D AND F BLOCK

ELEMENTS

High Yield Notes

 NOTES
D AND F BLOCK
ELEMENTS
TRANSITION ELEMENTS
Transition elements may be
defined as those elements which
have partially filled d or f-subshells
in the atomic state or in any of
their commonly occurring
oxidation states.
The D-block and the F-block
2 elements are called transition
elements because they are
located between the S and P-
block elements
Their properties are in
transition between the metallic
elements of the S-block and
nonmetallic elements of the P-
block.
NOTES
The coinage metals
Cu, Ag and Au are transition metals,
since Cu2+ has a 3d9 configuration,
Ag+2, 4d9 and Au+3, 5d8
configuration.
Inner and outer transition elements:
F- Block elements i.e. Lanthanides and
Actinides are also called inner
transition metals, whereas D-block
elements are called outer transition
metals.

Typical
Non
transition
typical transition elements
elements

Do not have a partially filled d-subshell

the remaining
either as elements or in any of their
transition
ionic state. Neither do they show typical
series except
properties of transition elements
group 2B and
to any appreciable extent (except complex
3B
formation)

Group IIB elements (Zn, Cd and Hg)

IIIB (Sc, Y and La)

PreMed.PK 1
 NOTES
PROPERTIES OF TRANSITION ELEMENTS

1. They are all metals in true

sense, some of which play
important role in industry, e.g.
Ti, Fe, Cr, Ni, Cu, Mo, W, Zr, Nb,
Ta, Th, etc.
2. They are all hard and strong
metals with high melting and
boiling points. They are also
good conductors of heat and
electricity.
3. They form alloys with one
another and also with other
elements.
4. With few exceptions, they show
2 variable valency or oxidation
state.
5. Their ions and compounds are
colored in solid state as well as
in solution form at least in one
if not all the oxidation states.

Melting Covalent
Binding
and boiling and ionic
energies
points radii

Transition metals show

Transition Changes in the
good mechanical properties.
ionic radii along the
They are tough, malleable metals have very
series
and ductile. The toughness high melting and are much less
of these metals indicate boiling points regular, so that
strong metallic binding.
due to strong periodic trends in
This is because, apart from
binding forces the properties of
s-electrons of the outer
these
most shell, the electrons of present between
ions are difficult
underlying half-filled d- their atoms. to rationalize
orbitals also
participate in binding.

PreMed.PK 2
 NOTES
PROPERTIES
Binding OF TRANSITION
Melting ELEMENTS
Covalent
and boiling
energies and ionic radii
points

Trends:
In moving from left to
right in any transition
series, the number of
unpaired electrons increases
up to groups VB
and VIB, after that
pairing takes place and
number of unpaired
electrons goes
on decreasing until it
becomes zero at group IIB.
2 Therefore, binding is
stronger up to group VIB
and weakens progressively
upto group IIB.
Trends: Trends:
Melting points The covalent radii decrease
increases up to rapidly at the start of
the series, then become
the middle of almost constant and
the series and then finally begin to increase
decrease to a at the end of the series.
minimum level at The increase in covalent
radii is possibly due to
the end of the
the fact that the filled 3d
series. This trend in orbitals have contracted
melting points into the electron core and
correlates well so shield the outer 4s
with the strength electrons more effectively
from the nucleus,
of binding forces

Example:
In the first transition
series, the general
increase in binding energy
ends at Vanadium. This is
due to changes in metallic Example:
Example:
structure, e.g. Mn . In the Ptb figure 6.2
Fig 6.3 ptb
third transition series, graph
the increase in binding
energy ends at Tungsten
when all the 5d electrons
contribute to binding

PreMed.PK 3
 NOTES
PROPERTIES
OxidatiOF TRANSITION ELEMENTS
Interst
Alloy
Paramagn itial
on Colour formatio
etism compo
state n
unds

In transition
elements, the d
orbitals are
responsible for
the color
development in
their
compounds.
When these
orbitals are
involved in
bonding, they
2 split up into
two energy levels,
When small
One set has a
Substances non-metal
higher energy
which are weakly atoms like Owing to the
than the other.
attracted by a H, B, C, N similarity in
The electrons
strong magnetic enter the their sizes,
residing in low
field are called They interstices some transition
energy
paramagnetic exhibit of metal atoms
d-orbitals
substances. transition are able to
variable absorb a part of
Those substances metals and replace one
valency the visible light
which are weakly impart another in the
oxidation and jump to
repelled by a useful metallic lattice
state. high energy d
strong magnetic features to and form
orbitals. This is
field are called them, they substitutional
called d-d
diamagnetic are called alloys among
transition.
substances. Interstitial themselves.
The energy
compounds
difference of d-
orbitals varies
from ion to ion.
Thus, every ion
absorbs a
different
wavelength and
transmits
the remaining
set of
wavelengths that
gives different
colors to the
ions.

