SHRI RAM GLIBAL SCHOOL , GOMTINAGAR
CLASS- XII
SUBJECT- CHEMISTRY
CHAPTER - d&f BLOCK ELEMENTS
PART-1
d –Block elements and transition metals
The elements lying in the middle of periodic table belonging to groups 3 to 12 are
known as d – block elements.The position of d-block elements are in between
s−block and p−block elements in periodic table. These d-block elements are called
transition elements because they exhibit transitional behavior between s− and
p−elements. Their properties are transitional between highly reactive metallic
elements of s−block which are typically ionic compounds and elements of p−block
which are large - covalent
The general electronic configuration of d-block elements is (n −1)d1-10 ns1-2, where (n
−1) stands for the inner d orbitals and n = 4,5 and so on.
The d-block elements having incompletely filled d-subshell are called transition
metals.Zinc, cadmium, mercury having the general electronic configuration as (n
–1)d10 ns2, are not regarded as transition metals due to completely filled d –
orbital.
There are mainly three series of the transition metals:
• 3d series starts with Sc (Z = 21) and ends with Zn (Z = 30)
• 4d series starts with Y (Z = 39) and ends with Cd (Z = 48)
• 5d series starts with La (Z = 57) and ends with Hg (Z = 80)
Metallic character
Almost all the transition elements display metallic properties such as metallic luster,
high tensile strength etc.They have high enthalpy of atomisation because of
unpaired electrons.
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Atomic and ionic radii
Due to the addition of a new electron to a
d-orbital each time the effective nuclear
charge increases which causes the atomic
radii to decrease in a series in the starting of
series. However, in the middle of series the
atomic size of Fe, Co, Ni is almost the same
because the attraction due to increase in
nuclear charge is cancelled by the
repulsion because of increased shielding
effect. At the end The atomic size increases
because of interelectronic repulsion.
The size of the 4d series elements is almost the same as the size of the 5d series
elements. This phenomenon is associated with the intervention of the 4f orbitals
which must be filled before the filling starts in 5d subshell.This phenomenon is
known as Lanthanoid contraction
Lanthanoid contraction
The filling of the 4f (having poor shielding effect) before the 5d orbital results in a
regular decrease in size called lanthanoid contraction. This compensates for the
expected increase in the atomic size with increasing atomic number. The net result
of the lanthanoid contraction is that the 4d and 5d series elements exhibit similar
radii and show similarity in their physical and chemical properties.
Melting point
Due to the strong interatomic bonding
which involves both (n−1)d and ns
electrons participation, transition metals
have high melting points.In any row,
the melting point of these metals rises to
a maximum at d5 and after that as the
electrons start pairing up so the melting
point decreases regularly as the atomic
number increases with an exception of
Mn and Tc are exception.
2
Ionization enthalpy
In a particular transition series, there is an increase in ionization enthalpy from left to
right which is due to the increase in effective nuclear charge along a series. But the
trend is not very regular. The exceptions are chromium and copper which have
notably larger ionization enthalpy than their neighbours. These exceptions are
due to the extra stability associated with the half-filled and fully-filled set of
d-orbitals.
PART-2
Oxidation States
● Transition metals show variable oxidation states due to tendency of (n-1)d as
well as ns electrons to take part in bond formation because they have a little
distinction in energies. Both energy levels can be utilized as a part of bond
formation.
● The most common oxidation state of 3d series is +2 with the exception of
scandium, because of the loss of two ns electrons. This demonstrates d
orbitals are more stable than s orbitals after scandium.
● The oxidation condition of a metal in solvents relies upon the solvent's nature.
For instance, Cu in +1 state in water is unstable as it might experience
oxidation while Cu in +2 states is stable.
● The elements in the start of the series display less oxidation state in view of
having smaller number of electrons to lose or contribute. The elements amidst
the series demonstrate the best number of oxidation. For instance; Mn
demonstrates all the oxidation states from +2 to +7.
● The most elevated oxidation state appeared by any transition metal is eight
which is demonstrated by Ru and Os.
Formation of complexes
The transition metals form a large number of complexes. This is due to their
● Comparatively small sizes of the metal ions
● High ionic charges.
● Availability of vacant d atomic orbitals
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Formation of coloured compounds
Transition metals and their compounds show colour. The colour is due to the
excitation of electron from one d atomic orbital to higher energy d atomic orbital
in the same subshell.This process is called d-d-transition
The frequency of the light absorbed generally lies in the visible region. The colour
observed is due to the colour of the complementary light. The colour is due to the
presence of unpaired electrons. All Zn2+ compounds are colourless.
Formation of interstitial compounds
Transition metals have lattice structure in which the unoccupied space is called
void or hole or interstices. Transition metals entrap smaller but electronegative
elements in these interstices and results in the formation of interstitial compounds.
Interstitial compounds have high melting points, hardness and retain metallic
conductivity. The interstitial compounds are chemically inert. Examples are TiC,
steel.
