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SPUC Tumakuru d- & f-block elements Vedavathi R

The elements of the groups 3-12 in which the d-orbitals are progressively filled are called d-block elements (transition
metals) i.e., the differentiating electrons goes to the d-orbitals.
There are mainly three series of the transition metals, 3d series (Sc to Zn), 4d series (Y to Cd) & 5d series (La to Hg,
omitting Ce to Lu). The fourth 6d series which begins with Ac is still incomplete.
The Transition Elements
A transition element is defined as the one which has incompletely filled d-orbitals in its ground state (neutral
atom) or in any one of its oxidation states(ions).
Zn, Cd & Hg of group 12 have full d10 configuration in their ground state as well as in their common oxidation states
& hence, are not regarded as transition metals.
Position in the Periodic Table
The name ‘transition’ given to the elements of d-block is only because of their position between s- & p-block
elements.
Electronic Configurations of the d-Block Elements
The electronic configuration of 3d-series elements is as shown bellow
Element Symbol Atomic Electronic
Number Configuration
Scandium Sc 21 [Ar]183d 14s2
Titanium Ti 22 [Ar]183d24s2
Vanadium V 23 [Ar]183d34s2
Chromium Cr 24 [Ar]183d54s1
Manganese Mn 25 [Ar]183d54s2
Iron Fe 26 [Ar]183d64s2
Cobalt Co 27 [Ar]183d74s2
Nickel Ni 28 [Ar]183d84s2
Copper Cu 29 [Ar]183d104s1
Zinc Zn 30 [Ar]183d104s2
• General electronic configuration of d-block elements is [noble gas] ns1-2(n-1) d1-10.
• The valence shell electronic configuration is (n-1) d1-10ns1-2.
The (n-1) stands for the inner d-orbitals which may have 1-10 electrons & the outermost ns-orbital may have 1-2
electrons.
• Electronic configuration of Cr is [Ar]3d54s1 instead of [Ar]3d44s2 due to extra stability of half-filled d5 orbitals than d4
orbitals.
• Electronic configuration of Cu is [Ar]3d104s1 instead of [Ar]3d94s2 due to extra stability of completely filled d10
orbitals than d9 orbitals. Because of very little energy difference between (n-1) d & ns-orbitals. Further, half &
completely filled sets of orbitals are relatively more stable. Hence, the electronic configurations of Cr (3d54s1) & Cu
(3d104s1).
• The electronic configurations of Zn, Cd & Hg have the general formula of(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.
General Properties of the Transition Elements (d-Block)
Physical Properties
Transition metals show metallic properties such as high tensile strength, ductility, malleability, high thermal and
electrical conductivity and metallic lustre.
The transition metals (except Zn, Cd and Hg) are very much hard & have low volatility. Their melting and boiling
points are high. The high melting points of these metals are due to the involvement of greater number of electrons from
(n-1) d in addition to the ns-electrons in the interatomic metallic bonding.
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They have high enthalpies of atomisation. The maxima at about the middle of each series indicate that one unpaired
electron per d-orbital is particularly favourable for strong interatomic interaction.
In general, greater the number of valence electrons, stronger is the resultant bonding. Metals with very high enthalpy
of atomisation (i.e., very high boiling point) tend to be noble in their reactions. The metals of the 2nd & 3rd series have
greater enthalpies of atomisation than the corresponding elements of the first series because of the occurrence of much
more frequent metal – metal bonding in compounds of the heavy transition metals.
NOTE: Transition elements exhibit higher enthalpies of atomisation this is because of large number of unpaired
electrons in their atoms, they have stronger interatomic interaction & hence stronger bonding between atoms resulting
in higher enthalpies of atomisation.
Variation in Atomic and Ionic Sizes of Transition Metals
The atomic radius of 3d-series elements is as follows
Element Sc Ti V Cr Mn Fe Co Ni Cu Zn
Atomic 144 132 122 117 112 117 116 115 117 125
radii
The atomic radius decreases in the beginning, becomes constant and then increases up to end this is because,
As the atomic number increases the effective nuclear charge increases and the screening effect is low because the
added electrons are added to the same inner 3d- orbital. Hence the 4s-electrons are drawn toward the nucleus and the
atomic radius decreases in the beginning.
As the atomic number increases the number of 3d-electrons increases and the screening also increases. The
increase in screening compensates the increase in effective nuclear charge. Hence the atomic radius remains constant.
Towards the end due to increase in electron-electron repulsion due to pairing of electrons in Zinc the atomic
radius increases.

