SYLLABUS : d and f Block Elements

Position in the periodic table, occurrence, electronic configuration and

characteristics of transition metals, general trends in properties of the 3d-series of
transition metals - metallic character, ionisation enthalpy, oxidation states, ionic
radii, colour of ions, catalytic property, magnetic properties.

Lanthanoids and actinoids.

(i) d-Block: 3d, 4d and 5d series

Study in terms of metallic character, atomic and ionic radii, ionisation enthalpy,
oxidisation states, variable valency, formation of coloured compounds, formation of
complexes.

(ii) f-Block: 4f and 5f series

Electronic configuration, atomic and ionic radii, oxidisation states, formation of
coloured compounds, formation of complexes. Lanthanoid contraction and its
consequences.
Actinoids - oxidation states and comparison with lanthanoids.
What are Transition Elements?
Transition elements (also known as transition metals) are elements that have partially
filled d orbitals.
IUPAC defines transition elements as an element having a d subshell that is partially
filled with electrons, or an element that has the ability to form stable cations with an
incompletely filled d orbital.

It is important to note that the element’s mercury, cadmium, and zinc are
not considered transition elements because of their electronic
configurations, which corresponds to (n-1)d10 ns2.
These elements have completely filled d orbitals in their ground states and
even in some of their oxidation states. One such example is the +2
oxidation state of mercury, which corresponds to an electronic
configuration of (n-1)d10.
General Properties of Transition Elements

•These elements form coloured compounds and ions. This colour is explained by the d-d
transition of electrons.
•There is a relatively low gap in energy between the possible oxidation states of these elements.
The transition elements, therefore, exhibit many oxidation states.
•Many paramagnetic compounds are formed by these elements, because of the unpaired electrons
in the d orbital.
•A large variety of ligands can bind themselves to these elements. Due to this, a wide variety of
stable complexes are formed by transition elements.
•These elements have a large ratio of charge to the radius.
•Transition metals tend to be hard and they have relatively high densities when compared to other
elements.
•The boiling points and the melting points of these elements are high, due to the participation of
the delocalized d electrons in metallic bonding.
•This metallic bonding of the delocalized d electrons also causes the transition elements to be
good conductors of electricity.
Atomic (Covalent) and Ionic Radii
•The covalent radii of the elements decrease from left to right across a row in the transition series. This is
because of the poor screening by the d electrons due to which, the nuclear charge attracts all of the electrons
more strongly, hence a contraction in size occurs.

•The atomic radii for the elements from Cr to Cu are very close to one another. This closeness in atomic radii is
due to the shielding of outer 4s electrons by 3d electrons from the inward pulls of nucleus. As a result of these
two opposing effects, the atomic radii do not alter much on moving from Cr to Cu.

•The elements in the first group in the d-block show the expected increase (due to the addition of extra
shell) in size Sc → Y → La. However in the subsequent groups there is an increase between first and
second members, but hardly any increase between second and third elements. This is due to lanthanide
contraction
Atomic Radii

The atomic and ionic radii of the transition elements decrease

from group 3 to group 6 due to the poor shielding offered by the
small number of d-electrons. Those placed between groups 7
and 10 have somewhat similar atomic radii and those placed in
groups 11 and 12 have larger radii. This is because the nuclear
charge is balanced out by the electron-electron repulsions.

While traversing down the group, an increase in the atomic and

ionic radii of the elements can be observed. This increase in the
radius can be explained by the presence of a greater number of
subshells.
 LANTHANIDE CONTRACTION
The atomic size or the ionic radii of tri positive lanthanide ions
decrease steadily from La to Lu due to increasing nuclear
charge and electrons entering the inner (n-2) f orbital.
This gradual decrease in the size with an increasing atomic
number is called lanthanoid contraction.
Lanthanoid contraction is also known as lanthanide contraction

