CHAPTER-8

d and f BLOCK
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
elements constituting the f -block are those in which the 4 f and 5 f orbitals are
progressively filled in the latter two long periods; these elements are formal
members of group 3 from which they have been taken out to form a separate f-
block of the periodic table
The names transition metals and inner transition metals are often used to refer to the elements
of d-and f-blocks respectively.

THE TRANSITION ELEMENTS

(d-BLOCK)
The name ‘transition’ given to the elements of d-block is only
because of their position between s– and p– block elements. The d–
orbitals of the penultimate energy level in their atoms receive
electrons giving rise to the three rows of the transition metals, i.e., 3d,
4d and 5d. The fourth row of 6d is still incomplete.
Electronic Confriguration of 3-d series
Electronic Confriguration of 4-d and 5-d series
Electronic Confriguration of 6-d series
The transition elements are those elements having a
partially filled d or f subshell in any common oxidation
state. The term "transition elements" most commonly
refers to the d-block transition elements.
Note: The electronic configurations of Zn, Cd and Hg are
represented by the general formula (n-1)d10ns2 . The orbitals
in these elements are completely filled in the ground state as
well as in their common oxidation states. Therefore, they are
not regarded as transition elements.
The d orbitals of the transition elements project to the periphery of an
atom more than the other orbitals (i.e., s and p), hence, they are more
influenced by the surroundings as well as affecting the atoms or
molecules surrounding them. In some respects, ions of a given dn
configuration (n = 1 – 9) have almost similar properties.
 Physical Properties of 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.

Why transition elements have high melting and boiling point?

In general, transition metals possess a high density and high melting
points and boiling points. These properties are due to metallic bonding by
delocalized d electrons, leading to cohesion which increases with the
number of shared electrons.
Enthalpy of Atomization, Δ H , is the change in
a
0

enthalpy when one mole of bonds is completely broken to obtain

atoms in the gas phase.
Why does manganese have lower melting point even though it has a higher number of
unpaired electrons for bonding?

Melting point depends on the intermolecular or interatomic forces. More stronger these
forces higher the melting point. d block elements undergoes additional covalent bond
formation due to presence of vacant d orbital along with the metallic bond. But in Mn
there is half filled 3d subshell (3d5) whuch is stable and hence does not undergoes
additional covalent bond and hence it had less melting point. Similarily in case of Tc
Variation in Atomic and Ionic Sizes of Transition Metals
❑The gradual decrease in the values of ionic radius
across the series of transition elements is due to the
increase in the effective nuclear charge.

❑Radii of the third (5d) series are virtually the same as

those of the corresponding members of the (4d)
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 due to poor shielding effect of f orbitals
known as Lanthanoid contraction which essentially
compensates for the expected increase in atomic size
with increasing atomic number.
IONISATION ENTHALPY OF
TRANSITION ELEMENTS
Why the ionisation enthalpy (first and second) in the first series of the transition elements is
found to be vary irregular?

❑ In the first transition series, the first and second ionization enthalpy values increases slowly from
left to right with certain irregularities. As the nuclear charge increases, the attraction between the
nucleus and outer electron increases due to which the ionization enthalpy increases.

❑ The removal of electron alters the energies of 4s and 3d orbitals which results in reorganization
energy accompanying ionization with some gains in exchange energy with increase in the number of
electrons in the dn configuration and from transference of s electrons into d orbitals. This results
in irregularities in the ionization enthalpy values.

Why 5d series have high 1st ionisation energy as compared to 4d and 3d?

1st ionisation energies of 5d elements are higher than those of 3d or 4d elements this is due to
the greater effective nuclear charge acting on outer valence electrons because of weak shielding
by 4f electrons.
Why the First ionization energy of chromium is lower and zinc is higher?
The value of Cr is lower because of the absence of any change in the d configuration and the value for Zn higher because it
represents an ionisation from the 4s level.

Why the second ionsiation energy of chromium and copper is high and for zinc the value is low?
The second ionisation enthalpy for Cr and Cu is very high due to the presence of d5 and d10 configurations which
disrupted the M+ ions , with considerable loss of exchange energy. On the other hand the second ionisation energy of Zn
is correspondingly low as the ionisation consists of the removal of an electron which allows the production of the stable d10
configuration.

Why the third ionisation energy of Manganese and zinc is high?

The third ionisation enthalpies is not complicated by the 4s orbital factor and shows the greater difficulty of removing an
electron from the d5 (Mn2+) and d10 (Zn2+) ions because of half filled d orbital and completely filled d orbital

What is the lowest common oxidation state of transition metals?

The lowest common oxidation state of transition metals is +2.
Oxidation State

Why do transition elements show variable oxidation states?

These elements show variable oxidation state because their valence electrons in two different sets of
orbitals, that is (n-1)d and ns. The energy difference between these orbitals is very less, so both the
energy levels can be used for bond formation. Thus, transition elements have variable oxidation states.
OR 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
❑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 lesser number of oxidation states at the extreme ends stems from either too few
electrons to lose or share (Sc, Ti) or too many d electrons (hence fewer orbitals
available in which to share electrons with others) for higher valence (Cu, Zn).
Ques: When transition elements show low oxidation states?
Ans: Low oxidation states are found when a complex compound has ligands capable of π-
acceptor character in addition to the σ-bonding. For example, in Ni(CO)4 and Fe(CO)5, the
oxidation state of nickel and iron is zero.