Ionic radii: The ionic radii of transition elements follow the same trends as that of atomic radii. For ions carrying
identical charges the ionic radius decreases gradually as the atomic number increases.
Ionisation Enthalpies: The ionisation enthalpy increases along each series of the transition elements as we move
from left to right due to an increase in nuclear charge.
The numerical value of first ionisation enthalpy of the 3d metals show irregular trend this is because the unipositive
ion is formed by the removal of one electron from 4s-orbital and the other s-electron is transferred to the d-orbital.
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This alters the relative energies of 4s & 3d orbitals due to the transfer of electron from s- to d-orbital. Hence the
unipositive ions have dn configurations with no 4s electrons.
Elements Sc Ti V Cr Mn Fe Co Ni Cu Zn
∆H KJ/mol 631 656 650 652 717 762 758 736 745 906
Note:
1. The IE value of Cr is lower because of no change in the d-configuration & IE value for Zn is higher because it does
not involve the transition of s-electron to d-orbital due to the completely filled d-orbital and the removal of an electron
take place from the 4s orbital only.
2. The IE2 values for Cr & Cu are high due to the disruption of their d5 & d10 configurations.
3. The IE2 value for Zn is low because the removal of an electron gives the stable d10 configuration.
Oxidation States:
One of the main features of a transition element is the exhibition of variable oxidation states. The variable oxidation
states in the transition metals are due to the comparable energies of 3d- and 4s-orbitals. During the formation of
compounds, the electrons present in both 4s and 3d-orbitals are involved in the bond formation.
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 oxidation states of the 3d-series elements are as follows
Element Atomic Number Oxidation state
Sc 21 (+2), +3
Ti 22 +2, +3, +4
V 23 +2, +3, +4, +5
Cr 24 +2, +3, (+4), +6
Mn 25 +2, +3, +4, (+6), +7
Fe 26 +2, +3, +4, (+6)
Co 27 +2, +3, (+4)
Ni 28 +2, (+3)
Cu 29 +1, +2
Zn 30 +2
The common oxidation state of the transition elements is +2 and it increases by one-unit up to manganese and then
decreases. The oxidation states shown in the bracket are less common oxidation states.
NOTE:
➢ The element which does not show variable oxidation state is Sc.
➢ The only oxidation state of Zn is +2 since no d-electrons are involved in the bonding.
➢ The maximum oxidation state is equal to the sum of electrons present in both s and d-orbitals.
➢ Fe+3 is more stable than Fe+2 since it has half-filled 3d5 orbital which is more stable.
➢ The compounds in which the transition metals in lower oxidation states are good reducing agents. This is because in
the lower oxidation state the metal ion has the tendency to lose electrons.
Ex: Fe+2 Fe+3 + e-
➢ The compounds in which the transition metals in higher oxidation states are good oxidizing agents. This is because in
the higher oxidation state the metal ion has the tendency to accept electrons.
Ex: KMnO4
NOTE: Cr2+ is reducing & Mn3+ is oxidising when both have d4 configuration, because in Cr2+the configuration
changes from d4 to d3 (d3 has half-filled t2g level) which is stable and hence behaves as reducing agent. But in the case
of change from Mn3+ to Mn2+results in the half-filled (d5) configuration which has extra stability hence behaves as
oxidising agent.
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Trends in the M3+/M2+ Standard Electrode Potentials:

