1.

d-Block Elenents: The d-block elements are those elements in which the last electron enters the d--subshell
of penultimate shell. The general electronic configuration of these elements is (n - 1) d ns, where n is
outermost shell. The d-block consisting of groups 3-12 occupies the large middle section of the periodic table.
2. Transition Elements: The elements of d-block are known as transition elements as they possess properties
that are transitional between the s and p block elements. Atransition element is defined as an element which
has incompletely filled d-orbitals in its ground state or any one of its oxidation states. There are four series
of transition elements spread between group 3 and 12.
iolt so First transition series or 3d-series: Scandium (6,Sc) to Zinc (s0Zn)alst
Second transition series or 4d-series: Yttrium (39Y) to Cadmium (4;Cd)om l
at alu Third transition series or Sd-series: Lanthanum (5,La) and Hafnium ,Hf to Mercury (soHg)
borisorU e (Omitting ssCe to 1Lu)
OeFourthtransition series or 6d-series: Begins with Actinium (goAc) is still incomplete.
Zinc, cadmium and mercury of group 12 have full d configuration in their ground state as well as in their
being the end elements
common oxidation states and hence, are not regarded as transition metals. However,
of he three transition series, their chemistry is studied along with the chemistry of the transition elements.
3.General Characteristics of Transition Elements
those of s-block elements
a (a) Atomic radii: The atomic radii of transition elements are smaller than
and larger than those ofp-block elements in a period. In a transition series, as the atomic number
increases, the atomic radi first decreases till the middle, becomes almost constant and then increases
towards the end of the period. The decrease in atomic radii in the beginning is due to the increase
the effective nuclear charge with the increase in atomic number. However, with the increase in the
number of electrons in (n 1)d-subshell, the screening effect of these d-electrons on the outermost
ns-electrons also increases. This increased screening effect counterbalances the effect of increased
nuclear charge, therefore, the atomic radii remain almost constant in the middle of the series. Increase
in atomic radii towards the end may be attributed to the electron-electron repulsion. The pairing of
electrons inthe d-orbitals of the penultimate shell occurs only after the d-subshell is half flled. The
repulsive interactions between the paired electrons in d-orbitals (of the penultimate shell) become
verydominant towards the end of the series and causes the expansion of the electron cloud and thus,
aneresulting in increased atomic size.lutsiod 0s0
The atomic radii usually increase down the group. But the atomic radii of the elements of second
and third transition series belonging to a particular group are almost equal. This is due to lanthanoid
contyaction.
(b)Aoniç radii: The ionic radii of the transitional elements follow the same order as their atomic radii. In
geheral, the ionic radii decrease with increase in oxidation state.
lonisation enthalpies: The first ionisation enthalpies of transition elements are higher than those of
s-block elements but lower than p-block elemnents. In a particular transition series, ionisation enthalpy
increases gradually with increase in atomicnumber, though some irregularities are
observed.
 Reason: The increase in ionisation enthalpy is due to increase in nuclear charge with
atomic number which tends to attract the electron cloud with greater force. increase in
The addition of d-electron in penultimate shell with increase in atomic number provides a
scr
effect and shield the outer s-clectrons from inward nuclear pull. Thus, the effect of increased
charge and increased magnitude of screening effect tend to oppose each other. Consequently
eening
mt3
increase in ionisation enthalpy along the series of transition element is very small. The irrem
variationsof first and second ionisation enthalpies in the first transition series is mainly due to yar
degree of stability of diferent 3d-configuration. For example, Cr has low first ionisation enthal
because loss of one clectron gives stable 3a configuration and Zn has very high first ionisati
enthalpy because the electron has to be removed from 4s-orbital of the stable 3d"4s configuration
The first ionisation enthalpies of 5d-transition elements are higher than those of 3d and 4d elemente
This is due to greater effective nuclear charge acting on the outer valence electrons in these element
betause of the ineffective shielding of the nucleus by 4f-electrons.
(dy Metalliccharacter: All the transition elements are metallic in nature. They show gradual decrease in
electropositive character in moving from left to right in a series. The metallic bond in transition metals
are very strong. This is due to greater effective nuclear charge, low ionisation energies and larpe
number of vacant orbitals in their outermost shell. Nearly, all the transition metals are hard, posses
high density and high enthalpy of atomisation. This isdue to presence of strong metallic bonds.
LeyMelting and boiling points: Except zinc, cadmium and mercury allthe other transition elements
generally have high melting and boiling points. This is due to strong metallic bonds and presence of
partially illed d-orbitals in them. Because of these half-filled orbitals some covalent bonds also exist
between atoms of transition elements. As zinc, mercury and cadmium have fully filled d-orbitals,
therefore, there is no covalent bonding amongst the atoms of these elements. This accounts for their
low melting and boiling points. nond
In moving along series from left to right, the melting and boiling points of transition elements first
increase to a maximum and then decrease towards the end of the period. As the number of unpaired
electrons increases,the tendency to form metallic and covalent bonds also increases. In first transition
series after chromium, the number of unpaired electrons decreases, hence the melting point also
decreases. Manganese possesses anomalous melting and boiling points because it has stable 34s
configuration, i.e., electrons are held tightly by nucleus so that the delocalisation is less andthe metalic
bÍnd is much weaker than that of preceding element.
nOxidation states: Alltransition elements except first and last member of the series exhibit varable
oxidation states as (n - 1)d and ns orbitals have comparable energies so that both can enter into
chemical bond formation. The maximum oxidation state shown by first series increases from Scto Nn
and then decreases. The common oxidation state of first series is +3 (except Sc). The highest oxidatilon
state of transition elements is 8 (Os and Ru).
The compounds of transition elements in lower states +2 and +3 are mostly ionic and of higne
oxidation states are covalent, e.g., ZnCl, and CdCI, are ionic whereas Cr,0 and Mn, are covae
in nature,higher oxidation state of transition elements are shown in oxides and oxoacids (e.g., Mn
Transition metals with fluorine and oxygen exhibit higher oxidation state due to higher electronega
nature of fluorine and oxygen. Transition metals also exhibit +l and 0 oxidation states. For exaty
Cu,Cl, AgCI, Hg,Cl, (OS of metal is +1)
Ni(CO),, Fe(CO),e(0S of metal is 0)ob c standard
When the metal exhibit more than one OS, their relative stabilities can be known from their
electrode potential, e.g.,
Cu²(aq) +2e Cu(s) Ered =0.34 volteedb t
Cu*(aq) + e Cu(s) Ered =0.52 volt
Lwer standard reduction potential indicates Cu² is more stable than Cu in aqueous mediu
(gStandard electrode potential: Electrode potential is the electric potential developedthe tode
from enthalp.
electrode when it is in equilibrium with a solution of its own ions, taking electronsionisation
There is irregular variation in electrode potential due to irregular variation in acrossthe
sublimation energy and energy of hydration. The E value decreases from left to right
 series; Mn, Ni and Zn have higher values than expected because of their half-flled or completely filled
3j-órbitals in case of Mn" and Zn respectively and the highest negative enthalpy of hydration, Ni.
Magnetic prOperties: Substances containing unpaired electrons are said to be paramagnetic. A
diamagneticsubstance is one in which all the electrons are paired. Except the ions of d (Sc, Ti)
and d" (Cu", Zn)configurations, all other simple ions of transition elements contain unpaired
electrons in their (n-1) dsubshell and are, therefore, paramagnetic. The magnetic moments () of
the elements of first transition series can be calculated with the unpaired electrons (n) by the spin only
formula.

