THE d- AND f-BLOCK ELEMENTS

Introduction to d-block 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 metals are 3d series from Sc to Zn, 4d
series from Y to Cd and 5dseries from La to Hg.
• The fourth 6dseries begins from Ac and is incomplete till now.

Position of d-block in periodic table

CHEMISTRY THE d- AND f-BLOCK ELEMENTS

• The d-block elements are found in the middle section of s- and p- block
elements in the periodic elements.
• This lead to its name ‘transition’ due to its position between s- and p- block
elements.

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 outer shells.
• Where (n–1) = Inner d orbitals having electrons from 1-10.
• ns = Outermost orbital may have one or two
• (n-1) d10 n s2 represents the electronic configurations of Zn, Cd and Hg.
• They exhibit variable valency that differ by units of one.
CHEMISTRY THE d- AND f-BLOCK ELEMENTS

Physical Properties

• The transition metals are hard and tough. They have low volatility butZn,
Cd and Hg are an exception.

• They have high melting and boiling points due to the greater quantity of
electrons from (n- 1) d along with the ns electrons metallic
CHEMISTRY THE d- AND f-BLOCK ELEMENTS

Fig. The trends in melting point of d-block elements.

• Metals possessing high boiling point are noble
• The metals belonging to second and third series have greater enthalpies
of atomisation than the elements belonging to first series.

Fig. Enthalpies of atomisation

Metallic characteristics:

• All transition metals exhibit metallic character.

CHEMISTRY THE d- AND f-BLOCK ELEMENTS

• They are good conductors of heat and electricity.

Fig. Metal is used at the tip of the plug that is inserted into the socket
• They are hard and tough.
• Being metal they exhibit the property of malleability, ductility and sonorousity.

• EG: Aluminium is beaten into thin sheets to make aluminium foil used to
pack food (Malleability)

• Bells in temples are made of metal that when struck against hard surface produces
sound (Sonorousity)

• Metals are drawn into wires (Ductility)

• They form alloys by combining with some other metals.
• They are found to exist in face- centered cubic (fcc) structure,
hexagonal close-packed (hcp) structure and body-centered cubic (bcc)
structure.
• The transition elements exhibit covalent as well as metallic bonding within the
atoms.

Atomic radii

• The atomic radii of the elements of 3d-series decreases as the atomic number
increases.
• The atomic radii increase from 3d to 4d, the atomic radii of the 4d and 5d
transition series are very close due to lanthanoid contraction. For example,
Zirconium and Hafnium.
• This decrease in the metallic radius due to increase in the atomic mass
leads to an increase in the density of elements. Consequently the density
increases from titanium to copper.
CHEMISTRY THE d- AND f-BLOCK ELEMENTS

Ionisation Enthalpies

• Transition elements have small size which results in high ionization energy.
• They exhibit less electro positivity than the s-block elements due to
their ionization potentials lying between S and P block elements.
• They form covalent compounds.
• The d-block elements exhibit an increase in the ionization potentials from
left to right due to the screening effect of the new electrons added into the
(n-1) d subshell.
• The first transition series exhibit an increase in the second ionisation
energies with the increase in atomic number due to stable electronic
configuration.
• Ionization energy decreases down the group.
• Ionization energy increases across the period.
CHEMISTRY THE d- AND f-BLOCK ELEMENTS

Oxidation States

• The number allotted to an element in a compound representing the number

of electrons lost or gained by an atom of the element of the compound is
called oxidation state.
For example, the electron configuration of copper is [Ar] 3d10 4s1. It attains noble
gas configuration by losing one electron. The energy required to lose one more
electron is very less and hence copper loses 2 electrons and forms Cu2+ ion.
Therefore copper exhibits +1 and +2 oxidation state. But +2 oxidation states are
more common.
It forms compounds like CuCl2 and also with oxygen like CuO. In both the cases
the oxidation state of Cu is +2.
• Transition elements exhibit varying oxidation states due to the minor
energy difference between ns and (n -1) d orbitals.
• Along with ns electrons, (n -1) d electrons takes part in bonding. But due to
the availability of few electrons for bonding Scandium does not show
variable oxidation states.
• Due to presence of more d electrons, zinc has less orbital available for
bonding and hence does not exhibit varying oxidation state.
• Among d-block elements the elements belonging to 8th group exhibit
maximum oxidation state.
• Among the elements of 3d –series Manganese belonging to 7th group
exhibits maximum oxidation state.
• Among the elements of 4d-Series Ruthenium belonging to 8th group
exhibits maximum oxidation state.
• Among the elements of 5d-Series Osmium belonging to 8th group
CHEMISTRY THE d- AND f-BLOCK ELEMENTS

exhibits maximum oxidation state.