Note: The lower oxidation states are favoured by lighter members and the higher
oxidation states are favoured by heavier members.

Therefore Mo(IV) and W(IV) are found to be more stable than Cr(IV)

Ques: Out of Cr(IV), Mo(IV) and W(IV) which one is strong oxidising agent?
Ans: Cr(IV)
Trends in the M2+/M Standard Electrode Potentials
• The unique behaviour of Cu, having a positive EO, because for its
inability to liberate H2 from acids. Only oxidising acids (nitric and
hot concentrated sulphuric) react with Cu, the acids being reduced.

• The stability of the half-filled d sub-shell in Mn2+ and the

completely filled d10 configuration in Zn2+ are related to their Eo
values, whereas Eo for Ni is related to the highest negative ΔhydHO.
Trends in the M3+/M2+ Standard Electrode Potentials
• The low value for Sc reflects the stability of Sc3+ which has a noble gas
configuration.

• The highest value for Zn is due to the removal of an electron from the stable d10
configuration of Zn2+

• The comparatively high value for Mn shows that Mn2+(d5 ) is particularly stable,
whereas comparatively low value for Fe shows the extra stability of Fe3+ (d5 ).

• The comparatively low value for V is related to the stability of V2+ (half-filled t2g
level)
 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 but MnO3F is known, and beyond Mn
no metal has a trihalide except FeX3 and CoF3.
• 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.
• Although VV is represented only by VF5, the other halides, however, undergo
hydrolysis to give oxohalides, VOX3. Another feature of fluorides is their
instability in the low oxidation states e.g., VX2 (X = CI, Br or I) and the same
applies to CuX.
• All CuII halides are known except the iodide. In this case, Cu2+ oxidises I– to I2
• The ability of oxygen to stabilise the highest oxidation state is demonstrated in the
oxides.
• The highest oxidation number in the oxides coincides with the group number and is
attained in Sc2O3 to Mn2O7.
• Beyond Group 7, no higher oxides of Fe above Fe2O3, are known, although ferrates
(VI)(FeO4) 2–, are formed in alkaline media but they readily decompose to Fe2O3 and
O2.
• Besides the oxides, oxocations stabilise Vv as VO2+ , VIV as VO2+ and TiIV as TiO2+.
• 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.
• In the covalent oxide Mn2O7, each Mn is tetrahedrally surrounded by O’s including a
Mn–O–Mn bridge. The tetrahedral [MO4]-n ions are known for VV , CrVl, MnV , MnVl
and MnVII.
Ques: Which is a stronger reducing agent Cr2+ or Fe2+ and why ?
Ans: Cr2+ is a better reducing agent. As it attains a d3 configuration
on loosing an electron while Fe2+ attains d5 configuration. In an
aqueous medium d3 (half filled t2g orbital) is more stable than d5.
Mn3+ and Co3+ ions are the strongest oxidising agents in aqueous solutions. The ions Ti2+, V2+ and Cr2+ are strong
reducing agents and will liberate hydrogen from a dilute acid, e.g.
SOME IMPORTANT
QUESTIONS
Why transition metals and many of their compounds show
paramagnetic behavior.
Transition elements and many of their compounds are paramagnetic, i.e., they are weakly attracted by a
magnetic field. This is due to the presence of unpaired electrons in atoms, ions or molecules. The
paramagnetic character increases as the number of unpaired electrons increases. The paramagnetic
character is measured in terms of magnetic moment and is given by

where n = number of unpaired electrons.

 Why transition elements form coloured compounds?

Transition metal ions generally possess one or more unpaired electrons. When
visible light falls on a transition metal compound or ion, the unpaired electrons
present in the lower energe d-orbital get promoted to high energy d-orbitals, called
d-d transition, due to the absorption of visible light. Since, the energy involved in
d-d transition is quantised, only a definite wavelength gets absorbed, remaining
wavelengths present in the visible region got transmitted. Therefore, transmitted
light shows some colour complementary to the absorbed colour.

Predict which of the following will be coloured in aqueous solution Ti3+, V3+, Cu+ , Sc3+, Mn2+, Fe3+ and Co2+? Give
reasons for each.
 Why transition metals and their compounds show catalytic activities.
Transition metal and their compounds show catalytic properties because of
following reasons:
1. Due to their variable oxidation state, they form intermediate complex, thereby
providing new path for reaction.
2. Availability of empty d-orbital which provide good surface area for reaction.
Why do transition elements form coordination complexes?
Transition-metal ions form coordination complexes because they have empty valence-
shell orbitals that can accept pairs of electrons from a lewis base. ligands must
therefore be lewis bases: they must contain at least one pair of nonbonding electrons
that can be donated to a metal ion.

