d- & f- Block Elements

d-and f-Block Elements:

• General introduction, electronic configuration, occurrence and characteristics of transition
metals, general trends in properties of the first row transition metals – metallic character,
ionization enthalpy, oxidation states, ionic radii, colour, catalytic property, magnetic
properties, interstitial compounds, alloy formation.
• Lanthanoids - Electronic configuration, oxidation states and lanthanoid contraction and its
consequences.
d-Block Elements

• The elements lying in the middle of Periodic Table

between s- and p-block elements (group 2 -13) are
known as d-block elements.

• The d– Block elements are also known as transition elements.

• These elements have their properties which are intermediate between those of s
and p block elements.

• All these elements are metals.

THE TRANSITION ELEMENTS (d-BLOCK)

• 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.
• For example:-
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.
Classification of d- Block Elements
These are four main transition series.
• 3d-series- It involves the filling of 3d orbitals and has 10 elements from
scandium to zinc in the fourth period.

• 4d-series- It involves the filling of 4d orbitals and has 10 elements from

ytterium to cadmium in the fifth period.

• 5d-series- It involves the filling of 5d orbitals and has 10 elements from

lanthanum and hafnium to mercury in the sixth period.

• 6d-series- It involves the filling of 6d orbitals, starting with Actinium

and rutherfordium to copernicium in the seventh period.
 Electronic Configuration d-Block Elements-

The general electronic configuration of outer orbitals of these elements is (n-1)d1-10 ns1-2.
General Properties of the Transition Elements (d-
Block)
• Physical Properties
• Metallic properties:
Nearly all the transition elements display typical metallic properties
such as high tensile strength, ductility, malleability, high thermal and
electrical conductivity and metallic lustre.
The transition metals (with the exception of Zn, Cd and Hg) are very
much hard and have low volatility.
Melting and Boiling points

• Their melting and boiling points are high.

• The high melting points of these metals are attributed to the
involvement of greater number of electrons from (n-1)d in addition to
the ns electrons in the interatomic metallic bonding. In any row the
melting points of these metals rise to a maximum at d5 except for
anomalous values of Mn and Tc and fall regularly as the atomic
number increases.
Trends in the melting points of the 3d, 4d and
5d transition metals.
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 and 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 same trend is observed in the atomic radii of a given series.
However, the variation within a series is quite small.
Atomic and Ionic Radius
• Generally the atomic radii of d-
block elements decreases with
increase in atomic number but
the decrease in atomic size is
small after midway.
• At the end of the period , there is
a slight increase in the atomic
radii.
• The atomic radii of the second
and third transition series are
almost the same- due to
lanthanide contraction.
 Ionisation Enthalpies
• Due to an increase in nuclear charge which accompanies the filling of the inner d-
orbitals, there is an increase in ionization enthalpy along each series of the
transition elements from left to right. However, many small variations occur.
Although the first ionization enthalpy,
• in general, increases, the magnitude of the increase in the second and third
ionization enthalpies for the successive elements, in general, is much higher. In 3d
series, 1st I.E of zinc is ,however, very high because of fully filled (n-1) d10 ns2
configuration.
• There is a fall in 2nd I.E from Cr to Mn and from Cu to Zn because after the removal
of first electron, Cr and Cu acquire a stable configuration(d5 and d10) and the removal
of 2nd electron is very difficult.
• 3rd I.E of Mn is very high because the 3rd electron has to be removed from the stable
half filled 3d orbital.
Oxidation States (O.S)
• Transition metals show variable oxidation states due to tendency of (n-1)d
and ns electrons to take part in bond formation, since there is a very little
difference in the energies of these orbitals.

• Except for scandium and zinc, all the other elements show more than one
oxidation state. Scandium, due to the availability of very few electrons for
bonding, does not show variable oxidation states.
• On the other hand, zinc, due to the presence of too many d electrons, has fewer
orbitals available for bonding, and thus, does not exhibit variable O.S.
• The elements from titanium to zinc, with the exception of copper, show a
minimum O.S of +2. Copper shows a minimum oxidation state of +1 (+2 O.S is
due to the loss of two ns2 electrons.
• Mostly ionic bonds are formed in +2 and +3 oxidation states. In compounds of
higher O.S, the bonds formed are mostly covalent since they are formed by
sharing of d- electrons. For example all the bonds between manganese and oxygen
are covalent in MnO4- (permanganate ion).
• The elements which show the greatest number of oxidation state occur in or near
the middle of the series. For example, Mn shows all the O.S from +2 to +7.
• The maximum O.S is given by the sum of the s and d electrons for the first five
elements. Ex: Sc, Ti, V, Cr and Mn exhibit maximum O.S of +3, +4, +5, +6 and
+7. The maximum O.S of reasonable stability in the first transition series is equal
to the sum of s and d electrons up to Mn followed by an abrupt decrease in the
stability of higher O.S.
• The variability of O.S of transition elements, which is due to incompletely filled d-
orbitals arises in such a way that successive oxidation states differ by unity, example VII,
VIII, VIV, VV. This is unlike non-transition elements where O.S normally differs by two
units example PbII, PbIV.

• In a group of d- block elements, the higher O.S are more stable for heavier elements for
example, in group 6, Mo(VI) and W(VI) are found to be more stable then Cr(VI). For this
reason, Cr(VI) in the form of dichromate is a stronger oxidizing agent in acidic medium
whereas MoO3 and WO3 or not.

• Low oxidation states are found when a complex compound has ligands capable of pi –
acceptor character in addition to the sigma – bonding. For example, in Ni(C0)4 and
Fe(CO)5 , the oxidation state of nickel and iron is zero.
Trends in the stability of Higher Oxidation States

• TiX4, VF5 and CrF6 have the highest oxidation numbers.

• 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 stabilize 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 example VF5 and CrF6.
• Although V directly shows an oxidation state of +5 only in VF5, other halides,
however, undergo hydrolysis to give oxohalides, VOX3 in which oxidation state
of V is +5.
• In the low oxidation state, fluorides are unstable, example TiX2, VX2, CuX but
not F-. Cu(II) halides are known except the iodide. In this case Cu2+ oxidises I-
to I2.
2Cu2+ + 4I- → Cu2I2(S) + I2
• Cu(I) compounds are unstable in aqueous solution and undergo
disproportionation.
Cu+ → Cu2+ + Cu
 Trends in the stability of higher oxidation states of
transition metal oxides

• The highest oxidation state in the oxides is same as that of group number upto group 7(Sc2O3
and Mn2O7).
• Beyond group 7, the maximum oxidation is +3 (Fe2O3), although in the ferrates (FeO4)2-
forward in the alkaline medium, Fe has oxidation state of +6. But these readily decomposed to
Fe2O3 and O2.
• Besides the oxides, higher oxidation states are found in the oxocations and oxoanions eg. V(V)
in VO+, V(IV) in VO2+, Ti(IV) in TiO2+, Mn(VII) in MnO4- .
• The stability of oxygen to stabilize these high oxidation states exceeds that of fluorine. The
highest MN fluoride is MNF4 whereas the highest oxide is MN207.
• The stability of oxygen to stabilise high oxidation states exceeds that of
fluorine. The highest Mn fluoride is MnF4 whereas the highest oxide is
Mn207. The ability of oxygen to form multiple bonds to metals explains its
superiority.
 Electrode Potential
The oxidative and reductive strengths of a variety of substances can be
compared using standard electrode potentials. Apparent anomalies can be
explained by the fact that electrode potentials are measured in aqueous
solution, which allows for strong intermolecular electrostatic interactions,
and not in the gas phase.

Thermodynamically Electrode potential depends upon the sum of :

• enthalpy of sublimation,
• ionization enthalpy(ies)/ electron gain enthalpy
• and hydration enthalpy.
Trends in the M2+/M standard electrode potentials

• There is no regular trend in

the E0 (M2+/M) values. This
is because their ionization
enthalpies (IE1 + IE2) and
sublimation enthalpies do
not show any regular trend.
• The general trend towards
less negative E0 values
along the series is due to
the general increase in the
sum of first and second
ionization enthalpies.
• Copper shows a unique behaviour (positive value for E0). This explains why is
does not liberate H2 gas from acids. It reacts only with the oxidizing acids
(HNO3 and H2SO4) which are reduced. The reason for positive E0 value for
copper is that the sum of enthalpies of sublimation and ionization is not
balanced by hydration enthalpy.
• The values of E0 for Mn, Ni and Zn are more negative than expected from the
general trend. This is due to greater stability of half-filled d-subshell (d5) in
Mn2+, and completely filled d-subshell (d10) in Zn2+. The exceptional behaviour
of Ni towards E0 value from the regular trend is due to its high negative
enthalpy of hydration.
Trends in the M3+/M2+ Standard Electrode Potentials
• A very low value for E0 (Sc3+/Sc2+) reflects the stability of Sc3+ ion which has a
noble gas configuration. (shown in table 8.2)
• The highest value for Zn is on account of very high stability of Zn2+ ion with
d10 configuration. It is difficult to remove an electron from it to change it into +3
states.
• The comparatively high value of E0 (Mn3+/Mn2+) shows that Mn2+ is very stable
which is on account of stable d5 configuration of Mn2+.
• The comparatively low value of E0 (Fe3+/Fe2+) is on account of extra stability of
Fe3+ (d5), i.e., low third ionization enthalpy of Fe.
• The comparatively low value for V is on account of the stability of V2+ ion due to
its half-filled t2g3 configuration.
Chemical Reactivity and E0 Values
• The transition metals vary widely in their chemical reactivity. Some of them are
highly electropositive and dissolve in mineral acids whereas a few of them are
‘noble’, i.e., they do not react with simple acids.
Chemical reactivity of transition metals are related to their E0 values:
• The metals of the first transition series (except copper) are relatively more reactive
than the other series. Thus, they are oxidized by H+ ions though the actual rate is
slow, e.g., Ti and V are passive to dilute non-oxidizing acids at room temperature.
• Less negative E0 values for M2+/M along the series indicate a decreasing tendency
to form divalent cations.
• More negative E0 values than expected for Mn, Ni and Zn show greater stability
for Mn2+, Ni2+ and Zn2+.
• E0 values for the redox couple M3+/M2+ indicate that Mn3+ and Co3+ ions are the
strongest oxidizing agents in aqueous solution whereas Ti2+, V2+ and Cr2+ are
strongest reducing agents and can liberate hydrogen from a dilute acid, e.g.,
 MAGNETIC PROPERTIES
• Substances which contain species (Atoms/ions/molecules) with unpaired electrons
in their orbitals – PARAMAGNETIC.
• PRAMAGNETIC SUBSTANCES are weakly attracted by the magnetic field. Strongly
attracted called FERROMAGNETIC.
• Substances which do not contain any unpaired electrons and are repelled my
magnetic field - DIAMAGNETIC.
• Transition metals usually contains unpaired electrons – so it is paramagnetic.
• Paramagnetic behavior increases with increase in unpaired electron.
• Para magnetism expressed in terms of Magnetic moment., it is related to no. of unpaired
electrons.
• The magnetic moments calculated from the ‘spin-only’ formula and those derived
experimentally. Magnetic moment μ = √ n(n+2) BM
• Magnetic moment of an electron is due to its spin angular momentum and orbital
angular momentum
• Magnetic moment of transition elements is due to spin angular momentum only, The orbital
momentum is quenched
 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.
• 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. (CFT)
• Zn 2+ / Cd 2+ - all d orbitals are fully filled
• Ti 4+ - all d orbitals are vacant so, no d – d transition occurs. Therefore
they do not absorb radiations. So they are colourless.
 Formation of Complex Compounds
• Metal ions bind to a number of anions or neutral molecules giving complex compounds
• For example-[Fe(CN)6]3–, [Fe(CN)6]4–, [Cu(NH3)4]2+ and [PtCl4]2– .
• The transition metals form a large number of complex compounds. This is due to
• Comparatively smaller sizes of the metal ions,
• Their high ionic charges and
• The availability of d orbitals for bond formation.
 Formation of 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 •example, TiC, Mn4N, Fe3H, VH0.56
and TiH1.7
• Properties
(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
• Alloys are a homogeneous solid solution in which the atoms of one
metal are randomly distributed among the other.
• Condition for formation of alloy- the atoms of alloying metals should
have their radii within 15 percent of each other.
• Because of similar radii and other characteristics of transition metals,
• The alloys so formed are hard and have often high melting points
• ferrous alloys: chromium, vanadium, tungsten, molybdenum and
manganese 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),
 CATALYTIC ACTIVITY
• 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.
• 2 I- + S2O82-→I2 +2 SO42-
• 2 Fe3+ + 2 I- → 2 Fe2+ + I2
• 2 Fe2+ + S2O82- →2 Fe3+ + 2 SO42-
 DISPROPORTIONATION
• When a particular oxidation state becomes less stable relative to other
oxidation states, one lower, one higher, it is said to undergo
disproportionation. For example, manganese (VI) becomes unstable
relative to manganese(VII) and manganese (IV) in acidic solution.
• 3 MnVIO4 2– + 4 H+ → 2 MnVIIO–4 + MnIVO2 + 2H2O
 THE INNER TRANSITION ELEMENTS
( f-BLOCK)
• The elements in which the additional electrons enters (n-2)f orbitals are
called inner transition elements. The valence shell electronic configuration of
these elements can be represented as
• (n – 2)f0-14(n – 1)d0-1ns2.
• The lanthanoids resemble one another more closely than do the members of
ordinary transition elements in any series. They have only one stable
oxidation state +3.
• 4f inner transition metals are known as lanthanides because they come
immediately after lanthanum and 5f inner transition metals are known as
actinoids because they come immediately after actinium.
THE LANTHANOIDS
• Electronic configuration:
Atoms of these elements have electronic
Configurations with 6s2 common but with variable
occupancy of 4f level.
Oxidation States

• Predominantly +3 oxidation state.

• +3 oxidation state in La, Gd, Lu are especially stable ( Empty half filled
and Completely filled f – subshell respectively) •
• Ce and Tb shows +4 oxdn state ( Ce4+ 4fo & Tb4+ 4f7)
• Occasionally +2 and +4 ions in solution or in solid compounds are also
obtained. • This irregularity arises mainly from the extra stability of
empty, half filled or filled f subshell.
• The most stable oxidation state of lanthanides is +3. Hence the ions in
+2 oxidation state tend to change +3 state by loss of electron acting as
reducing agents whereas those in +4 oxidation state tend to change to
+3 oxidation state by gain of electron acting as a good oxidising agent in
aqueous solution. •
• Why Sm2+, Eu2+, and Yb2+ ions in solutions are good reducing
agents but an aqueous solution of Ce4+ is a good oxidizing agent?
 Atomic and Ionic Sizes
Lanthanoid contraction:
The steady decrease in atomic and ionic radii of lanthanoids with increase
in atomic number is called lanthanoid-contraction. The decrease in
atomic radii is not quite regular as it is regular in M3+ ions.
Cause of lanthanoid-contraction: This contraction is attributed to the
imperfect shielding of one electron by another in the same sub-shell.
However, the shielding of one 4 f electron by another is less than one d
electron by another with the increase in nuclear charge along the series.
There is fairly regular decrease in the sizes with increasing atomic
number.
 Consequences of lanthanoid contraction
• Lanthanoid Contraction causes the radii of the members of the third
transition series to be very similar to those of the corresponding
members of the second series.
• The almost identical radii of Zr (160 pm) and Hf (159 pm), a consequence
of the lanthanoid contraction, account for their occurrence together in
nature and for the difficulty faced in their separation.
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