• The oxidation number of a free element is always 0.

• Oxidation number of (group I) elements like Li, Na, K, Rb, Cs is +1.

• Oxidation number of (group II) elements like Be, Mg, Ca, Sr, Ba is +2.
• Oxidation number of oxygen is -2.
Trends in the M 2+/M Standard Electrode Potentials

• The unique behaviour of Cu, having a positive E V , accounts for its inability to liberate
H2 from acids.
• Only oxidising acids (nitric and hot concentrated sulphuric) react with Cu, the acids
being reduced.
• The high energy to transform Cu(s) to Cu+2 (aq) is not balanced by its hydration enthalpy.
• It is interesting to note that the value of E V for Mn, Ni and Zn are more negative than
expected from the trend.
• The stability of the half-filled d sub-shell in Mn2+ and the completely filled d 10
configuration in Zn2+ are related to their E o values, whereas E o for Ni is related to the
highest negative hydration enthalpy.

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 d 10
configuration of Zn2+.
• The comparatively high value for Mn shows that Mn+2 (d 5 ) is particularly stable,
whereas comparatively low value for Fe shows the extra stability of Fe3+ (d 5 ).
• The comparatively low value for V is related to the stability of V2+
Magnetic Properties
Substances, depending on their behaviour in an external magnetic field, are
classified into 2 types:
Paramagnetic
• They are weakly attracted on application of magnetic field due to
presence of one or more unpaired electrons that gets attracted by the
magnetic field.
• Application of a magnetic field magnetizes the paramagnetic
substances in the same direction but lose their magnetism in the
absence of magnetic field.
• O2, Cu2+, Fe3+, Cr3+ are some examples of such substances.
CHEMISTRY THE d- AND f-BLOCK ELEMENTS

Eg:A trickle of liquid oxygen is deflected by a magnetic field, illustrating its

paramagnetism.
Diamagnetic
• They are weakly repelled by a magnetic field due to the absence of unpaired electrons.
• They are weakly magnetized on application of magnetic field in opposite direction.
• Pairing of electrons cancels out their magnetic moments and they lose
their magnetic character.
• For example, H2O, NaCl and C6H6 are some examples of such substances.
•
In 3d series the orbital angular momentum of the electrons of the elements is less
due to which they exhibit less contribution.

The magnetic moment for these elements is calculated using the spin only formula
μ = √(n(n+2))
Where n = number of unpaired electrons
μ = magnetic moment in units of Bohr Magneton (BM).

Formation of Coloured Ions

• 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

• The colour of the transition metal ions is due to the presence of unpaired or
incomplete d- orbitals.
CHEMISTRY THE d- AND f-BLOCK ELEMENTS

• The absorption of visible light and hence coloured nature of the transition
metal cations is due to the promotion of one or more unpaired d-electron from
a lower to a higher level within the same d-subshell. This promotion requires
small amount of energy available in the visible light.

• Sc3+, Ti4+, Cu+ and Zn2+ have either entirely empty or entirely filled 3d-orbital,
i.e. they do not have any unpaired d-electron, and hence appear colourless.

Formation of Complex Compounds

• The cations of transition metals have great tendency to form
complexes with several molecules or ions called ligands.
• The bonds involved in the formation of complexes are coordinate and hence
CHEMISTRY THE d- AND f-BLOCK ELEMENTS

the complexes are called coordinate complexes.

