SHORT NOTES

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,Preparation and properties of K2Cr2O7 and
KMnO4.
Lanthanoids ‐ Electronic configuration, oxidation
states and lanthanoid contraction and its
consequences.
Actinoids - Electronic configuration, oxidation states
and comparison with lanthanoids.
 The d and f block elements
The elements lying in the middle of periodic
table belonging to groups 3 to 12 are known
as d – block elements.
Electronic configuration of d-block elements:
The general electronic configuration of d-block
elements is (n −1)d1─10 ns1─2, where (n −1) stands
for the inner d orbitals.
In d-block, each horizontal row consists of ten
elements as d-subshell can accommodate a
maximum of 10 electrons.
• Half and completely filled sets of orbitals are relatively
more stable.
• For example, consider the case of Cr, which has
3d5 4s1 configuration instead of 3d44s2; the energy
gap between the two sets (3d and 4s) of orbitals is
small enough to prevent electron entering the
3d orbitals. Similarly in case of Cu, the configuration is
3d104s1 and not 3d94s2.
• The transition metals and their compounds also
exhibit catalytic property and paramagnetic
behaviour.
• With partly filled d orbitals these elements exhibit
certain characteristic properties such as display of a
variety of oxidation states, formation of coloured ions
and entering into complex formation with a variety of
ligand
There are mainly three series of the transition
metals:
• 3d series starts with Sc (Z = 21) and ends
with Zn (Z = 30)
• 4d series starts with Y (Z = 39) and ends with
Cd (Z = 48)
• 5d series starts with La (Z = 57) and ends
with Hg (Z = 80)
Position in the periodic table: The d-orbitals of
the penultimate energy level of atoms receive
electrons giving rise to four rows of the
transition metals i.e 3d, 4d, 5d, 6d.
• The d-block elements having incompletely
filled d-subshell are called transition metals.
Zinc, cadmium, mercury having the general
electronic configuration as (n –1)d10 ns2, are not
regarded as transition metals due to completely
filled d – orbital.[Non-typical transition elements]
The chemical properties were transitional between
those of s and p-block elements.
• Precious metals like silver, gold and platinum and
industrially important metals like iron and copper
and titanium belong to transition metal series.
On what ground can you say that scandium (Z = 21) is a
transition element but zinc (Z = 30) is not?
On the basis of incompletely filled 3d orbitals in case of
scandium atom in its ground state (3d1), it is regarded
as a transition element. On the other hand, zinc atom
has completely filled d orbitals (3d10) in its ground state
as well as in its oxidised state, hence it is not regarded
as a transition element.
Silver atom has completely filled d orbitals 4d10 5s1.
How it is a transition element?
Silver Ag belongs to group-11 of d-block and its ground
state electronic configuration is 4d105s1. It shows an
oxidation state of +2 in its compounds like AgO and
AgF2 in which its electronic configuration is d9 so it is
an transition element.
ELECTRONIC CONFIGURATION OF D BLOCK ELEMENTS IN THEIR
GROUND STATE.
• Exceptional configuration of Cr and Cu: The
exceptions observed in the first series are in
case of electronic configurations of chromium
(Z=24) and copper (Z=29). It may be noted that
unlike other elements, chromium and copper
have a single electron in the 4s orbital.
• This is due to the gain of additional stability by
the atom by either having half-filled
configuration or completely filled configuration.
The 3d level in case of chromium gets exactly
half-filled with configuration 3d54s1 and in that
in case of copper, it get completely filled with
configuration 3d10 4s1. This can be explained on
the basis of exchange energy.
 General Properties of transition elements:
Metallic character
• Almost all the transition elements display
metallic properties such as metallic lustre,
high tensile strength, ductility, malleability
and high thermal and electrical conductivity.
• In any row, the melting point of these metals
rises to a maximum at d5 and after that as the
electrons start pairing up so the melting point
decreases regularly as the atomic number
increases with an exception of Mn and Tc are
exception.
• Trends in melting point of transition elements:
Transition metals have high melting points which is
due to their strong metallic bond. The metallic
bonding depends upon the number of unpaired
electron. The melting point first increases(Sc-Cr),
reaches a maximum value(cr) and then decreases
(Fe-Zn).