PreMed.PK 4
 NOTES
PROPERTIES OF TRANSITION ELEMENTS
Interstit
Alloy
Paramagn Oxidation ial
Colour format
etism state compoun
ion
ds

Example:
All 3d series
elements show
an oxidation
state of +2 in
Cause: addition to
Paramagnetic higher
behavior is oxidation
caused by the states. Examples:
presence of Alloy steels
+2 oxidation
unpaired are an
state is
electrons in an important
2 atom, molecule shown when Example: In example of
or ion because only the [Ti(H2O)6]3+ this type of
there is a 2s electrons yellow light is material in
magnetic are involved in absorbed, which iron
moment bonding. In while most These are non- atoms are
associated with the highest of the blue stoichiometric substituted
the spinning of oxidation and red compounds. by
electron. lights are Sometime they Chromium,
states of the
It increases with transmitted, are also Manganese
first five
increase in the therefore termed as and Nickel
number of elements all the solution interstitial atoms, etc.
unpaired the s and d of alloys. to give the
electrons. electrons are [Ti (H20)6]3+ steel more
When the used for ions looks useful
electrons are bonding. After violet in properties.
paired in an Mn, the color. Other
orbital, then number of examples
magnetic are brass,
oxidation
moments are bronze and
states
cancelled coinage
out, and the decreases as alloys.
substances the d-
become subshells fill
diamagnetic. up and fewer
unpaired
electrons are
available for
bond
formation.

PreMed.PK 5
 NOTES
PROPERTIES OFOxidation
TRANSITION ELEMENTS Interstitial Alloy
Paramagnetism state
Colour
compounds formation

Example:
The paramagnetic behavior is
the strongest for Fe3+ and
Mn2+ and decreases on both
sides of the first transition
series. The reason is that both
Mn2+ and Fe3+ have 5 unpaired
electrons each. The number of
unpaired electrons decreases
gradually to zero on both side.

PreMed.PK 6
 NOTES
COMPLEX COMPOUNDS

Definition:
Compounds containing the
complex molecules or complex
ions and capable of
independent existence are
called coordination
compounds or complexes.
A complex compound may
contain
a. A simple cation and a
complex anion
b. A complex cation and a
simple anion
2
Example:
when the aqueous solutions of
Fe (CN)2 and KCN are mixed
together and evaporated, a
new compound is obtained,
which in aqueous solution does
not ionize as Fe2+ and CN ions
but ionizes as K+ ion and [Fe
(CN)6 ] 4- ion (Ferrocyanide
ion).
On this basis it has been given
a formula K4 [Fe (CN)6 ]. Here
[Fe (CN)6 ]-4 is called a
complex ion.

PreMed.PK 7
 NOTES
components description example

e.g. K4 [Fe(CN)6 ],
[Ag(NH3 ) 2 ]Cl
The atoms or ions or In the above examples, CN- and
neutral molecules, which NH3 are the anionic and neutral
surround the central ligands, respectively. Ligands
having two donor atoms are
metal ion and donate
ligand: called bidentate
electron pairs to it are ligands, e.g Oxalate ion is a
called ligands. They may bidentate ligand and its
be anions or neutral coordination
molecules, with the metal COO ion occur
through its both negatively
charged oxygen atoms

2
The number of lone pair
of electrons provided by
K4 [Fe(CN)6 ] ,
the ligands to the [Cu(NH3 ) 4 ]SO4
Coordination central metal atom or In the above examples, the
number: ion is called the coordination number of iron is
6 and that
coordination number of
of copper is 4.
the central
metal atom or ion,