• The structure of these complex ions is linear, square, planar,
tetrahedral, octahedral depending upon nature of hybridization of
metal ions.
• The weak ligand like CO, NO forms complexes only when transition metals
are in zero due to the availability of vacant orbitals in the donor atom of the
ligand in addition to lone pair.
• The highly electronegative and basic ligand like F-, Cl- can form complexes
with transition metals even though there are in high oxidation states due to
the presence of small, highly charged or neutral ligands with lone pair of
electrons that can form strong sigma bond by donating a lone pair of
electrons.
• In a transition series the stability of complexes increases with the rise in atomic number.
• The transition metal atom reveals multiple oxidation state; the higher valent ion
forms more stable complexes.
• A few examples are: [Fe (CN)6]3–

• [Fe(CN)6]4–

• [Cu(NH3)4]2+
CHEMISTRY THE d- AND f-BLOCK ELEMENTS

• [PtCl4]2–

Formation of Interstitial Compounds

• Transition elements in combination with small atoms like H, B, C, N
etc. leads to the formation of interstitial compounds that are non-
stoichiometric in composition.
E.g.: TiH1.3, VH0.54
• The interstitial compounds so formed are chemically inert having higher
melting points as compared to pure metals. These componds are hard and
tough and keeps metallic conductivity.

Alloy Formation
• Alloys are homogeneous mixtures of more than one metal that can displace
another metal from the crystal lattice due to their comparable sizes. This
CHEMISTRY THE d- AND f-BLOCK ELEMENTS

leads to the formation of alloys.

• The alloys so formed are hard with high melting points. For example,
chromium, vanadium, tungsten, manganese, molybdenum are the ferrous
alloys.
• Some other examples are brass (alloy of copper + zinc), stainless steel,
bronze (alloy of copper + tin), etc.
Non-stoichiometric Compounds
• The compounds in which the there is no conformity in chemical composition
with the ideal chemical formula are called non-stoichiometric compounds.
• These compounds are formed due to variable valency in transition metals
and also due to the defects arising in solid state.
• The compounds formed with O, S, Se, Te, Fe, Zn etc. are the examples of such
compounds.

Preparation of K2Cr2O7
Potassium dichromate, (K2Cr2O7) is an orange-ish inorganic chemical reagent. In
different laboratory or industry it is basically used as an oxidizing agent usually
for alcohols.
It can be prepared through the following process:

• At first the fusion of chromite ore FeCr2O4 with sodium or potassium

carbonate in the presence of access of air.
4FeCr2O4 + 8Na2CO3 + 7O2 --> 8Na2CrO4 + 2FeO3 + 8CO2
• Solution of sodium chromate is first filtered and then acidified with a solution
of sulfuric acid which results in an orange sodium dichromate solution
Na2Cr2O7 2H2O can be crystallized.
2Na2CrO4 + 2H+ --> Na2Cr2O7 + 2Na+ + H2O
• Sodium dichromate is more soluble than potassium dichromate and therefore it
is fused with KCl that leads to the formation of orange crystals of potassium
dichromate.
Na2Cr2O7 + 2KCl --> K2Cr2O7 + 2NaCl
• At pH equal to 4 the dichromates and chromates exists in equilibrium
CHEMISTRY THE d- AND f-BLOCK ELEMENTS

and can be inter convertible.

• The yellow colour of chromate changes to orange coloured dichromate in
the presence of acidic medium whereas the dichromate changes into
chromate in the presence of basic medium.
• The chromate ion is tetrahedral and the dichromate ion consists of two
tetrahedral sharing at one corner, with Cr-O-Cr bond angle 126 degree.
Properties of Potassium dichromate (K2Cr2O7)
Oxidizing properties
Potassium dichromate is a powerful oxidizing-agent in an
acidic medium.

Cr2O7 2- + 14H+ + 6 electron --> 2Cr3+ +7H2O

It oxidizes iodides to iodine.
Cr2O7 2- + 14H+ + 6I- --> 2Cr 3+ + 7H2O + 3I2
It oxidizes ferrous salts to ferric salts.

Cr2O7 2- + 14H+ + 6 Fe2+ --> 2Cr 3++ 7H2O + 6Fe3+

It oxidizes stannous salts to stannic salts.

Cr2O7 2- + 14H+ + 3Sn 2+ --> 2Cr 3+ + 7H2O + 3Sn 4+

It oxidizes H2S to sulphur.