Tungsten (W) has highest melting point
Mercury (Hg) has the lowest melting point.
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.[Because of stable Electronic
configuration of Mn and Tc.
Lattice Structures of Transition Metals:
• The metals of the second and third series have
greater enthalpies of atomisation than the
corresponding elements of the first series, this is
an important factor in accounting for the
occurrence of metal-metal bonding in
compounds of the heavy transition metals.
Greater the number of unpaired electrons, stronger
is the bonding due to the overlapping of unpaired
electrons between different metal atoms.
Enthalpy of Atomisation: It is the change in
enthalpy when one mole of bonds are completely
broken to obtain atoms in the gas phase.
• The metals of the second and third series have
greater enthalpies of atomisation than the
corresponding elements of the first series.
• Variation in atomic and ionic sizes of transition
metals
The atomic and ionic radii of transition elements
are smaller than those of S-Block elements and
larger than those of P-block elements.
In general atomic radius decreases with increasing
atomic number(Sc-Cr).
Two factors:
• Electron-electron repulsion
• Electron-proton attraction
• From Sc-Mn Zeff> Shielding effect –less number
of electron in d sub shell
• Fe-Ni Zeff=Shielding effect
• Cu-Zn Zeff<shielding effect -More number of
electrons in d sub shell.
• The atomic radii increase down the group. This means
that the atomic radii of second series are larger than
those of first transition series. But the atomic radii of the
second and third transition series are almost the same.
• The atomic radii of the elements of the second and third
transition metals are nearly same due to lanthanide
contraction.
With an increase in the atomic number, the positive charge
on nucleus increases by one unit and one more electron
enters same 4f subshell.
The electrons in 4f subshell imperfectly shield each other.
Shielding in a 4f subshell is lesser than in d subshell.
With the increase in nuclear charge, the valence shell is
pulled slightly towards the nucleus. This causes lanthanide
contraction.
• Lanthanide contraction:
• The decrease in ionic radii from 𝐿𝑎+3 to 𝐿𝑢+3
due to imperfect shielding of 4fe- from
nuclear charge.
• Due to increasing the 4f orbital electrons from
Ce to Lu.
Ionization Enthalpy:
The ionisation enthalpy gradually increases with
increase in atomic number along a given
transition series through some irregularities are
observed.
• The variation in ionization enthalpy along a
series of transition elements is much less in
comparison to the variation along a period of
non-transition elements.
• The first ionization enthalpy in general increases
but the magnitude of the increase in the second
and third ionisation enthalpies for the successive
elements is much higher along a series.
1
• IonizationEnergy 𝐴𝑡𝑜𝑚𝑖𝑐 𝑅𝑎𝑑𝑖𝑢𝑠
The value of ionization energy depends upon
i.Attractive forces,ii.Repulsive forces,iii.Exchange
energy.
• A general trend of increasing values of second
ionisation enthalpy is expected as the effective
nuclear charge increases because one d electron
does not shield another electron from the
influence of nuclear charge because d orbitals
differ in direction.
• As we move along a period in 3d series we see
that nuclear charge increases from Sc to Zn but
electrons are added to the orbital of inner
subshell, 3d orbitals.
• These 3d electrons shield the 4s electrons from
the increasing nuclear charge . Thus ionization
energies increase only slightly along the 3d
series.
• A general trend of increasing values of
second ionization enthalpy is expected as the
effective nuclear charge increases because
one d electron does not shield another
electron from the influence of nuclear charge
.
• The trend of steady increase in second and
third ionisation enthalpy breaks for the
formation of Mn2+, and Fe3+ respectively.
• In both the cases, ions have d5 configuration.
• 𝑴𝒏+ has 𝟑𝒅𝟓 𝟒𝒔𝟏 configuration and
configuration of 𝑪𝒓+ is d5, therefore ionization
enthalpy of 𝑴𝒏+ is lower than 𝑪𝒓+ .