Formation of alloys
Alloy is a homogeneous mixture of two or more metals. Due to the comparable
size of transition metals, one metal can displace other metal in the crystal lattice
and this results in the alloy formation. The alloys so formed are hard and have high
melting points. The best known are ferrous alloys; chromium, vanadium, tungsten,
manganese are used for the production of a variety of steels and stainless steels.
PART-3
Catalytic properties
Most of transition metals are used as catalysts.This is due to the
(i) presence of incomplete or empty d-orbitals,
(ii) large surface area and
(iii) variable oxidation state. For example Fe, Ni, V2O3 etc are used as catalyst
Oxide Formation
Transition metals form oxides on reaction with oxygen at elevated temperature.
Transition metal form oxide in oxidation state of + 1 (in Ag2O) to + 7 (Mn2O7) to + 8
(in OsO4). As the oxidation number increases in case of same elements,
(a) The covalent character of oxides increases.
(b) The acidic strength of the oxides increases.
(c) The oxidizing power of oxides increases.
4
Magnetic Properties
Most of the transition elements show paramagnetic behavior. The unpaired
electrons in (n-1) d orbitals are responsible for the magnetic properties.Substances
that are attracted by the magnetic field and are called paramagnetic. This
phenomenon is called paramagnetism. Paramagnetic property is only shown when
the substance contains one or more unpaired electrons. When a substance
acquires a permanent magnetic moment, it is known as ferromagnetic and the
phenomenon is called ferromagnetism. On the other hand, substances which are
repelled by magnetic field and are called diamagnetic substances. A substance
shows diamagnetism when it contains only paired electrons.
The magnetic character of a substance is expressed as a magnetic moment. The
magnetic moment can be calculated by
μ = √{n(n + 2)} BM (Bohr Magneton)
where, n = number of unpaired electrons.
PART-4
POTASSIUM DICHROMATE
Potassium dichromate is an important chemical used in industries as an oxidizing
agent and for the preparation of many other compounds
Preparation : By chromite ore
4FeCr2O4 + 8Na2CO3 + 7O2 → 8Na2CrO4 + 2Fe2O3 + 8CO2
2Na2CrO4 + 2H+ → Na2Cr2O7 + 2Na+ + H2OH2O
Na2Cr2O7 + 2KCl → K2Cr2O7 + 2NaCl
(Orange colour)
Structure of chromate and dichromate ion
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Properties
● Potassium dichromate is used as a primary standard in volumetric analysis
and as an oxidizing agent. In acidic medium, the oxidation state of Cr changes
from + 6 in Cr2O72- to + 3 in Cr3+
● On heating potassium dichromate decomposes to form potassium chromate,
chromic oxide and oxygen.
4K2Cr2O7 → 4K2CrO4 + 2CrO3 + 3O2
POTASSIUM PERMANGANATE
Preparation
2MnO2 + 4KOH + O2 → 2K2MnO4 + 2H2O
3MnO42-+ 4H+ → 2MnO4- + MnO2 + 2H2O
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Structure of manganate and permanganate ion
Properties
The solution under examination loses its pink color once all the permanganate ions
are used up in the reaction. It suggests the end of the reaction and therefore a
self-indicator is called potassium permanganate, as it serves as an indicator apart
from being one of the reactants.
Potassium permanganate acts as a strong oxidizing agent in acidic, neutral or faintly
basic medium.
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PART-5
f - block elements
The elements in which the differentiating electron enters the penultimate energy
level i.e. (n−2)f, are called f-block elements. Due to such electronic configuration
where the last electron enters the 4f or 5f orbitals that are lower than the outermost
electrons, f-block elements are also named as inner transition elements.
Depending upon the fact whether the last
electron enters the 4f or 5f-orbitals, f-block elements are differentiated into
lanthanoids and actinoids.
Exceptions :
● Lu3+ ions do not show any colour due to the absence of any unpaired
electron in the 4f subshell which is fully filled.
● Cerium shows +4 O. S. Because of extra stability of 4f0 configuration.
● Europium shows +2 O. S Because of extra stability of 4f7 configuration.
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Formation of alloys: Lanthanoids are all used in the steel industry for making alloy
steels. Important and well-known alloy is misch-metal and it con-sists of
lanthanoid (90-95%), iron (4-5%) and trace amounts of S, C Ca and Al.
Lanthanide contraction
Lanthanoid contraction, also called lanthanide contraction,, the steady decrease in
the size of the atoms and ions of the rare earth elements with increasing atomic
number from lanthanum (atomic number 57) through lutetium (atomic number 71).
For each consecutive atom the nuclear charge is more positive by one unit,
accompanied by a corresponding increase in the number of electrons present in the
4f orbitals surrounding the nucleus. The 4f electrons very imperfectly shield each
other from the increased positive charge of the nucleus, so that the effective
nuclear charge attracting each electron steadily increases through the
lanthanoid elements, resulting in successive reductions of the atomic and
ionic radii.
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