these are
dipped in fused electrolyte ( Al2O3 + Na3 AlF6 + CaF2 ) . A high density
current is passed through the electrolyte.
The aluminium metal obtained at.catode. Al +3 + 3e − → Al
is about 99% pure. at.cathode.C ( s ) + O 2 − → CO + 2e −
C ( s ) + 2O 2 − → CO2 + 4e −
 Electrolytic Refining
• It is done by Hoop’s method using electrolytic cell in which pure
aluminum acts as a cathode and impure aluminum acts as anode.
• Cathode present at upper layer and anode present at lower layer.
The middle layer consists of a mixture of fluorides of Na, Ba and Al
that acts as an electrolyte.
• On passing electric current, aluminum ions from the fused
electrolyte pass into upper most layer and get discharged. Pure
aluminum gets collected in this layer.
Properties:
When alumina and coke with current of chlorine is heated, aluminium
chloride and carbon monoxide is formed.
Al2O3 + 3C + 3Cl2 → 2 AlCl3 + 3CO

Uses:
House hold utensils, foils, wire’s coils and paints
Metallurgy of Zinc
Ores: Zinc blende(ZnS), calamine(ZnCO3), Zincite(ZnO)
Extraction
a) Roasting and Calcination


2ZnS + 3O2 → 2ZnO + 2SO2 (roasting)

ZnCO3 → ZnO + CO2 (Calcination)

b) Reduction of ZnO
The roasted ore is heated with coke to about 11000 C
ZnO + C → Zn + CO
ZnO + CO → Zn + CO2

Electrolytic refining
The metal obtained contains iron, cadmium, antimony, arsenic, etc as
impurities. Electro refining of zinc is carried out to obtain very pure zinc.
In this process ZnSO4 serves as electrolyte, crude zinc acts as anode and
cathode is plates of pure zinc.
Metallurgy of iron (Fe)
Ores ; magnetite (Fe3O4), haematite(Fe2O3), iron pyrite(FeS2)
Extraction
a) Calcination
Fe2O3 .3H 2O → Fe2O3 + 3H 2O
FeCO3 → FeO + CO2
4 FeO + O2 → 2 Fe2O3
b) Smelting: extract (metal) from its ore by a process involving
heating and melting.
Calcined ore+ limestone + coke (blast furnace)
Calcined means reduce.
Reduction zone: 3Fe O + CO → 2 Fe O + CO
2 3 3 4 2

Fe3O4 + CO → 3FeO + CO2

FeO + CO → Fe + CO2
Pig iron: This form of iron is obtained from blast furnace. It contains
approximately 4% carbon and other impurities(S, P,Si, Mn,etc) in
small amounts.
Cast iron: this form of iron is formed by melting pig iron with scrap
iron and coke using hot air blast. It has slightly lesser carbon
content. It extremely hard and brittle.
Iron to be melted again and reworked.
Copper extracted from copper pyrites:
• Copper pyrites cocentrated by froth floatation
• Concentrated ore is subjected to roasting to remove moisture and
volatile impurities. Then Cu2S and FeS are formed
Cu2 S .Fe2 S3 + O2 → Cu2 S + 2 FeS + SO2

• Roasted ore is mixed coke and sand(flux), subjected to smelting in

blast furnase, then FeS is partly eliminated as FeSiO3 (slag). The
product of the blast furnace consists most of
Copper extracted from copper pyrites:
Crushing and Concentration:
The ore obtained from mines are broken down into small piece by
jaw crusher and then pulverized. The ore being sulphide ore is
concentrated by froth floatation process. Pulverized ore is kept in
water containing pine oil and the mixture is agitated by passing
compressed air. Ore forms froth with pine oil and comes to the
surface and is skimmed off while impurities are left in water.
The concentrated ore is heated in excess supply of air on the
Hearth of reberberatory furnace below its melting point. The
different changes during roasting are:
a. Moisture and volatile impurities are driven out.
b. Non-metallic impurities like sulphur, phosphorous, arsenic etc.
are removed as their oxides.
S + O2 → SO2
P4 + SO2 → 2P2O5
c. Copper pyrite dissociates into individual sulphide
2CuFeS2 + O2 → Cu2S + 2FeS + SO2
Small amount of metal sulphides are oxidized to oxides.
2FeS + 3O2 → 2FeO + SO2
2Cu2S + 3O2 → 2CuO + 2SO2
Smelting
The roasted ore, coke and silica (flux) is charged a water jacketed
blast furnace when hot air is passed into blast furnace. Fes if oxidized
to FeO which combines with S 1O2 to form ferrous silicate as slag.
2FeS + 3O2 → 2FeO + 2SO2
FeO + S1O2 → FeS1O3
Flux Ferrous Silicate
 As long as Fes is present in the mixture Cu2O can’t be formed as
copper has higher affinity for sulphur than oxygen. In molten state
FeS & Cu2S are miscible and the molten mixture of Cu 2S and FeS is
called copper malte. The lower end of blast furnace has two
openings for slag and copper matte.
Bassemerisation
The molten matte is mixed with little silica and charged into
a Bessemer converter. Lined internally by basic lining of CaO or MgO.
Hot air is blown into the mixture which converts remaining FeS. To
FeSiO3.
2FeS + 3O2 → 2FeO + 2SO2
FeO + SiO2 → FeSiO3 (slag)
The slag is removed and air is passed. The air oxidized Cu 2S partially
to Cu2O which then reduces remaining Cu2S to metallic copper.
During this process no external reducing agent is used so it is an
example of self-reduction.
2CuS + 3O2 → 2Cu2O + 2SO2
2Cu2O + Cu2S → 6Cu + SO2
The reaction is highly exothermic and copper obtained is in molten
state. During solidification, SO2 escapes forming blisters on the
surface of metal. This variety of copper containing about 2% of
impurity is blister copper.
Metallurgy of silver(Ag)
Ores: Argentite(silver glance) Ag2S, Horn silver AgCl
Extraction:
Cyanide process: The extraction of silver is mainly done from the ore
argentite by a process known as Mac Arthur-Forrest cyanide
process.
This process is based on the principle that silver dissolves in a dilute
solution of sodium cyanide to form a soluble complex sodium
argento cyanide.
Silver can be obtained from this complex by the addition of scrap zinc.
Ag 2 S + 4 NaCN  2 Na[ Ag (CN ) 2 ] + Na2 S
2 Na[ Ag (CN ) 2 ] + Zn → 2 Ag  + Na2 [ Zn(CN ) 4 ]
sodium tetra cyano zincate(II)
Electrolytic Refing (Moebius Process)
Cathode: Pure silver sheet
Anode: Impure silver block
Electrolyte: Silver nitrate solution

At.cathode : Ag + + electron(e − ) → Ag ( pure.silver )

− +
at. Anode : Ag − e → Ag

Uses:
Silver plating, ayurvedic medicine, dental amalgam