• In the same way 𝑭𝒆𝟐+ has d6 configuration and
𝑴𝒏𝟐+ has 3d5 configuration. Hence ionisation
enthalpy of 𝑭𝒆𝟐+ is lower than the 𝑴𝒏𝟐+
• The first ionization enthalpies of 5d elements are
higher as compared to those of 3d and 4d
elements. This is because the weak shielding of
nucleus by 4f electrons in 5d elements results in
greater effective nuclear charge acting on the
outer valence electron.
Why do the transition elements exhibit higher
enthalpies of atomisation?
Because of large number of unpaired electrons in their
atoms they have stronger interatomic interaction and
hence stronger bonding between atoms resulting in
higher enthalpies of atomisation.
In the series Sc (Z = 21) to Zn (Z = 30), the enthalpy of
atomisation of zinc is the lowest, i.e., 126 kJ mol–1.
Why?
The extent of metallic bonding, an element is under
going decides the enthalphy of atomisation.
In all transition metals (except Zn (3𝑑10 𝟒𝒔𝟐 ), there are
some unpaired e−s that accounts for strong metallic
bonding due to the absence of unpaired e− in zinc, the
inter-atomic electronic bonding is weakest in Zn, as
result has least enthalpy of atomisation.
 +2
The E°(𝑀 /M) value for copper is positive 0.34V.
Explain why?
• Oxidation state:
• The net numerical charge assigned to an atom
of an element in its combined state is known
as its oxidation state or oxidation number.
• With the exception of few elements, most of
the d-block elements show more than one
oxidation state, they show variable oxidation
states. The elements show variable oxidation
state because of following reasons:
• ‘(n-1)d’ and ‘ns’ orbitals in the atoms of d-
block elements have almost same energies
and therefore electron can be removed from
‘(n-1)d’ orbitals as easily as ‘s’ orbitals
electrons.
• After removing ‘s’ electrons the remainder is
called kernel of the metal cations.
• All transition element show variable oxidation
state except last element in each series.
• Minimum oxidation state= Total number of
electrons in 4s lost
• Maximum oxidation state=(total number of
electrons in 4s + number of unpaired
electrons in 3d lost).
• In 3d series all element contain 2 electrons in
4s and hence they all give a common
minimum oxidation state of +2.
• The maximum oxidation state is given by Mn
i.e Mn+7 in which two electrons are removed
from 4s and five unpaired electrons are
removed from 3d orbitals.
• The element which shows higher oxidation
state occur in the middle or near the middle of
the series.
• Transition metals also show zero oxidation
states in metal carbonyl complex(Nickel
tetracarbonyl) and Fe(CO)5
• The bonding in the compounds of lower
oxidation state (+2, +3) is mostly ionic and the
bonding in the compounds of higher oxidation
state is mostly covalent.
• Standard electrode potential (𝑬𝟎 ) and
chemical reactivity:
• In solution, the stability of the compounds
depends upon electrode potentials rather
than ionization enthalpies.
• Electrode potential values depend upon
factors such as enthalpy of sublimation(or
atomisation) of the metal, the ionization
enthalpy and the hydration enthalpy.
• Transformation of the solid metal atoms to
M2+ ions in solution and their standard
electrode potentials.
• 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.
• Trends in stability of Higher oxidation state:
The highest oxidation numbers are achieved
in TiX4, VF5 and CrF6. The +7 state for Mn is not
represented in simple halides but MnO3F is known
beyond Mn no metal has a trihalide except FeX3
and CoF3.
• The ability of fluorine to stabilise the highest
oxidation state is due to higher lattice energy.
Vanadium form VF5 all other halides undergo
hydrolysis to give oxohalides, VOX3. Vanadium
difluoride will not exist due to instability of
fluorine in the low oxidation state.
• Fluorine form higher oxidation state with
transition elements because Fluorine has ability
to stabilize higher oxidation state.
• Due to its higher lattice energy
• High bond enthalpy
• Nickel, copper, Zinc have stable +2 oxidation
state due to that it will not form trihalide.
• VF5 do not hydrolysed into oxohalide but all
other fluoride of vanadium hydrolysed.
• Due to the formation of V2O5 it will not form
oxohalides.
• Fluorides cannot form a stable compound with
lower oxidation state. Smaller anion and bigger
cation
All CuII halides are known expect the iodide. In this case, Cu2+ oxidises I- to I2.
