UNIT 8

THE d- and f- block Elements

d- block elements or Transition elements

A transition element is defined as the one which has incompletely filled d-

orbitals in its ground state or in any one of its oxidation states.In transition
elements, d-subshell in penultimate energy level is being progressively filled.

 Transition elements are lying between s- block and p- block elements.

These elements show transition in properties from s- block(
electropositive) to p- block( electronegative) elements.
 In the periodic table the d block consist of the elements of
group 3 to 12.
 The d orbital of the d-block elements in four periods are filled.
 The three series of the transition elements are
 3d series : Sc to Zn
4d series : Y to Cd
5dseries : La to Hg (excluding Ce to Lu)

Position of d-block in periodic table

Electronic Configurations of the d-Block Elements

 The electronic configuration of d-block elements is

(n-1) d1–10 ns1–2. They have two incomplete outershells.
where (n–1) = inner d orbitals having electrons from 1-10.
General characteristics of Transition elements

 Except Mercury which is a liquid, all transition elements have typical

metallic structure and show metallic properties.
 Their atomic radii are in between those of s- and p-block elements.
 They have high melting and boiling points , high enthalpies of vaporization,
high enthalpies of atomization and high enthalpies of hydration of their
ions.
 The first ionization energies are higher than those of s- block elements and
less than those of p-block elements.
 They are electropositive in nature.
 They show variable oxidation states.
 The stability of any oxidation state or the tendency for any transition metal
ion to act as oxidizing or reducing agent depends upon its electrode
potential.
 A number of these transition metals and their compounds show catalytic
properties.
 Most of them formed coloured compounds.
 They have a great tendency to form complexes.
 They form interstitial compounds with H,C, B and N.
 They form alloys.
Physical properties

Metallic character

Except Mercury, all the transition elements have metallic structure. The metallic
character is due to the relatively low I.E and presence of unpaired e-. The
hardness of metal suggest the presence of strong interatomic metallic bonding
due to the overlap of unpaired e- between metal atoms.

Metallic bond, force that holds atoms together in a metallic substance. Such a
solid consists of closely packed atoms. In most cases, the outermost electron shell
of each of the metal atoms overlaps with a large number of neighboring atoms. As
a consequence, the valence electrons continually move from one atom to another
and are not associated with any specific pair of atoms. The atoms that
the electrons leave behind become positive ions, and the interaction between
such ions and valence electrons gives rise to the cohesive or binding force that
holds the metallic crystal together.

Melting and boiling points

Melting and boiling point of transition metals are generally high. The high melting
point is due to the presence of strong interatomic bonding which involves the
participation of both (n-1) d & ns e-s. On moving along a period , melting points
of these elements increases to a maximum and then gradually decreases towards
the end. The maxima at about the middle of each series indicate that one
unpaired electron per d- orbital is particularly favorably for strong interatomic
interaction.

Among d- block elements, Tungsten (W) has highest melting point.

Note : Manganese (Mn) and Technetium (Tn) have abnormally low melting
points.

They have exactly half filled d-orbitals. As a result electronic configuration is

stable, electrons are held tightly by the nucleus so that the delocalization is less
and metallic bond is much weak.

As there are no unpaired electrons in Zn, Cd, Hg, they are soft and have low
melting points.
Atomic and ionic radii

Among the elements of a particular transition series, on moving from left to right

( Z value increases) and atomic size decreases. There is a steady decrease till the

middle, almost constant ( difference in size is very small) and then increases

towards the end.

3d series

Sc – Cr (decreases) Fe, Co, Ni (constant) Cu – Zn(increases)

On moving from left to right, nuclear charge increases (Sc- Cr) , but the
corresponding electron goes to inner d- subshell. Since the shielding effect due to
inner d- e- is very small, effective nuclear attraction on the outermost e- increases
and the size decreases.

But from Fe – Ni , increase in nuclear charge is partially balanced by the increase

in screening effect as the number of d- electrons increases and therefore size
remains constant.

The increase in size at the end of the period is due to e- - e- repulsion between the
paired electrons.
On moving down a group , the size is not varying regularly. The atomic size of the
4-d series is more than that of 3d series. But the atomic size of 5d series is almost
same as that of 4-d series due to Lanthanoid contraction. It has been observed
that Zirconium and Hafnium have almost equal atomic radii.

Ionic radii: The ionic radius is similar to the pattern of atomic radii. Thus, for ions
of a given charge, the radius decreases gradually with increase in atomic number.

Enthalpy of atomization

[Energy required to convert metallic crystal into individual atom.]

The transition elements have high enthalpy of atomization is due to the

presence of strong interatomic bonding which involves the participation of both
(n-1) d and ns electrons. Greater the number of valence electrons greater is the
enthalpy of atomization and stronger is the resultant metallic bonding.

In any transition metal series, enthalpy of atomization increases from left to right,
reaches a maxima at the middle. This maxima indicate that one unpaired electron
per d- orbital favorable for interatomic bonding.
Enthalpy of atomization is an important factor in determining the standard
electrode potential of a metal, thus metals with high value of enthalpy of
atomization tend to be noble in their reactions.

Metals of the 2nd and 3rd transition series have higher enthalpies of atomization
than the corresponding elements of the first transition series. This is due to the
occurrence of more frequent M-M bonding in compounds of heavy transition
metals.

Density

The decrease in metallic radius coupled with increase in atomic mass results in
general increase in the density of these metals from left to right. Thus there is an
increase in density from Ti – Cu in the first series (due to its large size, Zn has low
density).

Among transition elements , Osmium (22.59g/cm3) and Iridium (22.61g/cm3)

have highest density.

Ionization Enthalpies

Ionisation enthalpy is generally high for each series of transition elements due to
increase in nuclear charge which accompanies the filling of d- orbitals leading to
small size of atoms.

In d- block elements, d- subshell being progressively filled. But the shielding effect
due to d- e-s is very weak. On moving from left to right, effective nuclear
attraction increases. As a result, I.E increases along each transition series. But this
increase is not as high as in representative elements.

But irregularities also observed in the first I.E of 3-d metals.

Removal of one electron alters, the energies of 4s and 3d orbitals. So the

unipositive ion will have dn configuration with no ‘4s’ electrons. There is thus, a
reorganization energy accompanying ionization with some gains in exchange
energy as the number of electrons increases and from the transfer of s electrons
to d- orbitals.

The first I.E of Cr is less (653 KJ/mol) as it involves the removal of one 4s electron
and results in the formation of stable, half filled configuration.

Cr → *Ar+ 3d54s1 Cr+ → *Ar+ 3d54s0

The first I.E of Zn is very high (906 KJ/mol) as it involves the removal of an e form
a stable conf. [Zn => [Ar] 3d10,4s2]

Second I.E. is usually high for Cr & Cu.

[Cr+ = [Ar] 3d5, Cu+= [Ar] 3d10]. Both Cr+ & Cu+ are highly stable. Therefore it is very
difficult to remove the second e-.

Second I.E. of Zn is lower than that of Cu. This is because removal of 2nd e- leads
to formation of highly stable completely filled configuration (3d10 ).

Third I.E. of Mn & Zn are very high[Mn2+→*Ar+3d5 Zn2+→*Ar+3d10]

Third I.E. of Fe (2962 Kg/mol) is lower than of Mn [3260 Kg/mol ].

[Fe2+=>[Ar]3d6, Fe3+=> [Ar]3d5]

The first ionization enthalpies of 5d elements are higher as compared to those of

3d and 4d elements. This is because the weak shielding of nucleus by 4f electrons
in 5d elements results in greater effective nuclear charge acting on the outer
valence electrons.
Oxidation state

All transition elements except first and last member of the series exhibit variable
oxidation state.

The variable oxidation state of a transition metal is due to the participation of

both ns and (n-1) de-s in bond formation. This is because the energy difference
between (n-1)d and ns is less. The lower O.S is exhibited when ns e- participated
in bonding and higher O.S is exhibited when ns & (n-1)de-s take part in bonding.
The elements which show the greatest number of O.S occur in or middle of the
series.

Oxidation state first increases from Sc to Mn due to increase in number of

unpaired electrons and then decreases because pairing takes place.

Highest number of oxidation states

 The elements which give the greatest number of oxidation states occur in
or near the middle of the series. Eg : Mn
 In d- block elements, on moving down a group, stability of higher oxidation
state increases due to increase in the distance from the outermost shell.
Eg : In Group 6, Cr (VI) – less stable
Mo(VI)& W(VI) – highly stable
[In p-block elements, on moving down a group stability of lower oxidation
state increases due to inert pair effect.]
 In lower O.S, bonds formed by a transition element are ionic, but in higher
O.S, bonds are covalent.
 Eg : Mn2+ (ionic) and MnO4- & CrO42- bonds are covalent.

 Low oxidation states are found if a complex compound has ligands capable
of π-acceptor character and sigma bonding .Eg : [Ni (CO)4], [Fe(CO)5]

Electrode potentials and oxidation states

The thermodynamic stability of an O.S of a transition element can be evaluated in

terms of the magnitude of I.E.

Smaller the I.E., more stable will be the O.S.

But in solution, stability of an O.S depends on electrode potentials (E0redn) rather

than I.E. .

Electrode potential depends upon the balance between the value of ∆hyH and the
sum of the values of ∆iH and ∆aH.

Lower the value of E0redn (more –ve), greater will be the stability of that
oxidation state.

The standard electrode potentials for M2+/M for the first row transition metal is
as follows:

Element: V Cr Mn Fe Co Ni Cu Zn

E0(M2+/M): -1.18v -0.91v -1.18v -0.44v -0.28v -

0.25 +
0.34 -
0.76

There is no regular trends in E0values.

(i) The values of E0 across the series are less negative because of general increase

in the sum of ∆1H &∆2H. E0 for Mn & Zn are more –ve because of half filled and

fully filled orbitals. The exceptional value of Ni is due to its highly negative

enthalpy of hydration

(ii)Copper shows a unique behaviour in the series as it is only metal having a +ve
 E0 value. This is because the high values of ∆subH & ∆iH are not compensated by

enthalpy of hydration. Because of this +ve E0value, Cu does not displace H2 from

acids.

[But strong oxidising agents (eg:- HNO3 & hot conc. H2SO4) react with Cu and
oxidise Cu to Cu2+.

Cu + 2H2SO4 - CuSO4+2H2O+SO2]

Trends in the M3+/M2+ standard electrode potentials:

E0(Sc3+/Sc2+) value is low, shows the greater stability of Sc3+.

E0(Zn3+/Zn2+) value is very high, indicates the greater stability of Zn2+.

E0(Fe3+/Fe2+) comparatively low, shows the greater stability of Fe3+(d5).

E0(Mn3+/Mn2+) comparatively high, indicates the greater stability of Mn2+ (d5)

Trends in the stability of higher oxidation states of transition metals

Transition metal shows their higher oxidation states with fluorine and oxygen
because F and O are small in size and the most electronegative elements.

3d transition elements forms stable halides.

Eg : TiF4, VF5, CrF6, MnO3F

Highest oxidation state is generally most stable with fluorine. This is due to either
high lattice energy (ionic compounds – eg: CoF3) or high bond enthalpy (covalent
compounds – eg: VF5, CrF6).

In lower O.S., fluorides are highly unstable.

Eg: VF2 is highly unstable. Similarly CuF is not existing but CuCl, CuBr, CuI exist.

Among Cu(II) halides, CuF2, CuCl2,CuBr2 exist but CuI2 does not exist. This is
because, Cu2+ oxidises I- to I2.
 2Cu2+ + 4I-→ Cu2I2 (S)+ I2

However most of the copper (I) compounds are unstable in aqueous solution and
undergo disproportionation.

2Cu+ →Cu2+ + Cu

The stability of Cu2+(aq) rather than Cu+ is due to the much more negative ∆hyH
of Cu2+ than Cu+ which compensates for the 2nd I.E. of Cu.

Oxygen also stabilizes the highest O.S. in the oxides more than fluorine.

Eg: Highest fluoride of Mn is MnF4

Oxide is Mn2O7

This is due to the ability of oxygen to form multiple bonds with metal atoms.

Eg : In covalent oxide Mn2O7, each Mn is tetrahedrally surrounded by O atom

Including Mn-O-Mn bridge.

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.)

The d- and f- Block Elements 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 due to the
presence of unpaired electrons, each such electron having a magnetic moment
associated with its spin angular momentum and orbital angular momentum.

The magnetic moment is determined by the number of unpaired electrons and is

calculated by using the ‘spin-only’ formula, i.e.,

where ‘n’ is the number of unpaired electrons and µ is the magnetic

moment in units of Bohr magneton (BM).

The magnetic moment increases with the increasing number of unpaired

electrons. Thus, the observed magnetic moment gives a useful indication about
the number of unpaired electrons present in the atom, molecule or ion.

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.
This frequency generally lies in the visible region. 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.

Majority of the transition metal compounds are coloured both in solid state and
in aqueous solution. This property have been used for the detection and
estimation of ions.

The colour of transition metal is due to the presence of incomplete d- subshell.

The occurance of colour can be explained on the basis of d-d transition of e- in
incomplete d- subshell.

Complexes

Complex compounds are those in which the metal ions bind a number of anions
or neutral molecules giving complex species with characteristic properties.
 Eg: [Fe(CN)6 ] 3–, [Fe(CN)6 ] 4– , [Cu(NH3)4] 2+

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.

Eg : Vanadium(V) oxide (in Contact Process),

Finely divided iron (in Haber’s Process),

Nickel (in Catalytic Hydrogenation)

Because of the presence of vacant d-orbital and ability to form multiple oxidation
states, transition elements can form intermediate complex compounds with
reactants. These intermediates provide reaction path of lower activation energy
and thus increases the rate of the reaction.

In many reactions, catalyst provide a surface for the reaction to take place.
Catalyst form bonds with reactant molecules and thus increases the
concentration of the reactants on the surface , also weakening of the bonds in the
reactant molecules.

Eg : iron(III) catalyses the reaction between iodide and persulphate ions.

2 I – + S2O8 2– → I2 + 2 SO4 2–

Catalytic action:

2 Fe3+ + 2 I– → 2 Fe2+ + I2

2 Fe2+ + S2O8 2– → 2 Fe3+ + 2SO4 2–

Interstitial compounds

Interstitial compounds are those which are formed when small atoms like H, C or
N are trapped inside the crystal lattices of metals. They are usually non
stoichiometric and are neither typically ionic nor covalent.

Eg : TiC, Mn4N, Fe3H, VH0 .56 ,TiH1.7

The formulas of these compounds do not correspond to any normal oxidation

state of the metal. Because of the nature of their composition, these compounds
are referred to as interstitial compounds.

The principal physical and chemical characteristics of these compounds are as

follows:

(i) They have high melting points, higher than those of pure metals.

(ii) They are very hard, some borides approach diamond in hardness.

(iii) They retain metallic conductivity.

(iv) They are chemically inert.

Alloy formation

An alloy is a blend of metals prepared by mixing the components. Alloys may be

homogeneous solid solutions in which the atoms of one metal are distributed
randomly among the atoms of the other. Such alloys are formed by atoms with
metallic radii that are within about 15 percent of each other.
Because of similar radii and other characteristics of transition metals, a few atoms
of one metal can be replaced by atoms of another metal ;so alloys are readily
formed by these metals.

The alloys so formed are hard ,have often high melting points and more resistant
to corrosion than the individual metal.

Eg : Cr, V, , Mo and Mn are used for the production of a variety of steels and
stainless steel.

Alloys of transition metals with non transition metals such as brass (copper-zinc)
and bronze (copper-tin), are also of considerable industrial importance.

The inner transition elements (f-block elements)

In these elements, ‘f’ subshell is being progressively filled and last e- goes to f-
subshell. They are also called inner transition elements as last e- occupies the

(n-2) f subshell, i.e. inner to the penultimate energy level (antipenultimate level).
Their general outer electronic configuration is

(n-2)f1-14(n-1)d0-1ns2. They occur very rarely, known as rare earth metals.

Depending upon the last electron entry, f-block elements are classified into:

 Lanthanoids :-

In these elements, last e enters into 4f orbital. They are called lanthanoids
because they come immediately after lanthanum. Lanthanoids include 14
elements Ce (Cerium) to Lu(Lutetium).

 Actinoids:-In these elements, last e- enters into 5f orbital. They are called
actinoids as they come after Actinium. Actinoids also include 14 elements,
Th(Thromium) to Lr(Laurenium).
 1. Electronic configuration

Only Ce, Gd and Lu have electron in 5d subshell.

Oxidation state:-

 The most common O.S. of Lanthoids is +3.

 +3 O.S. of La, Gd & Lu are especially stable due to empty, half filled &
completely filled 4f subshell respectively.
 Some elements exihibit +2 & +4, because by loosing 2 or 4 electrons, they
attain stable f0, f7& f14 configurations.

Eg: Ce (Ce4+ : {Xe] 4f0)

Tb (Tb4+:[Xe] 4f7)

Eu (Eu2+: [Xe] 4f7)

Yb (Yb2+: [Xe] 4f14)

General characteristics

1.Lantanoids are silvery white soft metals and tarnish rapidly in air.

2. Density and melting point : Lanthanoids are highly dense metals and have high

melting point.

3.Metallic property : They have typical metallic lustre and are good conductors of

heat and electricity.

4. Alloy formation : Lanthanoids are used for the production of alloy steel (to

improve the strength and workability) for plates and pipes. A well known alloy is

mischmetal which consists of a lanthanoid metal (95%) and iron (5% ) and traces

of S,C,Ca & Al.

Atomic and Ionic radii (Lanthanoid contraction)

The atomic and ionic radii decrease from La to Lu. This is due to the unique
property of lanthanoids known as lanthanoid contraction.
The steady decrease in atomic & ionic sizes of lanthanoid elements with
increasing atomic number is called Lanthanoid contraction.

Causes:-

In lanthanoid elements as the atomic number increases, for every additional

proton in the nucleus, the corresponding e- goes to inner 4f subshell. Due to the
poor shielding effect of inner 4f e-s, effective nuclear charge increases and
therefore the attraction of the nucleus towards the outermost shell increases
with atomic number and size of lanthanoids decreases.

The decrease in atomic radii is not regular but the decrease in ionic radii of their
M3+ ions are quite regular.

Consequences:

 Difficulty in separation of lanthoids-

Because of the similarity in radii, chemical properties of lanthanoid elements are

similar. This makes separation in pure state is difficult.

 Similarity in the size of second & third transition series

Due to lanthoid contraction, atomic size of 4d elements and corresponding 5d
elements are same. Eg: Size of Zr = Size of Hf

 Variation of basic strength of oxides and hydroxides

Due to lanthanoid contraction, the covalent nature of Ln- OH bond increases as

the basic character of oxides and hydroxides decreases from La(OH)3 to Lu(OH)3.

------------------------

Qn: Ce4+ & Tb4+can act as agents. Why?

Or

Sm2+, Eu2+ & Yb2+ can act as good reducing agents. Why?
Ans: The elements with +2 or+4 O.S. have the tendency to revert back to the most
stable O.S. , +3 . Therefore Ce4+ & Tb4+ undergo redn & Sm2+, Eu2+ & Yb2+ gets
oxidised to +3 O.S.

Note: The E0 value for Ce4+/Ce3+ is 1.74v, which suggest it can oxidize water. The rn
rate is very slow and Ce is used as a good analytical reagent.

Exception: Some elements show an O.S. of +2 or +4, even though their ions do not
have f0, f7 or f14 configuration.

Eg:- Pr, Nd, Tb & Dy also exhibits +4 state but only in oxides MO2. Sm exihibits +2
O.S. also.

Atomic and Ionic radii. (Lanthanoid contraction)

Atomic radii and ionic radii of tripositive lanthanoids show a steady and gradual
decrease in moving from La to Lu. Atomic radii show some regularities but ionic
radii show a steady decrease.

The steady decrease in atomic & ionic sizes of lanthanoid elements with
increasing atomic number is called Lanthanoid contraction.

Causes:-

In lanthanoid elements as the atomic number increases, for every additional

proton in the nucleus, the corresponding e goes to inner 4f subshell. Due to the
poor shielding effect of inner 4f es, effective nuclear charge increases and
therefore the attraction of the nucleus towards the outermost shell increase in
atomic number, size of lanthoids decreases.

Consequences:-

 Difficulty in separation of lanthoids-

Because of the similarity in radii, chemical properties of lanthanoid elements are

similar. This makes separation in pure state is difficult.

 Similarity in the size of second & third transition series

Due to lanthoid contraction, atomic size of 4d elements and corresponding 5d
elements are same. Eg i e of r Size of Hf

 I.E. of elements is higher than that of 4d elements.

 Variation of basic strength of hydroxides

On moving from left to right, inlanthanoids as the size of the metal decreases, M-
OH bond strength increases. Therefore basic strength of the hydroxides decrease
from left to right.

La(OH)3 is more basic than LuCOH3

Uses:-

anthanoids are used for the production of alloy steel (to improve the strength
and wor ability) for plates and pipes. A well nown alloy is mischmetall which
consists of a lanthanoid metal ( 5 ) and iron (5 ) and traces of ,C,Ca & Al.