The standard E° values of the elements of 3d-series for the divalent cation M+2/M is as follows
Element E° in volts E° in volts
M+2/M M+3/M+2
Sc -
Ti -1.6 -0.37
V -1.2 -0.26
Cr -0.9 -0.41
Mn -1.18 +1.57
Fe -0.44 +0.77
Co -0.28 +1.97
Ni -0.24
Cu +0.34
Zn -0.76
Since Sc does not form the divalent cation its reduction potential value is not given. The above table shows trends
in reduction potential values is not regular. The E0 value for Zn is more negative is due to the removal of an electron
to form the stable d10 configuration of Zn2+. The high E0 value for Mn shows that Mn2+(d5) is stable, whereas low E0
value for Fe shows the extra stability of Fe3+ (d5). The low E0 value for V is due to the stability of V2+ (half-filled t2g
level).
Chemical Reactivity & E0 Values:
From the reduction potential values it is observed that the transition metals show variable chemical reactivity. Many of
them are electropositive to dissolve in mineral acids, but few are ‘noble’ i.e., they are unaffected by single acids.
(i)The metals of the first series except copper are more reactive since it has positive value of the reduction potential
values & are oxidised by 1M H+ to liberate hydrogen readily from dilute acids (though the rate of oxidation is slow).
M(s) + 2H+ M+2 +H2(g)
But in actual practice the rate of liberation of hydrogen is very slow. Actually, some of these metals get protected due
to the formation of inert metal oxide film on their surface.
Ex: chromium forms Cr2O3 coating on its surface. Titanium and Vanadium becomes passive in acidic medium due to
the same reason.
The E0 values for M2+/M indicate a decreasing tendency to form divalent cations across the series. This general trend
towards less negative E0 values is due to the increase in the sum of the first & second ionisation enthalpies.
(ii) With the exception of copper all other metals have negative value of the E° values and hence they are expected to
serve as good reducing agents. But their reducing nature is quite less compared to that of s-block elements which are
much more electropositive in nature. This is because of high enthalpy of sublimation, enthalpy of ionisation and low
enthalpy of hydration of their ions.
Magnetic Properties:
When a magnetic field is applied to substances, mainly two types of magnetic behaviour are observed: diamagnetism
& paramagnetism.
Diamagnetic substances are repelled by the applied field while the paramagnetic substances are attracted. Substances
which are attracted very strongly are said to be ferromagnetic. Ferromagnetism is an extreme form of paramagnetism.
Generally, the Transition metals and their compounds are paramagnetic in nature. They are weakly attracted by the
magnetic field. Some of the elements of 3d-series are highly paramagnetic i.e., ferromagnetic in nature.
Paramagnetism is due to the presence of unpaired electrons. Each such electron has a magnetic moment associated
with its spin angular momentum & orbital angular momentum. The paramagnetism increases with increases with
increase in number of unpaired electrons and the extent of paramagnetism is measured in terms magnetic moment.
The magnetic moment is calculated by the formula

where n is the number of unpaired electrons

µ is the magnetic moment in units of Bohr magneton (BM).
If a single unpaired electron has a magnetic moment of 1.73 Bohr magnetons (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.
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The magnetic moments calculated for 3d-series elements are given in Table

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 lies in the visible region.
The colour observed corresponds to the complementary colour of the light absorbed.
Most of the transition metal compounds and ions have colour both in solid state and in aqueous solution. The colour is
due to the absorption of light by the unpaired electron in the d-orbitals. When the light is passed through the solution
of transition metal compound, a part of the light is absorbed and the rest is transmitted. The transmitted light is called
as the complementary light. Thus, the colour of the substance is the complementary of the absorbed light.
Ex: If the absorbed colour of a substance is orange, then its colour is blue.
The aqueous solutions of the colour of the ions observed is as follows
Confuguration Example Colour
3d0 Sc+3 colourless
3d0 Ti+4 colourless
1
3d Ti+3 purple
3d1 V+4 Blue
3d2 V+3 Green
3d3 V+2 Violet
3
3d Cr+3 Violet
3d4 Mn+3 Violet
4 +2
3d Cr Blue
3d5 Mn+2 Pink
3d5 Fe+3 Yellow
3d6 Fe+2 Green
7 +2
3d Co Pink
3d8 Ni+2 Green
3d9 Cu+2 Blue
10 +2
3d Zn colourless

Formation of Complex Compounds:

The transition metals and metal ions form a large number of complex compounds. This is due to
(1) Availability of vacant d-orbitals.
(2) Higher nuclear charge.
(3) Small atomic and ionic size.
The vacant d-orbitals can accept lone pair of electrons from ligands to form coordinate bonds. The tendency to accept
the lone pair of electrons to form the coordinate bonds increases with increase in the nuclear charge and decrease in
the atomic or ionic radii.
Catalytic Properties:
A catalyst is a substance that varies the rate of a chemical reaction without undergoing permanent chemical change.
The transition metals & their compounds show catalytic activity. The catalytic activity is due to (i)their ability to show
variable oxidation states & to form intermediate complexes with the reactants. These intermediate complexes are
formed at lower energy and decomposes to give products. For example, iron (III) catalyses the reaction between iodide
& persulphate ions.
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(ii)Transition metals provide large surface area for the adsorption of the reactants.
Some of the examples of transition metals which are the industrially important catalysts are as follows.
a) Iron in the manufacture of ammonia by Haber’s process.
b) Vanadium pentoxide(V2O5) in the manufacture of sulphuric acid by contact process.
c) Nickel in the hydrogenation of oils.
Platinum-Rhodium in the manufacture of Nitric acid.
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 non-stoichiometric & are neither typically ionic nor covalent.
The small atoms like H, C, or N occupy the interstitial space in the transition metal crystals which have larger voids.
This forms the non-stoichiometric compounds like TiC, Mn4N, Fe3H, VH0.56 & TiH1.7, etc. and these are called as
interstitial compounds. They have high melting points than the pure metals. They are chemically inert and some
borides are as hard as diamond. They have metallic conductivity.
Alloy Formation:
Alloys are homogeneous solid solutions in which the atoms of one metal are distributed randomly among the atoms of
the other. The transition metals have similar atomic radii hence they can easily occupy the crystal lattice of other.
Hence transition metals are miscible with one another in molten state. These alloys so formed are harder, have often
high melting points & resist corrosion than the individual metals. The metals like chromium, vanadium, tungsten,
molybdenum and manganese are used for the production of alloys of steels & stainless steel.
Alloys of transition metals with non-transition metals such as brass (copper-zinc) & bronze (copper-tin) are of
industrial importance.
Oxides:
• All transition metals form the monoxides with the composition MO which are ionic. But Scandium forms Sc2O3 with
Sc in +3 state and Manganese forms Mn2O7 with Mn in +7 state.
• As the oxidation state of metal increases the ionic character decreases and melting point decreases. The Mn2O7 is a
green covalent liquid while Cr2O3 & V2O5 are low melting solids at room temperature.
• In lower oxidation states of metals, the metal oxides are basic in nature but as the oxidation state increases the metal
oxides becomes acidic in nature. The intermediate oxidation state oxides are amphoteric in nature.
Ex: (i)On treatment with water Mn2O7 gives Permanganic acid (HMnO4) & CrO3 gives chromic acid(H2CrO4) &
dichromic acid(H2Cr2O7).
(ii)V2O3 is basic in nature, V2O4 is less basic while V2O5 is amphoteric in nature.
Important compounds of transition metals
(1) Potassium dichromate (K2Cr2O7): It is an orange coloured crystalline solid used as an oxidizing agent in several
industries. Also, it is used in leather tanning industries.
Preparation:
It is prepared by the fusion of chromite ore (FeCr2O4) in free access of air.
When concentrated chromite ore is roasted with soda ash, the product was extracted with water to get a yellow
solution of sodium chromate is formed.
4FeO.Cr2O3+ 8Na2CO3+7H2O 8Na2CrO4+2Fe2O3+8CO2
The above yellow solution of sodium chromate is filtered & the filtrate is acidified with sulphuric acid to obtain the
orange red solution of sodium dichromate (Na2Cr2O7.2H2O) which can be crystallised.
2Na2CrO4 + H2SO4 Na2Cr2O7+Na2SO4+H2O
Sodium dichromate is more soluble than potassium dichromate.
The latter is therefore, prepared by treating the solution of sodium dichromate with potassium chloride.
Na2Cr2O7+KCl 2NaCl+K2Cr2O7
Orange crystals of potassium dichromate crystallise out.
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Structure
The structures of chromate ion, CrO42– & the dichromate ion, Cr2O72– are shown below.