2Cu2++4I-Cu2I2(s) +I2
Many copper (I) compounds are unstable in aqueous solution and undergo
disproportionation.
2CU+Cu2+ +Cu

Oxides in 3d Metals:
The highest oxidation number in the oxides coincides with the group number
and is attained in Sc2O3 to Mn2O7. Beyond Group 7 no higher oxides of Fe
above Fe2O are known.
Although ferrates(FeO4)2- with +6 oxidation state but decompose into iron
oxide and oxygen.
All the oxocations will be stable.
The ability of oxygen to stabilise the high oxidation states exceeds that of
fluorine. Thus the highest Mn fluoride is MnF4 whereas the highest oxide is
Mn2O7.
The ability of oxygen to form multiple bonds to metals explains its
superiority.
In the covalent oxide Mn2O7, each Mn is tetrahedrally surrounded by O
including a Mn-O-Mn bridge.
• Chemical Reactivity and 𝑬𝟎 values:
• Reactivity  [-𝐸 𝑜 ]
 Tendency of loosing electron
• The transition metals vary very 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. Some results of chemical
reactivity of transition metals as related to their
E0 values are given below.
• More negative value oxidation possible
• Reduction not favourable
• Mn+H2SO4MnSO4+H2(use oxidation state)
• 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. Ti and V are passive
to dilute non-oxidizing acids at room temperature.
• As already explained, less negative E0 values for
𝑴𝟐+ /M along the series indicate a decreasing
tendency to form divalent cations across a series.
All those metals which are in their in 𝑀2+ form and
shows high negative 𝐸 0 value are very good reducing
agent.
Why is Cr2+ reducing and Mn3+ oxidising when bot
h have d4 configuration?
Cr2+ is reducing as its configuration changes
from d4 to d3, the latter having a half-filled t2g level .
On the other hand, the change from Mn3+ to
Mn2+ results in the half
filled (d5) configuration which has extra stability.
• Magnetic Properties:
• When the magnetic field is applied to
substances, mainly two types of magnetic
behaviour are observed diamagnetism and
paramagnetism.
• Diamagnetic substance are repelled by the
applied field while the paramagnetic
substance are attracted. Substances which are
attracted very strongly are said to be
ferromagnetic.
• Paramagnetism arises from the presence of
unpaired electrons, each such electron having a
magnetic moment associated with its spin
angular momentum and orbital angular
momentum.
• The magnetic moment is determined by the
number of unpaired electrons and is calculated
by using the spin-only formula
• µ = 𝒏(𝒏 + 𝟐)
Where n is the number of unpaired electrons and
µ is the magnetic moment in units of Bohr
magneton(BM). 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.
• The magnetic moment can be calculated by
spin only formula.
• 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.
• 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 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 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.
Reason for complexes:
• Smaller size of the
metal ions.
• Their high ionic charges.
• Availability of vaccant
d-orbitals can accept lone pair of electrons
Donated by the ligands.
Catalytic property:
Most transition elements and their compounds
have good catalytic properties because
(i) They possess variable oxidation state.
(ii) They provide a large surface area for the
reactant to be absorbed.
(iii) Iron(III) catalyses the reaction between
iodide and persulphate ions.
• 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.
• Ex: TiC, Mn4N
• Chemical properties:
• They have high melting points, higher than
those of pure metals
• They are very hard.
• They retain metallic conductivity
• They are chemically inert.
• 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 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 are used in steel and
stainless steel industry.
• Some other examples are brass (alloy of copper
+ zinc), stainless steel, bronze (alloy of copper +
tin), etc.
Compounds of Transition Elements:
• The metals of the first transition series form
oxides with oxygen at high temperature.
• The oxide are formed in the oxidation state +1
to +7 .
• The highest oxidation state in the oxides of
any transition metals is equal to its group
number 7 in Mn2O7.
• All the metals except scandium form the
oxides with the formula MO which are ionic in
nature.
• As the oxidation number of the metal
increases, ionic character decreases.

• In general, the oxides in the lower oxidation

states of the metals are basic and in the higher
oxidation states they are acidic whereas in the
intermediate oxidation state, the oxides are
amphoteric. Mn2O7 dissolves in water to give
• HMnO4.