Why do transition elements form interstitial compounds?

Many of the transition elements are known to form interstitial compounds
because of unpaired electrons in the d-orbital. Transition elements have
vacant interstitial sites and are able to trap small atoms like H, C or N to
form such compound.
Why do transition elements form Alloys?
Alloy is the homogeneous mixture of two or more metals or metals with non-metals.
Alloys are made to confer the property of metals. Transition elements have great
tendency to form alloys because these elements have similar atomic size and can
mutually substitute their positions in their crystal lattice. Alloys are comparatively
hard and have higher m.p. than the elements form which they are made.
IMPORTANT POINTS TO REMEMBER
• As the oxidation number of a metal increases, ionic character decreases.
• In these higher oxidation states oxides, the acidic character is predominant.
 f -block

The f-block consists of the two series, lanthanoids (the fourteen elements
following lanthanum) and actinoids (the fourteen elements following
actinium). Because lanthanum closely resembles the lanthanoids, it is usually
included in any discussion of the lanthanoids for which the general symbol
Ln is often used.
• The overall decrease in atomic and ionic radii
from lanthanum to lutetium. The decrease in
atomic radii (derived from the structures of
metals) is not quite regular as it is regular in M+3

• The intervening of 4f orbital before 5d orbitals

results in poor shielding causes the contraction
of the lanthanoid series, known as lanthanoid
contraction due to which the radii of the
members of the third transition series (5d) to be
very similar to those of the corresponding
members of the second series (4d) . The almost
identical radii of Zr (160 pm) and Hf (159 pm).
 General Characteristics
• All the lanthanoids are silvery white soft metals and tarnish rapidly in air. The hardness increases with increasing atomic
number, samarium being steel hard.

• Their melting points range between 1000 to 1200 K but samarium melts at 1623 K.

• They have typical metallic structure and are good conductors of heat and electricity.

• Density and other properties change smoothly except for Eu and Yb and occasionally for Sm and Tm.

• Many trivalent lanthanoid ions are coloured both in the solid state and in aqueous solutions. Colour of these ions may be
attributed to the presence of f electrons

• Neither La3+ nor Lu3+ ion shows any colour but the rest do so. However, absorption bands are narrow, probably because of
the excitation within f level. The lanthanoid ions other than the f 0 type (La3+ and Ce4+) and the f 14 type (Yb2+ and Lu3+)
are all paramagnetic. The paramagnetism rises to maximum in neodymium.

• Third ionization enthaply have a certain degree of stability to empty, half-filled and completely filled orbitals f level.
 • In their chemical behaviour, in general, the earlier members of the series are quite reactive similar to calcium but,
with increasing atomic number, they behave more like aluminium.

• The best single use of the lanthanoids is for the production of alloy steels for plates and pipes. A well known alloy is
mischmetall which consists of a lanthanoid metal (~ 95%) and iron (~ 5%) and traces of S, C, Ca and Al. A good deal of
mischmetall is used in Mg-based alloy to produce bullets, shell and lighter flint. Mixed oxides of lanthanoids are
employed as catalysts in petroleum cracking. Some individual Ln oxides are used as phosphors in television screens and
similar fluorescing surfaces.
 Oxidation States
• In the lanthanoids, La(III) and Ln(III) compounds are predominant species. However, occasionally +2 and +4 ions in
solution or in solid compounds are also obtained.

• The formation of CeIVis favoured by its noble gas configuration, but it is a strong oxidant reverting to the common +3
state.

• Ce(IV) is a good analytical reagent.

• Pr, Nd, Tb and Dy also exhibit +4 state but only in oxides MO2

• Eu2+ is formed by losing the two s electrons and its f 7 configuration accounts for the formation of this ion. However, Eu2+
is a strong reducing agent changing to the common +3 state.

• Similarly Yb2+ which has f 14 configuration is a reductant. TbIV has half-filled f-orbitals and is an oxidant.

• The behaviour of samarium is very much like europium, exhibiting both +2 and +3 oxidation states.
 Some Applications of d- and f-Block Elements
• TiO for the pigment industry and MnO 2for use in dry battery cells. The battery industry
also requires Zn and Ni/Cd.

• The elements of Group 11 are still worthy of being called the coinage metals, UK
‘copper’ coins are copper-coated steel. The ‘silver’ UK coins are a Cu/Ni alloy ,
although Ag and Au 233 The d- and f- Block Elements are restricted

• Many of the metals and/or their compounds are essential catalysts in the chemical
industry. E.g V2O5 catalyses the oxidation of SO2 in the manufacture of sulphuric acid.

• TiCl4 with Al(CH3)3 forms the basis of the Ziegler catalysts used to manufacture
polyethylene (polythene).

• Iron catalysts are used in the Haber process for the production of ammonia from N2/H2
mixtures.
• In the Wacker process the oxidation of ethyne to ethanal is catalysed by PdCl2.
• Nickel complexes are useful in the polymerisation of alkynes and other organic
compounds such as benzene.
• The photographic industry relies on the special light-sensitive properties of AgBr.
 NCERT
QUESTIONS