The chromate ion is tetrahedral whereas the dichromate ion consists of two tetrahedra sharing one corner with the
Cr–O–Cr bond angle of 126°.
The chromates & dichromates are interconvertible in aqueous solution depending upon pH of the solution.
The oxidation state of chromium in chromate and dichromate is the same.
Properties
(i)With Alkali
Potassium dichromate forms yellow coloured solution of potassium chromate on reaction with alkali solution.
K2Cr2O7 + 2KOH 2K2CrO4 H2O
(ii)Oxidising Nature
Sodium & potassium dichromates are strong oxidising agents; the sodium salt has a greater solubility in water & is
widely 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:
K2Cr2O7 + 4H2SO4 K2SO4 + Cr2(SO4)3+ 4H2O + 3[O]
The oxidation number of chromium is changing from +6 to+3,
The ionic equation for the above reaction can be represented as
Cr2O72- +14H+ + 6e- 2Cr3+ + 7H2O
Thus, acidified potassium dichromate will oxidise iodides to iodine, sulphides to sulphur, stannous (II) to stannic (IV)
and ferrous (II) salts to ferric (III).
The half-reactions are represented below:
6I- 3I2 + 6e- 3S2- 3S + 6e-
3Sn2+ 3Sn4+ + 6e- 6Fe2+ 6Fe3+ +6e-
(2) Potassium Permanganate KMnO4:
It is prepared from pyrolusite mineral (MnO2) in the following steps
(i) conversion of MnO2 to potassium manganate (K2MnO4)
Powdered pyrolusite is fused with potassium hydroxide in the presence of oxidising agent like potassium nitrate to
obtained a green coloured mass potassium manganate.
MnO2 + 2KOH + KNO3 K2MnO4 + KNO2 + H2O
(ii) Electrolytic oxidation
The potassium manganate solution is electrolysed between iron electrodes separated by diaphragm. Oxygen evolved
at anode oxidises the manganate to permanganate.
2K2MnO4 + H2O + [O] 2KMnO4 + 2KOH
OR
2-
MnO4 MnO4- + e-
The solution is filtered and evaporated to obtain crystals of potassium permanganate.
Properties:
(i) Potassium permanganate is a dark purple crystalline solid which dissolves in water to farm pink coloured solution.
It decomposes on heating at 513K forming dark green coloured potassium manganate.
Both Manganate (MnO42-) and Permanganate (MnO4-) ions are tetrahedral in structure.
The manganate & permanganate ions are tetrahedral; the green manganate is paramagnetic with one unpaired
electron but the permanganate is diamagnetic.
The π-bonding takes place by overlap of p orbitals of oxygen with d orbitals of
manganese.
The green coloured manganate is paramagnetic in nature while the purple-coloured
permanganate is diamagnetic in nature.
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(ii) Oxidising Nature: Potassium permanganate acts as an oxidising agent in acidic, basic as well as in neutral
medium.
(a) In acidic medium in presence of dilute H2SO4 Potassium permanganate acts as a good oxidising agent.
KMnO4 + H2SO4 K2SO4 + MnSO4 + 3H2O + 5[O]
OR
- + -
MnO4 + 8H + 5e Mn+2 + 4H2O
(b) In neutral or slightly alkaline medium it acts as a moderate oxidising agent.
KMnO4 + H2O 2KOH + 2MnO2 + 3[O]
OR
-
MnO4 + 2H2O + 3e -
MnO2 + 4OH-
Acidified permanganate solution oxidises oxalates to carbon dioxide, iron (II) to iron (III), nitrites to nitrates and
iodides to free iodine. The half-reactions of reductants are:

Note: Permanganate titrations in presence of hydrochloric acid are unsatisfactory since hydrochloric acid is oxidised
to chlorine.
f-block elements:
The elements in which the pre-penultimate f-orbital is progressively filled or the elements in which the 4f- & 5f-
orbitals are progressively filled are called as f-block elements and are of two types (i)Lanthanoids
(ii) Actinoids. These are also called as inner transition elements.
The 14 elements (Thorium to Lawrencium) which comes after Actinium (Z=89) in which the 5f-orbital is partially
filled are called as Actinoids since they resemble the properties of Actinium.

Lanthanoids: The 14 elements (Cerium to Lutetium) which comes after Lanthanum (Z=57) in which the 4f-orbital is
partially filled are called as Lanthanoids since they resemble the properties of Lanthanum.
1. Electronic Configuration: In Lanthanoids the outermost 6s-orbital is filled followed by the filling of the 4f-orbital.
The electronic configuration of lanthanoids is as follows.
Element Symbol & At. Electronic
No configuration
Lanthanum La (57) [Xe]5d16s2
Cerium Ce (58) [Xe]4f 15d16s2
Praseodymium Pr (59) [Xe] 4f 35d06s2
Neodymium Nd (60) [Xe] 4f 45d06s2
Promethium Pm (61) [Xe] 4f 55d06s2
Samarium Sm (62) [Xe] 4f 65d06s2
Europium Eu (63) [Xe] 4f 75d06s2
Gadolinium Gd (64) [Xe] 4f 75d16s2
Terbium Tb (65) [Xe] 4f 95d06s2
Dysprosium Dy (66) [Xe] 4f 105d06s2
Holmium Ho (67) [Xe] 4f 115d06s2
Erbium Er (68) [Xe] 4f 125d06s2
Thulium Tm (69) [Xe] 4f 135d06s2
Ytterbium Yb (70) [Xe] 4f 145d06s2
Lutetium Lu (71) [Xe] 4f 145d16s2
In most of the lanthanoids, the single electron in the 5d-orbital moves to the 4f-orbital as this is energetically
favourable. In the case of Gd and Lu the 5d-orbital contains one electron as the 4f-orbital is half filled and completely
filled respectively which gives higher stability.
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2.Atomic and Ionic Sizes:

The atomic and ionic radii of the lanthanoids decreases from Lanthanum to Lutetium, this decrease in atomic radii is
not regular. The cumulative total decrease in ionic radii of about0.22Å from La to Lu is called as Lanthanoid
contraction.
The cause for lanthanoid contraction is due to (i) the progressive addition of electrons into the prepenultimate 4f-
orbital in lanthanoids. Because of this the distance between the outermost electrons and the nucleus remains the same
but the nuclear charge gradually increases. The increased nuclear charge pulls the outer electrons inward reducing the
size of the atom. (ii)The imperfect shielding of one 4f-electrons by another (which is less than the shielding of d-
electrons by one another).
Consequences of Lanthanoid contraction
Due to Lanthanoid contraction, the elements in the 3rd transition series in which 5d-orbital is partially filled have the
same ionic radii as the corresponding elements (immediately above) in the second transition series (in which 4d-
orbitals is partially filled). Thus Hf(159pm) and Zr(160pm) both have the same atomic radii. Hence, (i) the elements
of second and 3rd transition series resemble each other more closely than the elements of the first and second transition
series due to lanthanoid contraction. (ii)They occur together in nature and it is difficult to separate them.
3.Oxidation States:
The most common oxidation state of lanthanoids is +3. In addition to this +2 and +4 is mostly observed in the
elements in which these oxidation states lead to empty, half-filled and completely filled f-orbitals. Because of the
stable common oxidation state lanthanoids resemble one another closely in their properties.
4.General Characteristics of Lanthanoids:
• All the lanthanoids are silvery white soft metals & tarnish rapidly in air.
• Their hardness increases with increase in atomic number, samarium is hard as steel.
• Their melting points range between 1000 & 1200 K but samarium melts at 1623 K.
• They have typical metallic structure & are good conductors of heat and electricity.
• Many trivalent lanthanoid ions are coloured both in the solid state & in aqueous solutions. Colour of these
ions is due to the presence of f-electrons. But La3+ and Lu3+ ions are colourless as they have f0 and f14 state.
• All the lanthanoid ions are paramagnetic in nature except La3+ & Ce4+ (f0 type) & Yb2+ & Lu3+ (f14 type). The
paramagnetism of neodymium is maximum.
Chemical behaviour:
• The earlier members of the lanthanoid series are quite reactive as calcium but, with increase in atomic
number, they behave more like aluminium.
• The E0 values of lanthanoids for the half-reaction of the type: Ln3+(aq) + 3e– → Ln(s) are in the range of –2.2
to –2.4 V. But Eu has the value of – 2.0 V.
• The lanthanoid metals combine with hydrogen when gently heated with the H2 gas.
• They form carbides like, Ln3C, Ln2C3 & LnC2 when the metals are heated with carbon.
• They liberate hydrogen from dilute acids.
• They form halides when burnt in halogens.
• They form oxides like M2O3 & hydroxides M(OH)3. The hydroxides are basic like alkaline earth metal oxides
and hydroxides.
• The lanthanoids are used in the production of alloy of steels for plates & pipes.
Ex: mischmetal alloy [a lanthanoid metal (~ 95%) + iron (~ 5%) & traces of S, C, Ca & Al].
Mischmetal is used in Mg-based alloy to produce bullets.
Mixed oxides of lanthanoids are used as catalysts in petroleum cracking.
Ln oxides are used as phosphors in television screens & fluorescing surfaces.