• In vanadium there is a gradual change from
the basic V2O3 to less basic V2O4 and to
amphoteric V2O5.
• V2O4 dissolves in acids to give VO2+ salts .
• V2O5 reacts with alkalies as well as acids to
give VO4 3-. The CrO is basic but Cr2O3 is
amphoteric.
Potassium dichromate K2Cr2O7
Preparation
• The fusion of chromite ore (FeCr2O4) with sodium or
potassium carbonate in free access of air. The
reaction with sodium carbonate occurs as follows:
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. 2H2O can be crystallised.
• 2Na2CrO4 + 2 H+ → Na2Cr2O7 + 2 Na+ + 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 + 2 KCl → K2Cr2O7 + 2 NaCl
Structure of Chromate and dichromate:

Uses:
Potassium dichromate is used as a primary standard in
volumetric analysis and as an oxidizing agent. In acidic
medium, the oxidation state of Cr changes from + 6 in
Cr2O72‒ to + 3 in Cr3+.
Cr2O72‒ + 14 H+ + 6e‒ → 2Cr3+ + 7H2O (EƟ = 1.33V)
Potassium permanganate KMnO4:
Potassium permanganate is commercially prepared
by mixing solution of KOH and powdered manganese
oxide, with oxidizing agents like potassium chlorate.
6KOH + 3MnO2 + 6KClO3 → 3K2MnO4 + 6KCl + 3H2O
The solution of KMnO4 is drawn off from any
precipitate of MnO2 concentrated and crystallized.
The crystals are centrifuged and dried.
6K2MnO4 + 3Cl2 → 6KMnO4 (Potassium Permanganate) + 6KCl
• Potassium permanganate is prepared by fusion
of MnO2 with an alkali metal hydroxide and an
oxidising agent like KNO3. This produces the dark
green K2MnO4 which disproportionate in a
neutral or acidic solution to give permanganate.
• 2MnO2 + 4KOH + O2 → 2K2MnO4 + 2H2O
• 3MnO42– + 4H+ → 2MnO4– + MnO2 + 2H2O
• Potassium permanganate forms dark purple
(almost black) crystals which are isostructural
with those of KClO4. The salt is not very soluble in
water (6.4 g/100 g of water at 293 K), but when
heated it decomposes at 513 K.
• 2KMnO4 → K2MnO4 + MnO2 + O2
Properties:

The manganate and permanganate ions are

tetrahedral; the π-bonding takes place by overlap
of p orbitals of oxygen with d orbitals of
manganese.
The green manganate is paramagnetic because of
one unpaired electron but the permanganate is
diamagnetic due to the absence of unpaired
electron.
Acidified permanganate solution oxidises oxalates
to carbon dioxide, iron(II) to iron(III), nitrites to
nitrates and iodides to free iodine.

Fe2+ ion (green) is converted to Fe3+ (yellow):

• 5Fe2+ + MnO4– + 8H+ → Mn2+ + 4H2O + 5Fe3+
Oxalate ion or oxalic acid is oxidised at 333 K:
• 5C2O42– + 2MnO4– + 16H+ ——> 2Mn2+ + 8H2O + 10CO2
Nitrite is oxidised to nitrate:
5NO2– + 2MnO4– + 6H+ ——> 2Mn2+ + 5NO3– + 3H2O
(a) Iodine is liberated from potassium iodide :
10I– + 2MnO4– + 16H+ → 2Mn2+ + 8H2O + 5I2
(b) Fe2+ ion (green) is converted to Fe3+ (yellow):
5Fe2+ + MnO4– + 8H+ → Mn2+ + 4H2O + 5Fe3+
(c) Oxalate ion or oxalic acid is oxidised at 333 K:
5C2O42– + 2MnO4– + 16H+ -> 2Mn2+ + 8H2O + 10CO2
(d) Hydrogen sulphide is oxidised, sulphur being
precipitated:
H2S —> 2H+ + S2–
5S2– + 2MnO–4 + 16H+ ——> 2Mn2+ + 8H2O + 5S
(e) Sulphurous acid or sulphite is oxidised to a
sulphate or sulphuric acid:
5SO32– + 2MnO4– + 6H+ -> 2Mn2+ + 3H2O + 5SO42–
(f) Nitrite is oxidised to nitrate:
5NO2– + 2MnO4– + 6H+ ——> 2Mn2+ + 5NO3– + 3H2O
In neutral or faintly alkaline solutions:
(a) A notable reaction is the oxidation of iodide to
iodate:
2MnO4– + H2O + I– ——> 2MnO2 + 2OH– + IO3–
(b) Thiosulphate is oxidised almost quantitatively to
sulphate:
8MnO4– + 3S2O32– + H2O ——> 8MnO2 + 6SO42– + 2OH
Manganous salt is oxidised to MnO2; the presence of
zinc sulphate or zinc oxide catalyses the oxidation:
2MnO4– + 3Mn2+ + 2H2O ——> 5MnO2 + 4H+
Permanganate titrations in presence of hydrochloric
acid are unsatisfactory since hydrochloric acid is oxid
ised to chlorine.