Causes
•The positive charge on the nucleus increases by one unit as the
atomic number rises, and one additional electron enters the
same 4f subshell.
•The electrons in the 4f subshell shelter each other poorly. In a
4f subshell, shielding is less than in a d subshell.
•The valence shell is drawn somewhat closer to the nucleus as
the nuclear charge increases. Lanthanide contracts as a result of
this.
Ionization Enthalpy
•Ionization enthalpy refers to the amount of energy that must be supplied to an element for the removal of a
valence electron.
•The increase in ionization energy along the period of d-block elements is very small.
•The first ionization energy of transition elements are higher than those of s-block
elements but lower than p-block elements.
•In a particular transition series, ionization energy although increases gradually as
we move from left to right but this increase is not appreciable.
•The increase in ionization energy is due to increase in nuclear charge, the effect of
increase in nuclear charge is partly balanced by the increase in screening effect.
•Consequently, In transition elements, on moving along the period, the addition of
the extra electron in the (n-1) d level takes place. This electron provides a screening
effect and shields the outer ns electrons from the nucleus pull.
•Because of this shielding effect of d electrons, the effect of nuclear charge
(effective nuclear charge) on outer ns electrons is somewhat less than the actual
nuclear charge.
•Thus the effects of the increasing nuclear charge and the shielding effect created
due to the expansion of (n-1)d orbital oppose each other.
•On account of these counter effects, the ionization potentials increase rather slowly
on moving in a period of the first transition series
First Ionization Energy
•The first ionization energy for the first four 3d series elements (Sc, Ti, V and Cr) arte almost same
i.e. differ only slightly from one another.
•The values of first ionization energy for Fe, Co, Ni and Cu are also very close to one another.
•The value of first ionization energy for Zn is considerably high due to extra-stability of completely
filled 3d10 level.

Second ionization energy

•The second ionization emerges increases more or less regularly with the increase of atomic
number.
•The value of second ionization energy for Cr and Cu are higher than those of their neighbours.
This is due to the fact that the electronic configurations of Cr+ and Cu+ ions have extra stable 3d5
and 3d10 levels.
•There is a sudden fall in the values of ionization potentials in going from II B (Zn-group elements)
to IIIA sub-group. This is because in case of IIIA group elements the electron to be removed is from
a 4p-orbital which is incompletely filled, while in case of the II B group elements, the electron to be
removed is from completely filled 4s-orbital which required extra energy
Metallic properties:

The transition metals exhibit typical metallic properties

such as malleability, ductility, high tensile strength, and
metallic lustre. They are generally good conductors of heat
and electricity and tend to crystallize in BCC (body-
centred cubic), CCP (cubic close-packed), or HCP
(hexagonally close-packed) structures.
However, trends can be observed in the metallic properties
of the transition elements. For example, elements such as
chromium and molybdenum are some of the hardest
transition metals because they contain many unpaired
electrons.
Variable Oxidation State
Transition metals have unique property to show variable oxidation state. This
property arises from the fact that the energy levels of 3d, 4d and 5d orbitals
are very close to those of 4s, 5s and 6s orbitals respectively and, therefore,
electrons from both ns and (n-1)d orbitals can be used, infact they are used,
for the formation and bonds by transition metals.

They show variable oxidation states unlike s and p block elements. The
oxidation states changes in units of one, e.g. Fe2+ and Fe+3, Cu+1 and Cu+2.