Cr2O7 2- + 8H+ + 3H2S --> 2Cr 3+ + 7H2O + 3S

Action of heat

Application of heat leads to the decomposition of Potassium dichromate leading to the

formation of potassium chromate, chromic oxide and oxygen.
4K2Cr2O7 -Heat-> 4K2CrO4 + 2CrO3 + 3O2
Preparation of Potassium Permanganate (KMnO4)
Pottassium Permanganate (KMnO4) is a dark purple solid consisting of two ions: a
potassium ion (K⁺) and a permanganate ion (MnO− 4). It is a strong oxidizing agent
and also possess medication properties due to which it is extensively used to clean
wounds and in dermatitis.
• Fusion of powdered Pyrolusite ore (MnO2) with an alkali metal hydroxide
like KOH in the presence of air or an oxidizing agent like KNO3 leads to
the formation of dark
green potassium Manganate (K2MnO4) which disproportionate either in a
neutral or acidic medium and results in the formation of potassium
permanganate.
CHEMISTRY THE d- AND f-BLOCK ELEMENTS

2 MnO2 + 4 KOH + O2 --> 2K2MnO4 + 2H2O

3 MnO42- + 4H+ --> 2MnO4- + MnO2 + 2H2O
• Potassium permanganate is commercially prepared by an alkaline
oxidative fusion of Pyrolusite ore (MnO2) and again by the
electrolytic oxidation of manganate (4) ion.
2 MnO2 + 4KOH + O2 --> 2K2MnO4 + 2H2O
MnO42- + (electrolytic oxidation) --> MnO4- + e-
Introduction to f-Block Elements

• These elements are also called inner transition elements because the last
electron enters (n−2) f-orbital, i.e. inner to the penultimate energy level
and forms a transition series.
• The general electronic configuration of these elements
can be given as Hence, they have three incomplete
shells, viz. (n−2), (n−1) and nth.

Classification of f-block elements

✓ Lanthanoids:

▪ They are called Lanthanoids because they come immediately after

Lanthanum.
▪ They are also called 4f-block elements or first inner transition
series elements or lanthanides or lanthanons.

✓ Actinoids:

▪ They are called Actinoids because they come immediately after Actinium.
▪ They are also called 5f-block elements or second inner transition series
elements
CHEMISTRY THE d- AND f-BLOCK ELEMENTS

or actinides or actinons.

The Lanthanoids:

❖ Electronic Configuration:

• Lanthanoids have the common electronic configuration of 6s2 and

electrons occupying 4f level variably. The electronic configuration of
all the tri positive ions are of the form 4fn (n = 1 −14) with increasing
atomic number.
CHEMISTRY THE d- AND f-BLOCK ELEMENTS

• The electronic configuration of Europium (Z = 63) is 4f7 6s2 and that

of Gadolinium (Z = 64) is 4f7 5d1 6s2. This can be explained on the
basis of extra stability of the half-filled orbitals in their cores.
• The electronic configuration of Ytterbium (Z = 70) is 4f14 6s2 and
that of Lutetium (Z = 71) is 4f14 5d1 6s2. This is also explained on
the basis of extra stability of the filled orbitals in their cores.

❖ Oxidation states:

• The common oxidation state of the lanthanoids is +3.

• The +2 and +4 oxidation states are very less common. These are
exhibited by those elements which attain a stable electronic
configuration of f0, f7 or f14 by losing 2 or 4 electrons.
• Here, each element tries to attain the stable oxidation state by losing
or gaining electrons, i.e.
+3. Hence, Sm2+, Eu2+ and Yb2+ ions in solutions are good reducing
agents and aqueous solutions of Ce4+ and Tb4+ are good oxidising
agents.

❖ Atomic and ionic radii of Lanthanoids:

• In lanthanoids, if the atomic number increases, atomic and ionic

radii decrease from La3+ toLu3+.