The central metal atom

or ion alongwith ligands
K4 [Fe(CN)6 ] ,
is called the
[Cu(NH3 ) 4 ]SO4, [Ni(CO)4 ] In
coordination sphere.It the above examples,
Co ordination is usually placed in [Fe(CN)6 ] 4-, [Cu(NH3 ) 4 ] 2+
sphere: square brackets. It may and [Ni(CO)4 ] 0 are anionic,
cationic and
be
neutral coordination spheres,
anionic, cationic or respectively.
neutral,

[Fe(CN)6 ] 4- Charge on
It is the algebric sum iron = + 2 Total charge on
Charge on the
of the charges present six CN- ions = - 6
coordination
sphere: on the central metal Charge on the
ion and the total coordination sphere = -6 +
charge on the ligands, 2=-4

PreMed.PK 8
 NOTES Chelates:
When all the donor atoms of a
polydentate ligand get
coordinated with the same metal
ion, a complex compound is
formed which contains one or
more rings in its structure and
hence is called a Chelate.
Metal chelates are more stable
metal complexes.
When two oxalate ligands C2
O4 2- (bidentate ligand) get
coordinated with Pt2+ ion,
Dioxolane platinate (II) ion is
obtained.
Each oxalate ligand forms a
five-membered ring with the
cation.

PreMed.PK 9
 NOTES NOMENCLATURE OF COMPLEX
COMPOUNDS
Examples :
The nomenclature of complex
K4 [Fe(CN)6 ] Potassium
compounds is based upon the
ferrocyanide.
recommendations by the
[PtC1(NO2 )(NH3 ) 4 ]SO4
Inorganic Nomenclature
tetraamminechloronitroplatinum
committee of IUPAC.
(IV ) sulfate.
The rules for naming the complex
[CO (NO2 ) 3 (NH3 ) 3 ] Triammine
compounds are as follows.
trinitro-N-cobalt (III).
1. Cations are named before
anions.
Writing the formula of complex
2. In naming the coordination
compounds:
sphere, ligands are named in
In writing the formula of a
alphabetical order regardless of
complex ion, the usual practice is
the nature and number of
to place the symbol of the central
each, followed by the name of
metal atom first, followed by the
2 central metal ion.
formulas of the anionic ligands in
3. The prefixes di, tri, tetra, penta,
alphabetical order, then neutral
hexa, etc, are used to specify
ligands in alphabetical order and
the number of coordinated
the formula of the whole complex
ligands.
ion is enclosed in square brackets.
4. The names of anionic ligands
end in suffix O, e.g, hydroxyl,
Geometry of complexes:
(OH- ) carbonate (CO3 2-).
The geometry of complexes
5. The names of neutral ligands
depends upon the type of
are usually unchanged, e.g. for
hybridization taking place in the
NH3 , ammine and for H2O,
valence shell of the central metal
aqua. and for CO, carbonyl.
atom.
6. The suffix ‘ate’ comes at the
end of the name of metal if the
complex represents an anion,
otherwise it remains
unchanged.
7. The oxidation number of the
metal ion is represented by a
Roman numeral in parenthesis
following the name of the
metal.

PreMed.PK 10
 NOTES
CORROSION
Definition:
Any process of chemical decay of
metals due to the action of
surrounding medium is called
corrosion.
Explanation:
The simplest case of corrosion
occurs when metals come
into contact with gases of the
atmosphere. The surface of
metals becomes coated with
compounds such as oxides,
sulfides and carbonates. Such
compounds sometime form a
2 compact layer on the surface
protecting the metal from
further attack.
When the metal is in contact
with water. The compounds
formed in this case may
dissolve in water, allowing the
corrosion to penetrate further
into the metal. Besides
dissolving the compounds,
water also promotes
electrochemical process which
is one of the main causes of
rapid corrosion.
Electrochemical theory:
Pure metals are not easily
corroded, even iron hardly gets
corroded if absolutely pure. The
impurities present in the metal
promote corrosion.
Suppose, for instance, Cu is
brought in contact with Al. After
sometime, we will notice that
Aluminium gets corroded while
copper remains intact. This can be
explained by the electrochemical
theory.
PreMed.PK
According to this theory,
moisture and CO2 are present on
the surface of the metal. Water
ionizes into H+ and OH- ions. CO2
dissolves in water forming H2
CO3 which ionizes as follow
Copper and Aluminium are, in
a sense, immersed in the
solution containing H+, OH-
and HCO3 ions. This forms a
galvanic cell in which
Aluminium releases electrons
and changes to Al3+ ion (being
more reactive- than Cu) i.e it
acts as positive electrode and
Cu acts as a negative electrode.
Aluminium ions attract OH- ion
to form, Al (OH)3 i.e it starts
dissolving. The H+ ions present
on the Cu receive the electrons
and released as H2 . In this way,
Aluminium corrodes rapidly
when in contact with copper
which is lower in
electrochemical series. From
this, we can conclude that
when an active metal Al
(higher in the electrochemical
series) comes in contact with
less active metal Cu (lower in
the electrochemical series) a
galvanic cell is established. In
this process active metal
corrodes rapidly, while the
other remains intact.
11
 NOTES Prevention from corrosion
the amount of iron destroyed
each year by corrosion equals to
about one fourth of its annual
production. It is therefore
necessary to prevent such a
damaging process and avoid this
loss.
Different methods are used to
prevent corrosion.
The simplest of them consists
of protecting the surface of the
metal from coming in direct
contact with the surrounding
by coating it with oil, paint,
varnish or enamel.
It can also be prevented by
alloying the metals or by
coating the metal with a thin
2 layer of another metal.