Scandium can have an oxidation number of (+II) if both s electrons are used
for bonding and (+III) when two s and one d electrons are involved. Similarly
all the elements show variable oxidation states depending upon the number of
electrons available for bonding in their s and d sub-shells.
Except for scandium and zinc, all the other elements show more than one oxidation state.
Scandium, due to the availability of very few electrons for bonding, does not show variable
oxidation states.
On the other hand, zinc, due to the presence of too many d electrons, has fewer orbitals
available for bonding, and thus, does not exhibit variable oxidation states.
The elements from titanium to zinc, with the exception of copper, show a minimum
oxidation state of +2. Copper shows a minimum oxidation state of +1.
The maximum oxidation state is given by the sum of the s and d electrons for the first five
elements.
Ex: scandium, titanium, vanadium, chromium and manganese exhibit maximum oxidation
states of +3, +4, +5, +6 and +7 in the form of their oxides, oxyanions and oxycations.
The maximum oxidation states of the elements after manganese are not at all related to
their electronic configurations.
Ex: Cobalt shows +2 and +3 stable oxidation states.
The relative stabilities of various oxidation states of 3d series elements can be correlated
with the extra stability of 3d0, 3d5 and 3d10 configurations to some extent. Thus, Ti4+ ion
with 3d0 configuration is more stable than a Ti3+ ion with 3d1 configuration.
Minimum oxidation state: All the transition elements except Cr, Cu, Ag, Au and Hg which have a minimum
oxidation state of +1 exhibit a minimum oxidation state of +2.
Maximum oxidation state: Each of the elements in groups III B to VII B can show the maximum oxidation
state equal to its group number. For example, Cr in group VIB shows a maximum oxidation state of +6 in
Cr2O72– ion.
Most of the elements in VIII group show a maximum oxidation state equal to + 6. However, Ru and Os have a
maximum oxidation state equal to +8 which is the highest oxidation state shown by any element.

Relative stability of various oxidation states:

•The relative stabilities of various oxidation states of 3d-series elements are due to the extra stability of 3d0,
3d5 and 3d10 configurations.
•Ti4+ (3d0) is more stable than Ti3+ (3d1)
•Mn2+ (3d5) is more stable than Mn4+ (3d4).
•The higher oxidation state of 4d and 5d series elements are generally more stable than those of the elements of
3d series, e.g., Mo, Tc (4d series elements) and W, Re (5d-series elements) s.
•The highest oxidation states of second and third row elements are encountered in compounds containing the
more electronegative elements viz. F, O and Cl
Colour
Many compounds of transition elements are coloured in contrasts to those of s and p block elements. In
compound state due to the surrounding groups (ligands), the d-orbitals of transition elements are not
degenerate but split into two groups of different energy.

eg set: d x2- y2 and dz2 orbitals

t2g set: dxy, dxz and dyz orbitals.

When white light is incident on a transition metal ion, the electron in the lower energy d-orbital set absorbs
certain radiations and gets promoted to a d-orbital set of higher energy. The transmitted radiation devoid of
the absorbed radiations is the complementary colour of the absorbed light. This complementary colour is
the colour of the substance.
Some compounds of transition metals are white, for example ZnSO4 and TiO2.
In these compounds it is not possible to promote the electrons within the d-level.
• Catalytic Property
• Many transition metals and their
compounds have catalytic properties. For
e.g. V2O5, Fe, FeCl3, Ni, Pd etc. This is due
to following reasons:
• 1) Variable oxidation state: Due to
variable oxidation state they form unstable
intermediate compounds and provide a
new path with lower activation energy for
the reaction (Intermediate compound
formation theory)
• 2) Large Surface area: Finely divided
transition metals or their compounds
provide a large surface area for adsorption
and the adsorbed reactants react faster
due to the closer contact.
Complex Formation
The transition elements have an unparalleled tendency to form coordination compounds with the Lewis
bases, which are called as ligands.
CO3+ + 6NH3 → [CO(NH3)6]3+
Fe2+ + 6CN– → [Fe(CN)6]4–

The reason transition elements are so good at forming complex is that they have small, highly charged ions
and have vacant low energy orbitals to accept lone pairs of electrons donated by ligands.