Variation of ionic radii of trivalent lanthanoids

• Causes of lanthanoid contraction:

CHEMISTRY THE d- AND f-BLOCK ELEMENTS

1. When we move from left to right along the lanthanoid series, the
nuclear charge increases by one unit at each neighboring
element. The new electron is added to the same subshell. So, the
attractive force between the electron and nucleus increases, and
hence, the size decreases.
2. When a new electron is added to the f-subshell, the shielding
effect of one electron by another is not perfect due to the shape
of f-orbitals. Such a shielding cannot balance the effect of
increased nuclear charge. Hence, contraction occurs.

• Consequences of lanthanoid contraction:

(a) Difficulty in separation of lanthanoids:

1. Because of the slight difference in ionic radii of lanthanoids,

their chemical properties are similar. This makes separation
of lanthanoids more difficult.
2. Also, due to the difference in the size of lanthanoids,
properties such as solubility, complex ion formation and
hydration show differences. This helps separate the
individual lanthanoids by the ion exchange method.

(b) Similarity in the size of elements belonging to the same group of the
second

and third transition series:

1. The size of elements belonging to the second transition
series is always greater than that of the elements belonging
to the same group of the first transition series. Also, the size
of the atom of the third transition series, i.e. after lanthanum,
is nearly the same as that of the atom of the element
belonging to the same group of the second transition series.
2. Similarity in size of the atoms of the elements belonging to
the same group of the 2nd and 3rd transition series is due to
the effect of lanthanoid contraction.

(c) Effect on the basic strength of hydroxides:

Because the size of lanthanoid ions decreases from La3+ to
Lu3+, the covalent character of the hydroxides increases, and
hence, the basic strength decreases. Therefore, La(OH)3 is more
basic, while Lu(OH)3 is weakly basic.
CHEMISTRY THE d- AND f-BLOCK ELEMENTS

❖ Characteristics of Lanthanoids:

(a) Silvery appearance and softness:

All lanthanoids are silvery white soft metals and tarnish easily in air. As the
atomic number increases, their hardness also increases.

(b) Melting point:

They have a very high-melting point in the range 1000−1200 K
except samarium, which has ahigh melting point of about 1623 K.

(c) Electrical and thermal conductivity:

They have metallic characteristics, and hence, they are good
conductors of heat and electricity.

(d) Density:
They have high densities in the range of 6.77−9.74 gcm−3. Density
and other properties differ smoothly with increasing atomic number except in
Eu and Yb.

(e) Colour:
They are silvery white. Most of the trivalent ions are coloured in
solid and in aqueous solution. This is due to f–f transition.

(f) Magnetic behaviour:

All the lanthanoids except La3+ and Lu3+ show paramagnetism. This
property is due to the presence of unpaired electrons in the incomplete
4f subshell.

(g) Ionisation enthalpies:

The first ionisation enthalpies of lanthanoids are about 600 kJ mol−1
and the second is about 1200 kJ mol−1. The third ionisation enthalpy
is low if it leads to a stable electronic configuration,
i.e. empty, half-filled or completely filled.

(h) Electropositive character:

They are highly electropositive because they possess low ionisation enthalpy.

(i) Standard electrode potential:

The value of their standard electrode potential,
CHEMISTRY THE d- AND f-BLOCK ELEMENTS

lies in the range −2.2 to −2.4 V. Europium is an exception because

its Eo value is −2.0 V.

(j) Reducing agents:

They easily lose electrons; hence, they are good reducing agents.

(k) Complex formation:

Because of their large size and low charge density, they do not have
much tendency to form complexes. This tendency of complex
formation increases with increasing atomic number.

(l) Chemical behaviour:

The first few elements of the series are more reactive like calcium. As
the atomic number increases, their behaviour becomes similar to that
of aluminium. They show the following properties:

They combine with hydrogen on heating.

They form carbides when heated with carbon.

They form halides when burnt with halogens.

They react with dilute acids to liberate

hydrogen gas.

They form oxides and hydroxides.

❖ Uses of lanthanoids:

1. It is mainly used in the production of alloy steels to improve the

strength of steel. A well-known alloy is mischmetal which has the
following composition:
CHEMISTRY THE d- AND f-BLOCK ELEMENTS

✓ Lanthanoid metal = 95%

(about 50% Ce, 40% La and the rest other

lanthanoids)

✓ Iron = 5%

✓ S, C, Ca and Al = traces

The mischmetal is mostly used in making a magnesium-based alloy.