PreMed.PK 12
 NOTES
PROPERTIES OF TRANSITION ELEMENTS

Chromates and Dichromate are

the salts of chromic acid, H2CrO4,
and dichromic acid, H2 Cr2 O7
respectively. Both acids exist only
in aqueous solution and when
attempts are made to isolate them
from solution they decompose
immediately into chromic
anhydride (CrO3 ) and water. Their
salts are, however, quite stable.

Potassium chromate:
Potassium chromate:
2 Potassium Di
Potassium Di chromate:
chromate:

Preparation:
1. The chromates of alkali metals, which
are soluble in water, are obtained by
Preparation:
oxidizing trivalent chromium compounds
1. K2 CrO4 is converted to K2
in the presence of an alkali.
2KCrO2+ 3Br2 + 8KOH → 2K2CrO4 + 6KBr
Cr2 O7 by using the above
mentioned equilibrium. In an
+ 4H2O
acidic medium, the
equilibrium will shift in the
2. Chromates can also be produced by
forward direction i.e
fusing Cr2 O3 with an alkali in the
changing chromate ions into
presence of an oxidant, such as potassium
dichromate ions.
chlorate.
Cr2O3+ KClO3+ 4KOH → 2K2CrO4 + KCl
2K2CrO4+ H2O4 →
K2Cr2O7 + K2SO4 + H2O
+2H2O

