D – block

Introduction
All the transition elements are metals, Nowadays many of the d block metals are used as construction
materials. Nine of the elements are essential for life and compounds of the d-block elements are used as
catalysts, pigments and medicines. The d-block consists of the elements in group 3-12 of the periodic
table. These elements are also known as the transition metals. f-- block elements are called as inner
transition metals. Here only the d-block elements will be considered for discussion Generally, the d-
block elements become more electronegative from left to right across a period. Definition of transition
element: According to the IUPAC, whose atom has partially filled d orbitals is said to be transition
element. d- block elements are classified into four transition series.

They are The first transition series: Scandium to Zinc.

The second transition series: Yttrium to Cadmium.

The third transition series: Lanthanum and Hafnium to Gold.

The fourth transition series: Actinium to leutacium, which is incomplete at present.

The elements in the periodic table are arranged together in blocks according to their outer electronic
configurations. The elements with a half-filled or fully-filled outer s orbital comprise the s block
elements. Similarly, the elements with a partly filled or fully filled outer p orbitals comprise the p-block
elements. The elements between these two blocks that is, between the groups 3 and 12 in the periodic
table have at most two electrons in the outermost s orbital, and incompletely filled d-orbitals next to
outermost orbital. These elements in which successive addition of electrons takes place progressively in
the inner d-orbitals are called as d- block elements. Similarly, the elements in which filling up of
electrons takes place in inner to inner f-orbitals are known as f-block elements.

Catalytic properties: Definition of Catalyst. A catalyst is a substance that speeds up a chemical reaction,
but is not consumed by the reaction; hence a catalyst can be recovered chemically unchanged at the
end of the reaction it has been used to speed up, or catalyze. Transition metals have high catalystic
activity both as metals in heterogenous catalysis and as ions in homogenous catalysts in solutions.It is
likely that the 3 d electrons enable the transition metal catalysts to form temporary bonds with the
reaction molecules in heterogenous catalysis. In homogenous catalysis the existence of a varity of
oxidation states for each element explains how the transition metals is able to take part in a sequence of
reaction stages and emerge un-changed at the end. This activity is described to their ability to exhibit
multiple oxidation states and to form complexes, alloys and forms transition compounds. One of the
most popular example these days is the heterogeneous catalyst used in car exhausts. The transition
metals and their compounds show catalytic activity in a variety of chemical processes.

Atomic Size: In general, in a given period the atomic size of the transition metals decreases from left to
right, but the change is not as significant as observed for the main-group elements. Atomic size
decreases from Sc to Mn but then levels out. In groups, the period 5 transition metals are larger than
the period 4 transition metals but are the same size or only slightly smaller than the period 6 transition
metals. The size of a transition metal is determined by the size of the ns orbital, the highest energy filled
atomic orbital for a transition metal.

Ionization Energy Definition: The amount of energy required to remove an electron from a neutral atom
in the gas phase is said to be Ionization Energy Periods: In a given period IE generally increases as we
move from left to right across the periodic table, because of increasing effective nuclear charge Groups:
In a given group from top to down decreases, because of higher principal quantum number.

Colour: Many transition metal ions are coloured due to the d-d transitions. The energy absorbed in
excitation of an electron from a lower energy d orbital to a higher energy d orbital corresponds to the
frequency which generally lies in the visible region. The colour observed corresponds to the
complimentary colour of the light absorbed. The frequency of light absorbed is determined by the
nature of ligand and nature of the metals.

Magnetic properties: Atoms ions and molecules with unpaired electrons are attracted to a magnet.this
properiy s known as Paramagnetism. Many transition metal compounds are paramagnetic due to the
presence of unpaired electrons. Any substance which is weakly attracted by a magnetic field is said to be
paramagnetic while if it is repelled, is Diamagnetic. A substance in which all the electrons paired are
repelled by a magnet and are said to exhibit Ferromagnetism.Transition elements and their ions are
generally paramagnetic, whereas most others are diamagnetic. The greater the number of unpaired
electrons the more paramagnetic is the ion. Paramagnetism in transition elements is associated with
unpaired electrons found in their partially filled d-orbitals because there is a magnetic moment
associated with the spinning electron.The magnetic moment arises with the number of unpaired
electrons- and this gives a good indication of the number of unpaired electrons present in the atom or
ion.

Magnetic moment of each such electron is associated with its spin angular momentum and orbital
angular momentum. For these the magnetic moment is determined by the number of electrons and is
calculated by using ‘spin-only’ formula, i.e., µs = √n(n+2) where n is the number of unpaired electrons
and µs is the magnetic moment in Bohr magneton (BM).

Oxidation States: Most transition metals have at least two stable oxidation states. Below table shows
most common and less common oxidation states. For the Group 3B–7B elements, the maximum
oxidation state is equal to the group number.In general, the maximum oxidation state for a transition
metal is observed onlywhen the metal is combined with the highly electronegative elements oxygen and
fluorine.For example, manganese has an oxidation state of +7 in the permanganate ion(MnO4 −) and
chromium has a +6 oxidation state in the chromate ion (CrO4 2−).

Crystal field theory: Valance bond theory able to explains the bonding in complexes but this theory is
unable to explain for their color.This theory unable to explain the why some complexes are high –spin
whereas others are low.This properties is explained by crystal field theory. This model was first applied
to transition metal ions in ionic crystals –hence the name crystals field thoery- but it also applies to
metal complexes where the crystal field is the electric field due to the charges of the ligands. Note the
difference between crystal field theory and valence bond thoery. Valence bond theory depends on
various factors like covalent bonds, shared electrons, hybrid orbitals. In crystal field theory , there are no
covalent bonds , no shared electrons , and no hybrid orbitals. But crystal field theory depends on just
electrostatic interactions of metals of d-oribitals and ligands. In crystal field approach the following
assumptions are made. Ligands are treated as point charges.

Octahedral complexes: According to the crystal field theory, the bonding is ionic and involves
electrostatic attraction between the positively charged ion and negatively charge ligands. Of course the
ligands repel one another, which is why they adopt the geometry (octahedral) that locates them as far
apart from one another as possible. Because the metal – ligand attractions are greater than the ligand –
ligand repulsions the complex is more stable than the separated ions, thus accounting for the bonding.In
an isolated metal atom the five d orbitals have identical energies and are said to be degenerate. If the
metal atom were surrounded by a spherical shell of negative charge, called a spherical field, their
electrostatic interaction between this field and the d electrons electrostatic repulsion leads to all the d-
orbitals increase in energy.