It is pyrophoric alloy, [Link] alloy which emits sparks when struck. It
is used in making bullets, shells and lighter flints.
2. Their oxides are used in the glass industry—for polishing glass and
to make optical glass.
3. Mixed oxides of lanthanoids are used as catalysts in petroleum cracking.
4. Ceric sulphate is a well-known oxidising agent used in volumetric analysis.

Actinoids

❖ Electronic Configuration:

• All the actinoids have common 7s2 configuration, and filling of the 5f
and 6d subshells is variable.
• The 14 electrons are being added to 5f, except in thorium (Z =
90), but this filling of the 5fsubshell continues further after thorium
till 5f orbitals are complete at Z = 103.
• Irregularities in the electronic configurations of actinoids are
concerned with the stabilities of f0,f7 and f14 configurations.
• Although the 4f and 5f orbitals have similar shapes, 5f is less deeply
buried than 4f. Hence, 5felectrons can participate in bonding.

❖ Oxidation state:
• The common oxidation state of all actinoids is +3.
• Actinoids also possess the oxidation state of +4. Some of them show
higher oxidation state. The oxidation state gradually increases from
CHEMISTRY THE d- AND f-BLOCK ELEMENTS

the extreme left to the middle of the series and then decreases.
• The compounds of actinoids with +3 and +4 oxidation states undergo hydrolysis.

❖ Ionic radii and actinoid contraction:

• Like lanthanoids, actinoids also show contraction due to the poor
shielding effect of the 5f ectrons.

• So, the radii of the atoms or ions of actinoids decrease gradually along the
series.
• This contraction is greater from element to element in a series
because 5f orbitals extend in the space beyond 6s and 6p orbitals.

❖ Characteristics of Actinoids:

(a) Silvery appearance:

Actinoids are metals with silvery appearance.

(b) Structural variability:

They have much more regularities in their metallic radii; hence,
they show great structural variability.

(c) Colour:
They are silvery white metals. Their cations are generally coloured.
The colour of these cations depends on the number of 5f-electrons.
The cations containing zero 5f electrons or seven 5f electrons
are colourless. The cations containing 2−6 5f electrons are coloured.
This colour mainly arises because of f–f transition.

(d) Melting and boiling points:

Actinoids have high melting and boiling points. They do not show
any gradual change even with increasing atomic number.

(e) Density:
With the exception of thorium and americium, all actinoids have high
densities.
(f) Ionisation enthalpies:
They have low ionisation enthalpies than lanthanoids. This is because 5f
is less penetrating than 4f and hence is more effective in shielding from
nuclear charge.

(g) Electropositive character:

They are highly electropositive.
CHEMISTRY THE d- AND f-BLOCK ELEMENTS

(h) Magnetic behaviour:

They are strongly paramagnetic. The change in magnetic
susceptibility of actinoids with increasing number of unpaired
electrons is the same as lanthanoids, but the values are higher for
actinoids.

(i) Reducing agents:

All the actinoids are strong reducing agents.

(j) Radioactivity:
All the actinoids are radioactive. The first few members of the series
have long half- lives. The remaining have half lives ranging from very
few days to few minutes.

(k) Chemical behaviour:

They are highly reactive in the crushed form. They show the following
properties:

❖ Uses of actinoids:
CHEMISTRY THE d- AND f-BLOCK ELEMENTS

Uses of thorium Uses of uranium Uses of plutonium

• It is used in atomic • It is used as nuclear • It is used as a fuel for

reactors and in fuel. atomic reactors.
treatment of cancer. • Its salts are used in • It is also used for
• Its salts are used in glass, textile, ceramic making bombs.
making incandescent industries and in
gas mantles. medicines.

Comparison of Lanthanoids and Actinoids

➢ Similarities:

Actinoids show
actinoid
Both show Both are Both exhibit contraction and
common electropositive magnetic and lanthanoi ds
oxidation state and very spectral show
of +3. reactive. properties.
lanthano id
contraction.

➢ Differences:
CHEMISTRY THE d- AND f-BLOCK ELEMENTS
CHEMISTRY THE d- AND f-BLOCK ELEMENTS