2. Sometimes sodium
3. Chromates are usually prepared from
dichromate is converted into
natural chromite ( FeO. Cr2 O3 ) if the
potassium dichromate by
latter is strongly heated with potassium
reacting it with KCl.
carbonate in the presence of oxygen. The
resulting fused mass will contain
potassium chromate, which can be
Na2Cr2O7+ 2KCl →
K2Cr2O7 + 2NaCl
extracted with water.
4FeCr2O4+ 8K2CO3+ 7O2
→
8K2CrO4 + 2Fe2O3 + 8CO2
PreMed.PK 13
 NOTES
Properties:
Almost all the chromates are yellow
in colour.
● Some of them are used as pigments.
●
For instance, insoluble lead chromate,
PbCrO4 , is employed for the
preparation of yellow oil color called
yellow crown.
2 ● K2 CrO4 and K2 Cr2 O7 show similar
properties because in an aqueous
solution Cr2 O7 2- and CrO4 2- ions
exist in equilibrium.
If an alkali is added to such a solution
the hydroxyl ions will bind the hydrogen
ion in solution, the equilibrium will
shift towards left and, as a result,
dichromate ions will be converted into
chromate ions. Similarly, on adding an
acid the equilibrium will shift towards
right and dichromate ions will be
formed.
PreMed.PK
Properties:
Physical properties:
It is an orange red crystalline solid which
melts at 396°C, it is fairly soluble in
water. Di-chromates are very powerful
oxidizing agents. Oxidation is carried out
in an acid solution. In this process,
hexavalent chromium ion is reduced to
trivalent chromium ion.
Chemical properties:
(a) Reaction with H2SO4 :
K2Cr2O7+ 4H2SO4 →
Cr[SO4]3 + K2SO4
+ 4H2O+3[O]
3[O]+ 3H2S 3H2O+3S
2Cr2O7+ 4H2SO4 +3H2S
→
Cr[SO4]3 + K2SO4 + 7H2O+3S
(b ) Reaction with Ferrous Sulfate:
Potassium dichromate oxidizes ferrous
sulfate to ferric sulfate in the presence of
sulfuric acid.
K2Cr2O7+ 7H2SO4 +6FeSO4
→
3Fe2[SO4]3 +Cr2[SO4]3+ K2SO4 + 7H2O
(c ) Reaction with Potassium Iodide:
Potassium dichromate also oxidizes KI in
the presence of H2 SO4,
K2Cr2O7+ 7H2SO4 +6KI
→
3I2 +Cr2[SO4]3+ 4K2SO4 + 7H2O
(d ) Chromyl Chloride Test:
When solid potassium dichromate is
heated with solid metal chloride in the
presence of concentrated sulfuric acid.
K2Cr2O7+ 7H2SO4 + 4NaCl
→
2KHSO4 + 2CrO2Cl2+ 4NaHSO4 + 3H2O
Uses .
K2 Cr2 O7 finds extensive use in dyeing.
It is used in leather industries for chrome
tanning.
It is used as an oxidizing agent.
14
 NOTES Potassium permanganate:
This compound is the salt of
permanganic acid, HMnO4 . It is an
unstable acid and exists only in
solution.
Preparation:
It is prepared by acidifying the
solution of potassium
manganate, K2 MnO4 by H2
SO4.
3K2MnO4+ 2H2SO4 →
MnO2+2KMnO4+ 2K2SO4 + 2H2O
On a large scale it is prepared
from the mineral pyrolusite,
MnO2 . The finely powdered
mineral is fused with KOH in
the presence of air or an
oxidizing agent like KNO3 or
KClO3 , etc. This treatment
2 gives us green colored
potassium manganate,
K2 MnO4 , in fused state.
2MnO2 + 4KOH+ O2 →
2K2MnO4 + 2H2O
MnO2 + 2KOH+ KNO3 →
K2MnO4 + KNO2 +H2O
3MnO2 + 6KOH+ KClO3 →
3K2MnO4 + KCl + 3H2O
The fused K2 MnO4 obtained as
above is extracted with water and
the solution, after filtration, is
converted into potassium
permanganate (KMnO4 ) by any of
the following methods.
(b) In this process CO2 is passed
though the green solution of K2
MnO4 until it becomes purple.
3K2MnO4+ 2H2O + 4CO2 →
MnO2+2KMnO4+ 4KHCO3
(c) Electrolytic Oxidation Process
In this process, manganate is
converted to permanganate by
electrolytic oxidation. During
electrolysis of an aqueous solution
of K2 MnO4 , water is decomposed
to evolve Hydrogen gas at the
cathode and Oxygen gas at the
anode. Oxygen liberated at the
anode oxidizes manganate ion
(MnO4 ) 2- into permanganate ion
(MnO4 ) 1-, while Hydrogen is
liberated at the cathode.
2K2MnO4+ H2O + [O] → 2KMnO4+
2KOH
The purple solution of KMnO4 ,
obtained as above is filtered
through asbestos, concentrated
and allowed to crystallize when
KMnO4 deposits as deep purple-
red rhombic prisms.

(a)Stadeler’s Process
In this method Cl2 is passed
through the green solution of
K2 MnO4 until it becomes purple
due to the formation of KMnO4 .
Here, Cl2 oxidizes K2 MnO4 into
KMnO4 .

2K2MnO4+ Cl2 → 2KCl +2KMnO4

PreMed.PK 15
 NOTES Properties of KMNO4:

Physical
Chemical properties:
properties:

(a ) Reaction with H2S: It oxidizes H2S to sulfur.

2KMNO4+ 3H2SO4 →
2MnSO4 + K2SO4 + 3H2O+5[O]

5[O]+ 5H2S → 5H2O+5S

2KMNO4+ 3H2SO4 +5H2S
→
2MnSO4 + K2SO4 + 8H2O+5S

2
(b ) Reaction with FeSO4 It oxidizes FeSO4 to Fe2 (SO4 )3.