Uses: ,
potassium permanganate is used as a favourite
oxidant in preparative organic chemistry.
Its uses for the bleaching of wool, cotton, silk and
textile fibres and for the decolourisation of oils are
also dependent on its strong oxidising power.
Uses of Potassium permanganate:Its uses for the
bleaching of wool, cotton, silk and other textile fibres
and for the decolourisation of oils are also dependent
on its strong oxidising power.
The inner Transition Elements:
The elements with gradually filled f orbitals are
called f-block elements.
The elements of 4f series of the inner transition
metals are called lanthanoids whereas the
elements of 5f series are called actinoids.
Electronic Configurations:
The general electronic configuration of the
lanthanoids is
Lanthanides have electronic configuration with
6s2 common but with variable occupancy of 4f
level. The electronic configuration of all the
tripositive ions are of the form 4fn(n=1-14).
Atomic and Ionic sizes:
Lanthanoid contraction:
• As we move along the lanthanoid series, the
atomic number gradually increases by one or
we can say number of electrons and protons
increases by one.
• Addition of electrons to the same shell
increases the effective nuclear charge.
• Increase in atomic number also increases the
number of electrons in the 4f orbital having
poor shielding effect due to which the
effective nuclear charge upon the outer
electrons also increases.
• Therefore the size of lanthanoids steadily
decreases with the increase in the atomic
number and phenomenon is called
lanthanoid contraction.
• As a result of lanthanoid contraction there is
a similarity in the properties of second and
third transition series.
• The decrease in atomic radii is not quite
regular as it is regular in M3+ ions.
Oxidation State:
In the lanthanoids, La(II) and Ln(III) compounds
are predominant species. However, occasionally
+2 and +4 ions in solution or in solid compounds
are also obtained.
This irregularity in ionisation enthalpies arises
mainly from the extra stability of empty, half-
filled or half-filled f sub shell.
The formation of 𝐶𝑒 𝐼𝑉 is favoured by its noble
gas configuration .
The 𝐸 0 value for 𝐶𝑒 4+ / 𝐶𝑒 3+ is +1.74V which
suggest it can oxidise water.
• Pr, Nd, Tb and Dy also exhibit +4 state but
only in oxides, 𝑀𝑂2 .
• 𝐸𝑢2+ is formed by losing the two s electrons
and its 𝑓 7 configuration accounts for the
formation of this ion.
• 𝑌𝑏 2+ which has 𝑓 14 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
state.
• General Characteristics:
• All lanthanoids are silvery white soft metals
and tarnish rapidly in air. The hardness
increases with increasing atomic number,
samarium being steel hard.
• They are good conductors of heat and
electricity.
• 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.
• 𝐿𝑎3+ and 𝐿𝑢3+ ions doesn’t show any colour
but the rest do so.
• The lanthanoid ions other than the 𝑓 0 type
• 𝐿𝑎3+ and 𝐶𝑒 3+ and 𝑓 14 (𝑌𝑏 2+ , 𝐿𝑢3+ ) are all
paramagnetic.
• The first ionisation enthalpies of the
lanthanoids are around 600kj/mol, the second
about 1200kj/mol .