=yn(n+2) BM (Bohr Magneton)

Y Complex formation: The tendency to form complex ions is due to
(i) the high charge on the transition metal ions,
)the availability of d-orbitals for accommodating electrons donated by the ligand atoms.
Catalytic property: Most of the transition metals and their compounds possess catalytic properties.
The catalyticactivity of transition metal ions is attributed to the following two reasons:
()Variable oxidation states due to which they can form a variety of unstable intermediate products.
(ii Large surface area so that the reactants are adsorbed on the surface and come close to each other
facilitating the reaction process.
(k) Colour: Most of the transition metal ions in solution as wellas in solid states are coloured.This is due
tothe partial absorption of visible light. The absorbed light promotes the electron from one orbital to
another orbital of the same d-subshell. Since the electronic transition occurs within the d-orbitals of
the transition metal ions, they are called d-d transitions. It is because of these d-d transitions occurring
in atransition metal ion by absorption of visible light that they appear coloured.
Aloy
(0Aloy formation: The transition metals have similar radi and other characteristics. Therefore, these
Zmetals can mutually substitute their position in their crystal lattices and form alloys. The alloys so
formed are hard and often have high melting point. Various types of steel, brass, bronze are examples
of this type of alloy.
(m)Anterstitiallcompounds: Interstitial compounds are those in which small atoms occupy the interstitial
sites in the crystal lattice. Interstitial compounds are well known for transition metals because small
sized atoms of H, B, CN, etc., can easily occupy positions in the voids present in the crystal lattices
of transition metals.1