The Actinoids:
The 14 elements (Thorium to Lawrencium) which comes after Actinium (Z=89) in which the 5f-orbital is partially
filled are called as Actinoids since they resemble the properties of Actinium. The actinoids are radioactive elements.
Earlier members have longer half-lives than the latter ones. The latter members could be prepared only in nanogram
quantities. Hence, their study is more difficult.
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Electronic Configurations:
Element Symbol & At. Electronic
No configuration
Actinium Ac (89) [Rn]6d17s2
Thorium Th (90) [Rn]6d27s2
Protactinium Pa (91) [Rn]5f 26d17s2
Uranium U (92) [Rn]5f 36d17s2
Neptunium Np (93) [Rn]5f 46d17s2
Plutonium Pu (94) [Rn]5f6 6d07s2
Americium Am (95) [Rn]5f 76d07s2
Curium Cm (96) [Rn]5f 76d17s2
Berkelium Bk (97) [Rn]5f 96d07s2
Californium Cf (98) [Rn]5f 106d07s2
Einsteinium Es (99) [Rn]5f 116d07s2
Fermium Fm (100) [Rn]5f 126d07s2
Mendelevium Md (101) [Rn]5f 136d07s2
Nobelium No (102) [Rn]5f 146d07s2
Lawrencium Lr (103) [Rn]5f 146d17s2

The electronic configuration of Actinoids do not follow the same pattern as that of Lanthanoids. Cm and Lr has 6d1
configuration, as the 5f- orbital is exactly half filled and completely filled which is extra stable. In the first four
elements the electrons can occupy 5f or 6d orbitals or sometimes both since the energy difference between them is
small.
Ionic Sizes:
There is a gradual decrease in atomic size as we move across the series from Th to Lr. This is known as the actinoid
contraction. The contraction is greater from element to element in this series resulting from poor shielding by 5f
electrons.
Oxidation States:
In actinoids the common oxidation state is +3, which is most stable oxidation state. From the elements Am to Lr the
most stable oxidation state is +3. In the first five elements the most stable oxidation states are Th (+4), Pa (+5), U
(+6), Np (+5) and Pu (+4)
General Characteristics:
• The actinoid metals are all silvery in appearance. but display a variety of structures.
• They show variable structures which is due to irregularities in metallic radii which is greater than that in
lanthanoids.
• The actinoids are highly reactive metals, especially when finely divided.
• They react with boiling water to give a mixture of oxides & hydrides.
• They combine with non-metals at moderate temperature.
• Hydrochloric acid acts on all actinoid metals but nitric acid has less action on them and forms protective oxide
layers on them. But alkalis have no action on them.
• The magnetic properties of the actinoids are more complex than those of the lanthanoids.
• Ionisation enthalpies of the early actinoids are lower than for the early lanthanoids. This is because 5f orbitals
will penetrate less into the inner core of electrons. Hence, the 5f electrons are more effectively shielded from
the nuclear charge than the 4f electrons of the lanthanoids. Because the outer electrons are less firmly held,
they are available for bonding in the actinoids.
Comparison with Lanthanoids:
Both lanthanoids and actinoids involves the filling up of f-subshell in the antepenultimate shells in their atoms. Hence,
they show some similarities as follows.
1) Both lanthanoids and actinoids show a prominent oxidation state of +3.
2) Both lanthanoids and actinoids are electro positive and they act as better reducing agents.
3) Lanthanoids and actinoids cations with unpaired electrons are paramagnetic.
4) Most of their ions are coloured.
5) Both show a steady decrease in the atomic and ionic radii along the series.
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Importance of d- & f-block elements

1. The metals like Fe, Cr, Mn, and Ni are used in making the alloys like stainless steel, surgical steel etc.
2. TiO is used in White pigment.
3. MnO2 is used in dry battery cells. Zn, Cd, Ni are used in special type of battery cells.
4. Cu, Au, Ag are used as coinage and jewellery metals. The ‘silver’ UK coins are alloy of Cu/Ni.
5. Many of the metals like Cu, Fe, Ni etc are used as industrial catalysts. Fe in Haber’s process & Ni in Hydrogenation of
oils are used as catalysts.
6. AgBr is used in photographic industry.
7. TiCl4 & A1(CH3)3 is the Ziegler catalysts used to manufacture polyethylene (polythene).
8. V2O5 catalyses the oxidation of SO2 in the manufacture of sulphuric acid.
9. In the oxidation of ethyne to ethanal by Wacker Process involves PdCl2 as catalyst.
10. In the polymerisation of alkynes Ni complexes are used as catalysts.