• The variation in third ionisation enthalpy
occur due to stability to empty, half-filled and
completely filled orbitals f level.
• The abnormal low value of the third ionisation
enthalpy of lanthanum, gadolinium and
lutetium.
• Formation of alloys: Lanthanoids are all used in steel
industry for making alloy steels. Important and well-
known alloy is misch-metal and it con-sists of
lanthanoid (90-95%), iron (4-5%) and trace amount of
S, C Ca and Al.
• Uses:
• (i) Misch-metal is used in (Mg-based alloy) making
tracer bullets, shell and lighter flint.
• Misch metal, alloy consisting of about 50 percent
cerium, 25 percent lanthanum, 15 percent
neodymium, and 10 percent other rare-earth metals
and iron.
• (ii) Mixed oxides of lanthanoids are used as a catalyst
in petroleum cracking. Some individual oxides of
lanthanoids are used as phosphors in television
screens and similar fluorescing surface.
• The Actinoids:
• The actinoids include the fourteen elements
from Th to Lr. The names symbols and some
properties of these elements.
• The actinoids are radioactive elements and
the earlier members have relatively long half-
lives, the latter ones have half-life values
ranging from a day to 3 minutes for
lawrencium(Z=103). The latter members could
be prepared only in nanogram quantities.
These facts render their study more difficult.
Actinoid contraction is greater from element to
element than lanthanoid contraction Why?
This is due to poor shielding by 5f electrons in
the actinoids than that by 4f electrons in the
lanthanoids.
Electronic configurations:
Actinides are the second series of elements of the f-
block having a terminal electronic configuration of
[Rn] 5f1-14 6d 0-17s2. The energy of 5f and 6d
electrons are close to each other, and so electrons
enter into the 5f orbital.

The irregularities in the electronic configurations of

the actinoids, like those in the lanthanoids are
related to the stabilities of the f 0, f 7 and f 14
occupancies of the 5f orbitals.
The 5f orbitals can participate in bonding to a far
greater extent than 4f orbitals.
Ionic Sizes
• The general trend in lanthanoids is observable in
the actinoids as well. 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 state:
The actinoids show in general +3 oxidation state.
The elements, in the first half of the series frequent
ly exhibit higher oxidation states. For example, the
maximum oxidation state increases from +4 in Th to
+5, +6 and +7 respectively in Pa, U and Np but decr
eases in succeeding elements.
• The actinoids resemble the lanthanoids in having
more compounds in +3 state than in the +4 state.
 Comparison of lanthanides and
• Lanthanoids Actinides:
• Filling of 4f orbital takes Actinoids
place.
Filling of 5f orbital take place.
• This series includes
elements from atomic This series includes elements
number 57 to 71. from atomic number 89 to
103.
• These elements are non-
radioactive except All the elements of this series
promethium. are radioactive.
• Lanthanoids have a low Actinoids show greater
tendency to form tendency to form complexes.
complexes Most of the actinides ions are
• Lanthanoids have a bright deeply coloured.
and silvery appearance.
• Some Applications of f-block elements:
• Iron and steels are the most construction
materials. Their production is based on the
reduction of iron oxides, the removal of
impurities and the addition of carbon and
alloying metals such as Cr, Mn and Ni .
• 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 elements of Group 11 are still
worthy of being called the coinage metals,
although Ag and Au are restricted to collection
items and the contemporary UK copper coins
and copper-coated steel.
• The Silver UK coins are a Cu/Ni alloy.
• V2O5 catalyses the oxidation of SO2 in the
manufacture of sulphuric acid.
• TiCl4 with Al(CH3)3 forms the basis of the
Ziegler catalysts used to manufacture
polyethylene .
• Iron catalysis are used in the Haber process for
the production of ammonia from N2/H2
mixtures.
• Nickel catalysis enable the hydrogenation of
fats to proceed.
• In the Wacker process the oxidation of ethyne
to ethanal is catalysed by PdCl2.
• Nickel complexes are useful in the
polymerisation of alkynes and other organic
compounds such as benzene.
• The photographic industry relies on the
special light sensitive properties of AgBr.