The transition elements have a tendency to form coordination compounds or complex compounds.
Complex compounds are those in which a central atom or ion is surrounded by a number of anions or
neutral molecules possessing a lone pair of electrons. These surrounding anions or molecules are called
ligands.
EX: Pentamine Cobalt (iii) Chloride, Potassiumferrocyanide (ll), and Nickel Tetra Carbonyl (0).
The tendency of the transition metal ions to form complexes is due to:
•Their relatively small size and resultant high positive charge density
•Presence of vacant n minus one d-orbitals
•Their ability to show multiple oxidation states
Magnetic Property
On the basis of behaviour in a magnetic field, substance are classified as paramagnetic,
diamagnetic and ferromagnetic. Those substance which are attracted by the applied magnetic
field are called paramagnetic whereas those which are repelled by the magnetic field are called
diamagnetic. Substances which are very strongly attracted by the applied field are called
ferromagnetic.
Para magnetism is a property due to the presence of unpaired electrons. Thus, most of the
transition metals are paramagnetic. As the number of unpaired electrons increases, the
paramagnetic character also increases.
The magnetic moment is calculated from the following formula μ = √n(n+2) BM where n is the
number of unpaired electrons and B. M stands for Bohr magneton.

When n=1, µ= 1.73 BM

When n =2, µ=2.83
In case of iron, cobalt and nickel, the unpaired electron spins are much pronounced. As
a result, these elements are much more paramagnetic than the rest of the elements.
These elements are called ferromagnetic substances.
Uses of Transition Metals:

Iron is widely used in the construction industry. It is usually alloyed into steel, which exhibits greater
tensile strength and versatility. Iron is also used as a catalyst for the industrial production of ammonia via
the Haber process.
Titanium is used in aircrafts, piping for nuclear power plants, and in artificial hip replacements.
Nickel is in used in the production of stainless steel.
Copper is used in electrical wiring because of its high tensile strength, malleability, ductility, and electrical
conductivity.
Classification of f Block Elements
The elements belonging to the f block are further differentiated into:
1. The first series of elements are called lanthanides and include elements
with atomic numbers beginning from 57 and ending at 71. These
elements are non-radioactive (except for promethium, which is
radioactive).
2. The second series of elements are called actinides and include elements
with atomic numbers beginning from 89 and ending at 103. These
elements generally have a radioactive nature.
• 4f series of Ce(58) to Lu (71)
• 5f series of Th (90) to Lw (103)
There are 14 elements filling up the ‘f’ orbital in each series.
LANTHANOIDS
Electronic Configuration of Lanthanides
• Lanthanides of first f-block have a terminal electronic configuration of [Xe] 4f1-14 5d 0-16s2,
• Promethium (Pm) with atomic number 61 is the only synthetic radioactive element.
• The energy of 4f and 5d electrons are almost close to each other and so 5d orbital remains vacant
and the electrons enter into the 4f orbital.
• Exceptions are in the case of gadolinium, Gd (Z = 64) where the electron enters the 5d orbital
due to the presence of half-filled d-orbital and lutetium (Z = 71) enters the 5d orbital.
Properties of Lanthanide Series
Lanthanides are the rare earth elements of the modern periodic table i.e. the elements with
atomic numbers from 58 to 71 following the element Lanthanum. They are called rare earth
metals since the occurrence of these elements is very small (3×10-4 % of Earth’s crust).
Like most metals, these elements have very high melting points (ranging from roughly 800 to
1600 degrees Celsius) and very high boiling points (ranging from roughly 1200 to 3500 degrees
Celsius).
All of the elements in the series closely resemble lanthanum and each another in their chemical
and physical properties. Some of the key characteristics and properties are:
• They have a lustre and are silvery in appearance.
• They are soft metals and can even be cut with a knife
• The elements have different reaction tendencies depending on basicity. Some are very
reactive while some take time to react.
• Lanthanides can corrode or become brittle if they are contaminated with other metals or non-
metals.
• They all mostly form a trivalent compound. Sometimes they can also form divalent or
tetravalent compounds.
• They are magnetic.
Lanthanide Contraction
The atomic size or the ionic radii of tri positive lanthanide ions
decrease steadily from La to Lu due to increasing nuclear
charge and electrons entering inner (n-2) f orbital. This gradual
decrease in the size with an increasing atomic number is
called lanthanide contraction.
Consequences of Lanthanide Contraction
1. