d and f-Block Elements

INTRODUCTION

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 periods. The f-
block consists of elements in which 4 f and 5 f orbitals are progressively filled.
The names transition metals and inner transition metals are often used to
refer to the elements of d-and f-blocks respectively.
Originally the name transition metals was derived from the fact that their
chemical properties were transitional between those of s and p-block
elements. 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.
Electronic Configurations of the d-Block Elements

In general the electronic configuration of outer orbitals of these elements

is (n-1)d1–10ns1–2. However, this generalization has several exceptions because
of very little energy difference between (n-1)d and ns orbitals as we see in the
case of Cu and Cr.
There are greater similarities in the properties of the transition elements of
a horizontal row in contrast to the non-transition elements.

Related Questions:
 On what ground can you say that scandium (Z = 21) is a transition
element but zinc (Z = 30) is not?
 Silver atom has completely filled d orbitals (4d10) in its ground state. How
can you say that it is a transition element?
Physical 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.
With the exceptions of Zn, Cd, Hg
and Mn, they have one or more
typical metallic structures at
normal temperatures.
Transition metals have high
melting point and boiling point.
This is due to the strong metallic
bonding.
Variation melting point in the three transition series.
Enthalpy of atomization:
Transition elements
have very high enthalpy
of atomization due to the
strong metallic bonds they
form. The exceptionally
low value in the middle of
each series is due to the
stability of their electronic
configurations.

Variation of enthalpy of atomization in the three transition series.

Atomic and ionic sizes
The variation of atomic size
within a series is quite small. The
radii of the third (5d) series are
virtually the same as those of the
corresponding members of the
second series (4d).
This is because of lanthanoid
contraction. Lanthanoid contraction
is caused due to imperfect
shielding of f electrons. 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 properties.
The decrease in metallic
radius coupled with increase in
atomic mass results in density of
these elements. Variation of atomic size in the three transition series.
Ionization enthalpy:
There is an increase in ionization enthalpy along each series of the
transition elements from left to right due to an increase in nuclear charge.
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 stabilization
of energy state.
The successive enthalpies of these elements do not increase as steeply as
in the case of non-transition elements. The trend in change of first ionization
enthalpy in a series is irregular.
Ionization enthalpy will decrease when the resulting ion formed is either d5
or d10 as in the case of formation of Fe3+ ion.
The lowest common oxidation state of these metals is +2.
Related Questions:
 Why is the third ionization enthalpy of Zinc very high?
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 variability of oxidation
states, arises out of incomplete filling of d orbitals in such a way that their
oxidation states differ from each other by unity.
Oxidation Trends in the M2+/M Standard Electrode Potentials:
The general trend
towards less negative Eo
values across the series is
related to the general
increase in the sum of the
first and second ionisation
enthalpies. The value of Eo
for Mn, Ni and Zn are
more negative than
expected from the trend.
The positive value of
Cu is due to the high
energy to transform Cu(s)
to Cu2+ is not balanced by
its hydration enthalpy.
Trends in Stability of Higher Oxidation States:
The higher oxidation states in transition metals are usually seen oxides and
fluorides. This is due to there ability to form strong covalent bonds owing to the
small size and high electronegativity. The ability of oxygen to stabilise these high
oxidation states exceeds that of fluorine. The ability of oxygen to form multiple
bonds to metals explains its superiority.

Related Questions:
 Why is Cr2+ reducing and Mn3+ oxidising when both have d4 configuration?
 The Eo (M2+/M) value for copper is positive (+0.34V). What is possible
reason for this?
 Why is the Eo value for the Mn3+/Mn2+ couple much more positive than that
for Cr3+/Cr2+ or Fe3+/Fe2+? Explain.
 Which is a stronger reducing agent Cr2+ or Fe2+ and why ?
 Why is the highest oxidation state of a metal exhibited in its oxide or
fluoride only?
Magnetic Properties:
Most of the transition metal ions
are paramagnetic. This is because of
the presence of unpaired electrons.
The magnetic moment is determined
by the number of unpaired electrons
and is calculated by using the ‘spin-
only’ formula.
μ = √ n (n+2)
where n is the number of
unpaired electrons and µ is the
magnetic moment in units of Bohr
magneton (BM).

Related Questions:
 Calculate the magnetic moment of a divalent ion in aqueous solution if its
atomic number is 25.
Formation of Coloured Ions
Transition metal ions are mostly coloured. 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 in the visible region. The colour
observed corresponds to the complementary colour of the light absorbed.
The ions with d0 and d10 configuration will not exhibit colour because
transition of electrons among d-orbitals is not possible.

Formation of Complex Compounds:

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.

Related Questions:
 Why is that Zn2+ and Sc3+ are colourless in nature?
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. These metals and ions are also good adsorbents for
reactants.
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. Transition metals from
interstitial compounds because the void spaces in their crystals are large enough
to accommodate small molecules. The properties of metals are altered by
formation of interstitial compounds.
Formation of Alloys
Because of similar radii and other characteristics of transition metals, alloys
are readily formed by these metals. The alloys so formed are hard and have
often high melting points and also have great industrial importance.
Potassium dichromate. K2Cr2O7
Preparation:

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.
4 FeCr2O4 + 8 Na2CO3 + 7 O2 → 8 Na2CrO4 + 2 Fe2O3 + 8 CO2
The yellow solution of sodium chromate is filtered and acidified with
sulphuric acid to give a solution from which orange sodium dichromate, Na2Cr2O7
. 2 H2O can be crystallised.
2 Na2CrO4 + 2 H+ → Na2Cr2O7 + 2 Na+ + H2O
Potassium dichromate is prepared by treating the solution of sodium
dichromate with potassium chloride.
Na2Cr2O7 + 2 KCl → K2Cr2O7 + 2 NaCl
Orange crystals of potassium dichromate crystallise out.
Potassium dichromate. K2Cr2O7
Structure:

Properties:
The chromates and dichromates are interconvertible in aqueous
solution depending upon pH of the solution. The oxidation state of chromium in
chromate and dichromate is the same.
2 CrO42– + 2 H+ → Cr2O72– + H2O
Cr2O7 2– + 2 OH- → 2 CrO42– + H2O
Potassium dichromate. K2Cr2O7
Properties:
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. In acidic solution,its oxidising action can be
represented as follows:
Cr2O72– + 14 H+ + 6 e– → 2 Cr3+ + 7 H2O (Eo = 1.33V)
Thus, acidified potassium dichromate will oxidise iodides to iodine,
sulphides to sulphur, tin(II) to tin(IV) and iron(II) salts to iron(III). The half-
reactions are noted below:
6 I – → 3 I 2 + 6 e–
3 Sn2+ → 3 Sn4+ + 6 e–
6 Fe2+ → 6 Fe3+ + 6 e–
3 H2S → 6 H+ + 3 S + 6 e–
The full ionic equation is obtained by adding the half-reactions.
Cr2O72– + 14 H+ + 6 Fe2+ → 2 Cr3+ + 6 Fe3+ + 7 H2O
Potassium permanganate. KMnO4
Preparation:
Potassium permanganate is prepared by fusion of MnO2 (Pyrolusite) with
an alkali metal hydroxide and an oxidising agent like KNO3. This produces the
dark green K2MnO4 ( Potassium Manganate) which disproportionates in a neutral
or acidic solution to give permanganate.
2 MnO2 + 4 KOH + O2 → 2 K2MnO4 + 2 H2O
3 MnO42– + 4 H+ → 2 MnO4– + MnO2 + 2 H2O
Commercially it is prepared by the alkaline oxidative fusion of MnO2
followed by the electrolytic oxidation of manganate (Vl).
In the laboratory, a manganese (II) ion salt is oxidised by peroxodisulphate
to permanganate.
2 Mn2+ + 5 S2O82– + 8 H2O → 2 MnO4– + 10 SO42– + 16 H+
Potassium permanganate forms dark purple (almost black) crystals which
are isostructural with those of KClO4.
Potassium permanganate. KMnO4
Structure and physical properties:

Both manganate and permanganate ion has tetrahedral

structure, The structural difference being an extra Mn=O in the
permanganate ion. The π bonds present in these ions are
dπ – pπ bonds.
Permanganate ion has an intense purple colour which
can be attributed to charge transfer transition which is
explained using MO theory. Manganate ion has green colour.
Permanganate ion is diamagnetic while manganate ion
is paramagnetic due to the presence of an unpaired electron.
Permanganate is not very soluble in water and when
heated it decomposes at 513 K.
2 KMnO4 → K2MnO4 + MnO2 + O2
Potassium permanganate. KMnO4
Chemical properties:
Permanganate ion is a strong oxidizing agent. The oxidizing tendency
depends upon the pH of the medium. As the medium becomes more acidic the
product formed vary from MnO42–,MnO2 and Mn2+. The number of electrons
involved vary.
MnO4– + e– → MnO42– (Eo= + 0.56 V)
MnO4– + 4 H+ + 3e– → MnO2 + 2 H2O (Eo = + 1.69 V)
MnO4– + 8 H+ + 5e– → Mn2+ + 4 H2O (Eo = + 1.52 V)

A few important oxidising reactions of KMnO4 are given below:

In acid solutions:
(a) Iodine is liberated from potassium iodide :
10 I– + 2 MnO4– + 16 H+ → 2 Mn2+ + 8 H2O + 5I2
(b) Fe2+ ion (green) is converted to Fe3+ (yellow):
5 Fe2+ + MnO4– + 8 H+ → Mn2+ + 4 H2O + 5 Fe3+
Potassium permanganate. KMnO4
(c) Oxalate ion or oxalic acid is oxidised at 333 K:
5 C2O42– + 2 MnO4– + 16 H+ → 2 Mn2+ + 8 H2O + 10 CO2
(d) Hydrogen sulphide is oxidised, sulphur being precipitated:
5 S2– + 2 MnO4– + 16 H+ → 2 Mn2+ + 8 H2O + 5 S
(e) Sulphurous acid or sulphite is oxidised to a sulphate or sulphuric acid:
5 SO32– + 2 MnO4– + 6 H+ → 2 Mn2+ + 3 H2O + 5 SO42–
(f) Nitrite is oxidised to nitrate:
5 NO2– + 2 MnO4– + 6 H+ → 2 Mn2+ + 5 NO3– + 3 H2O
In neutral or faintly alkaline solutions:
(a) A notable reaction is the oxidation of iodide to iodate:
2 MnO4– + H2O + I– → 2 MnO2 + 2 OH– + IO3–
(b) Thiosulphate is oxidised almost quantitatively to sulphate:
8 MnO4– + 3 S2O32– + H2O → 8 MnO2 + 6 SO42– + 2 OH–
(c) Manganous salt is oxidised to MnO2; the presence of zinc sulphate
or zinc oxide catalyses the oxidation:
– 2+ +
f-block elements (Lanthanoides)
Introduction:
The f-block elements are called inner transition elements. The outermost
electron is filled in the f-orbital of the antepenultimate shell. The general
electronic configuration of lanthanides is [Xe] 4f1-14 5d0,1 6s2.
f-block elements (Lanthanoides)
Atomic and ionic sizes:
The overall decrease in atomic and
ionic radii from lanthanum to lutetium is called
lanthanoid contraction. This phenomenon is
caused due to the imperfect shielding 4 f
electrons. Lanthanoid contraction is a
cumulative effect
The consequences of lanthanoid
contraction are that the radii of the members
of the third transition series becomes similar
to 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.
f-block elements (Lanthanides)
Oxidation States :
The most common oxidation state is +3 oxidation state. Occasionally +2 and
+4 ions in solution or in solid compounds are also obtained. The stability of +2
and +4 oxidation states can be attributed to the stable electronic configurations
of these ions ( f0, f7 or f14).
Thus, the formation of Ce(IV) is favoured by its noble gas configuration, but it
is a strong oxidant reverting to the common +3 state. This also makes Ce(IV) a
good oxidizing agent and good analytical reagent.
Pr, Nd, Tb and Dy also exhibit +4 state. Eu2+ is formed by losing the two s
electrons and its f7 configuration accounts for the formationof this ion. However,
Eu2+ is a strong reducing agent changing to the common +3 state. Similarly Yb2+
which has f14 configuration is a reductant. Tb(IV) 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.
f-block elements (Lanthanoides)
General properties:
All the lanthanoids are silvery white
soft metals and tarnish rapidly in air.
The hardness increases with increasing
atomic number, samarium being steel
hard.
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.
The chemical reactivities are similar
to that of calcium and aluminium
metals.
f-block elements (Lanthanoides)
Uses:
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.

Related Questions:
 Why is Ce(IV) a good analytical reagent and a good oxidizing agent.
f-block elements (Actinoides)
Electronic configuration:
The general electronic configuration of actinoides is [Rn] 5f1-14 6d0,1 7s2.
The elements after Uranium are called trans-uranic elements and are artificial
and radioactive.
f-block elements (Lanthanides)
Atomic and ionic sizes:
There is a gradual decrease in the size of atoms or M3+ ions across the
series. This may be referred to as the actinoid contraction (like lanthanoid
contraction). The contraction is, however, greater from element to element in this
series resulting from poor shielding by 5f electrons.

Oxidation States:
There is a greater range of oxidation states, which is in part attributed to
the fact that the 5f, 6d and 7s levels are of comparable energies. The actinoids
resemble the lanthanoids in having more compounds in +3 state than in the +4
state.
f-block elements (Lanthanides)
General properties:
The actinoid metals are all silvery in appearance but display a variety of
structures. The structural variability is obtained due to irregularities in metallic
radii which are far greater than in lanthanoids.
The actinoids are highly reactive metals, especially when finely divided.
The magnetic properties of the actinoids are more complex than those of the
lanthanoids.
The ionization enthalpies of the early actinoids, though not accurately known,
but are lower than for the early lanthanoids.

Related Questions:
 Actinoid contraction is greater from element to element than lanthanoid
contraction. Why?
 Why do actinoids show more variety for oxidation state than lanthanoids.
Applications of d and f block elements:
 Iron and steels are the most important construction materials.
 Some compounds are manufactured for special purposes such as TiO for the
pigment industry and MnO2 for use in dry battery cells.
 The battery industry also requires Zn and Ni/Cd.
 The coinage metals Ag and Au are restricted to collection items and the
contemporary UK ‘copper’ coins are copper-coated steel. The ‘silver’ UK coins
are a Cu/Ni alloy.
 Many of the metals and/or their compounds are essential catalysts in the
chemical industry.
• V2O5 catalyses the oxidation of SO2 in the manufacture of sulphuric acid.
• TiCl4 with Al(CH3)3 is Ziegler catalyst used to manufacture polythene.
• Iron catalysts are used in the Haber process for the production of ammonia.
• Nickel catalysts enable the hydrogenation of fats to proceed.
• Wacker process for oxidation of ethyne to ethanal is catalysed by PdCl2.
 Nickel complexes are useful in the light light-sensitive properties of AgBr.
End of
Chapter