2KMnO4+ 3H2SO4 +5H2C2O4

● →
Potassium permanganate K2SO4 +2MnSO4 + 5Fe[SO4]3+ 8H2O
forms dark purple lustrous
crystals giving deep pink color
in solution.
● (c ) Reaction with Oxalic Acid It oxidizes oxalic acid to CO2 and
Its solubility in water at
H2O.
20°C is only about 7%, while it
dissolves more at higher
temperature (25% at 63°C). 2KMnO4+ 7H2SO4 +6FeSO4
● →
Potassium permanganate is
a powerful oxidizing agent. K2SO4 +2MnSO4 + 10CO2 + 8H2O
Oxidation is usually carried
out in an acid solution. (d ) Reaction with KOH When an alkaline solution of KMnO4 is
heated, O2 is evolved.
2KMnO2+ 4KOH
→
4K2MnO4 +2 [O] + 2H2O

Uses :
It is used
• as an oxidizing agent.
• as a disinfectant and as a germicide.
• in the manufacture of many organic compound

PreMed.PK 16
 NOTES Stainless steel:
Steel is an alloy of iron containing
0.25 to 2.5% of carbon and traces of
S, P, Si and Mn.
Classification of Steel
1. Mild Steel (0.1 - 0.2 % C) It is
fairly soft, malleable and
ductile, can be forged (shaped
by hammering and pressing
while hot). It is used in making
tubes, nuts, bolts, bars and
boiler plates.
2. Medium Carbon Steel (0.2 -
0.7 % C) It is harder than mild
steel. It is also malleable and
ductile. It is used in making
rails, axles, castings.
3. High Carbon Steel(0.7 -1.5 %
C) It is hard and can be forged,
2 when containing less than 1.0%
carbon. Steel containing more
than 1.0% carbon cannot be
forged. It is used to make
hammers, taps, dies, cutting
tools, machine tools, hard steel
parts of machinery and all sort
of engines. Steel is
intermediate in carbon
content between cast iron and
wrought iron.
It can be produced from: (i) Cast :
iron by removing some carbon
along with Sulfur, Phosphorus and
Silicon. (ii) By adding the required
amount of carbon to wrought iron,
then adding some special
constituents, e.g. Tungsten,
Chromium, Vanadium,
Molybdenum, Manganese, Nickel
and Cobalt which impart desired
properties to the steel. At present
most of the steel is manufactured
from cast iron.
PreMed.PK
Manufacture of Steel.
In can be manufactured by the
following processes.
Open hearth process ( using
cast iron, wrought iron or steel
scrap)
Bessemer’s process (using cast
iron only) Some other
processes are also used to
prepare special type of steel
from pure wrought iron.
Open Hearth Process
This is the most modern method
for the manufacture of steel. It is
carried out in an open hearth
furnace. This furnace has a low roof
to deflect the hot gases and flames
downward to melt the charge. The
open hearth furnace works on the
regenerative principle of heat
economy.
Open hearth process is of two
types.
1. Furnace with acidic lining like
SiO2 is used when the impurities
are Mn, Si ,etc.
2. Furnace with basic lining like
dolomite (CaO , MgO ) is used
when the impurities are P and S,
etc.
Bessemer's Process :
The furnace used in this process is
called Bessemer's Converter which
is a pear-shaped vessel made of
steel plates. At the bottom the
converter is provided with a
number of holes through which
hot air can be introduced. The
converter is held on a central axis
so that it can be tilted in any
desired position for feeding and
pouring out the finished materials.
17
 NOTES Tin plating:
The process of tin plating
consists of dipping the clean
sheet of iron in a bath of molten
tin and then passing it through
hot pair of rollers.
Such plates are used in the
manufacture of tin canes, oil
containers and other similar
articles.
Tin itself is very stable and
protects the metals effectively
as long as its coating on the
Iron is intact.
If the protective coating is
damaged, then Iron comes into
contact with moisture.

Galvanic cell establishment:

2 A galvanic cell is established in
which tin acts as a cathode and
Iron as an anode.
The electron flow from
Iron to Tin, where they discharge
H+ ions, leaving behind OH- in the
solution.
These hydroxide ions react with
iron forming Fe(OH)3 , which
dissolves rapidly in water.
From this, it can be concluded
that plated iron gets rust more
rapidly when the protective
coating is damaged than the
non-plated iron.

PreMed.PK 18