D and f-block

- By THE APRON BOY

- The d-block of the periodic table contains the elements of the groups 3-12 in which the d orbitals
are progressively filled in each of the four long periods.
- The f-block consists of elements in which 4 f and 5 f orbitals are progressively filled.
- There are mainly four series of the transition metals, 3d series (Sc to Zn), 4d series (Y to Cd), 5d
series (La and Hf to Hg) and 6d series which has Ac and elements from Rf to Cn.
- The two series of the inner transition metals; 4f (Ce to Lu) and 5f (Th to Lr) are known as
lanthanoids and actinoids respectively.
- Now according to IUPAC, transition metals are defined as metals which have incomplete d subshell
either in neutral atom or in their ions.
- Zinc, cadmium and mercury of group 12 have full d10 configuration in their ground state as well as
in their common oxidation states and hence, are not regarded as transition metals.
- Various precious metals such as silver, gold and platinum and industrially important metals like
iron, copper and titanium belong to the transition metals series.

THE TRANSITION ELEMENTS (d-BLOCK)

Electronic Configurations of the d-Block Elements

-In general the electronic configuration of outer orbitals of these elements is (n-1)d 1– 10 ns 1–
2 10 0
except for Pd where its electronic configuration is 4d 5s
-The (n–1) stands for the inner d orbitals which may have one to ten electrons and the outermost ns
orbital may have one or two electrons. .
-READ ALL ELECTRONIC CONF . FROM NCERT TABLE
- The transition metals and their compounds also exhibit catalytic property and paramagnetic
behavior
- There are greater similarities in the properties of the transition elements of a horizontal row in
contrast to the non-transition elements.

- Nearly all the transition elements display typical metallic properties such as high tensile strength,
ductility, malleability, high thermal and electrical conductivity and metallic lustre.
- With the exceptions of Zn, Cd, Hg and Mn, they have one or more typical metallic structures at
normal temperatures.
- The transition metals (with the exception of Zn, Cd and Hg) are very hard and have low volatility.
- Their melting and boiling points are high.
- In any row the melting points of these metals rise to a maximum at d 5 except for anomalous
values of Mn and Tc and fall regularly as the atomic number increases.
- Enthalpy of atomisation is an important factor in determining the standard electrode potential of
a metal, metals with very high enthalpy of atomisation (i.e., very high boiling point) tend to be noble
in their reactions (see later for electrode potentials).

Variation in Atomic and Ionic Sizes of Transition Metals

- In general, ions of the same charge in a given series show progressive decrease in radius with
increasing atomic number.
- This is because the new electron enters a d orbital each time the nuclear charge increases by
unity.
- It may be recalled that the shielding effect of a d electron is not that effective, hence the net
electrostatic attraction between the nuclear charge and the outermost electron increases and the
ionic radius decreases.
- The curves in Fig. 8.3 show an increase from the first (3d) to the second (4d) series of the
elements but the radii of the third (5d) series are virtually the same as those of the corresponding
members of the second series.
- This phenomenon is associated with the intervention of the 4f orbitals which must be filled
before the 5d series of elements begin.
- The filling of 4f before 5d orbital results in a regular decrease in atomic radii called Lanthanoid
contraction which essentially compensates for the expected increase in atomic size with increasing
atomic number.
- The net result of the lanthanoid contraction is that the second and the third d series exhibit
similar radii (e.g., Zr 160 pm, Hf 159 pm) and have very similar physical and chemical properties
much more than that expected on the basis of usual family relationship.
- The decrease in metallic radius coupled with increase in atomic mass results in a general increase
in the density of these elements.

Ionisation Enthalpies
- There is an increase in ionisation enthalpy along each series of the transition elements from left
to right due to an increase in nuclear charge which accompanies the filling of the inner d orbitals
- The variation in ionisation enthalpy along a series of transition elements is much less in comparison
to the variation along a period of non-transition elements.
- The first ionisation enthalpy, in general, increases, but the magnitude of the increase in the
second and third ionisation enthalpies for the successive elements, is much higher along a series.
- The irregular trend in the first ionisation enthalpy of the metals of 3d series, though of little
chemical significance, can be accounted for by considering that the removal of one electron alters
the relative energies of 4s and 3d orbitals.
- As we move along the period in 3d series, we see that nuclear charge increases from scandium to
zinc but electrons are added to the orbital of inner subshell, i.e., 3d orbitals. These 3d electrons
shield the 4s electrons from the increasing nuclear charge somewhat more effectively than the
outer shell electrons can shield one another.
- The three terms responsible for the value of ionisation enthalpy are attraction of each electron
towards nucleus, repulsion between the electrons and the exchange energy.
- Exchange energy is responsible for the stabilisation of energy state.
- Exchange energy is approximately proportional to the total number of possible pairs of parallel
spins in the degenerate orbitals.
- The loss of exchange energy increases the stability.
- Mn+ has 3d 5 4s 1 configuration and configuration of Cr+ is d 5
, therefore, ionisation enthalpy of
+ +
Mn is lower than Cr
-In the same way, Fe2+ has d 6 configuration and Mn2+ has 3d 5 configuration. Hence, ionisation
enthalpy of Fe2+ is lower than the Mn2+ .
- The value for Zn is correspondingly low as the ionisation causes the removal of one 4s electron
which results in the formation of stable d 10 configuration.

Oxidation States
- One of the notable features of a transition elements is the great variety of oxidation states
these may show in their compounds.
- The elements which give the greatest number of oxidation states occur in or near the middle of
the series. Manganese, for example, exhibits all the oxidation states from +2 to +7.
- The variability of oxidation states, a characteristic of transition elements, arises out of
incomplete filling of d orbitals in such a way that their oxidation states differ from each other by
unity.
- Although in the p–block the lower oxidation states are favoured by the heavier members (due to
inert pair effect), the opposite is true in the groups of d-block.
- Low oxidation states are found when a complex compound has ligands capable of π-acceptor
character in addition to the σ-bonding.

Trends in Stability of Higher Oxidation States

- The highest oxidation numbers are achieved in TiX4 (tetrahalides), VF5 and CrF6 .
- The +7 state for Mn is not represented in simple halides.
- The ability of fluorine to stabilise the highest oxidation state is due to either higher lattice
energy as in the case of CoF3 , or higher bond enthalpy terms for the higher covalent compounds,
e.g., VF5 and CrF6.
- The stability of Cu2+ (aq) rather than Cu+ (aq) is due to the much more negative ∆hydH of Cu2+ (aq)
than Cu+ , which more than compensates for the second ionisation enthalpy of Cu.
- The ability of oxygen to stabilise the highest oxidation state is demonstrated in the oxides.
- The ability of oxygen to stabilise these high oxidation states exceeds that of fluorine.
- Thus the highest Mn fluoride is MnF4 whereas the highest oxide is Mn2O7 .
- The ability of oxygen to form multiple bonds to metals explains its superiority.

Magnetic Properties
- When a magnetic field is applied to substances, mainly two types of magnetic behaviour are
observed: diamagnetism and paramagnetism.
- Diamagnetic substances are repelled by the applied field while the paramagnetic substances are
attracted.
- Substances which are attracted very strongly are said to be ferromagnetic.
- In fact, ferromagnetism is an extreme form of paramagnetism. Many of the transition metal ions
are paramagnetic.
- Paramagnetism arises from the presence of unpaired electrons, each such electron having a
magnetic moment associated with its spin angular momentum and orbital angular momentum.
- For the compounds of the first series of transition metals, the contribution of the orbital angular
momentum is effectively quenched and hence is of no significance.
- The magnetic moment increases with the increasing number of unpaired electrons.

Formation of Coloured Ions

- When an electron from a lower energy d orbital is excited to a higher energy d orbital, the energy
of excitation corresponds to the frequency of light absorbed
- The colour observed corresponds to the complementary colour of the light absorbed.
- The frequency of the light absorbed is determined by the nature of the ligand

Formation of Complex Compounds

- Complex compounds are those in which the metal ions bind a number of anions or neutral molecules
giving complex species with characteristic properties.
- The transition metals form a large number of complex compounds. This is due to the comparatively
smaller sizes of the metal ions, their high ionic charges and the availability of d orbitals for bond
formation.

Catalytic Properties
- The transition metals and their compounds are known for their catalytic activity
- This activity is ascribed to their ability to adopt multiple oxidation states and to form complexes.
- Vanadium(V) oxide (in Contact Process), finely divided iron (in Haber’s Process), and nickel (in
Catalytic Hydrogenation) are some of the examples.
- Catalysts at a solid surface involve the formation of bonds between reactant molecules and atoms
of the surface of the catalyst (first row transition metals utilise 3d and 4s electrons for bonding).
- iron(III) catalyses the reaction between iodide and persulphate ions.
2 I– + S2O8 2– → I2 + 2 SO4 2–

Formation of Interstitial Compounds/ Alloy Formation-NCERT

Potassium dichromate K2Cr2O7
-Potassium dichromate is a very important chemical used in leather industry and as an oxidant for
preparation of many azo compounds.
- Dichromates are generally prepared from chromate, which in turn are obtained by the fusion of
chromite ore (FeCr2O4 ) with sodium or potassium carbonate in free access of air.
READ ALL REACTIONS FROM NCERT
-The structures of chromate ion, CrO4 2– and the dichromate ion, Cr2O7 2– are shown below.

-The chromate ion is tetrahedral whereas the dichromate ion consists of two tetrahedra sharing
one corner with Cr–O–Cr bond angle of 126°.
- Sodium and potassium dichromates are strong oxidising agents; the sodium salt has a greater
solubility in water and is extensively used as an oxidising agent in organic chemistry.
- Potassium dichromate is used as a primary standard in volumetric analysis.

Potassium permanganate KMnO4

-Potassium permanganate is prepared by fusion of MnO2 with an alkali metal hydroxide and an
oxidising agent like KNO3 .
- This produces the dark green K2MnO4 which disproportionates in a neutral or acidic solution to
give permanganate.
-READ RXN. FROM NCERT.
- Potassium permanganate forms dark purple (almost black) crystals which are isostructural with
those of KClO4 .
- It has two physical properties of considerable interest: its intense colour and its diamagnetism
along with temperature-dependent weak paramagnetism.

-
- The manganate and permanganate ions are tetrahedral; the πbonding takes place by overlap of p
orbitals of oxygen with d orbitals of manganese.
- The green manganate is paramagnetic because of one unpaired electron but the permanganate is
diamagnetic due to the absence of unpaired electron.
- important oxidising reactions of KMnO4 are given in NCERT .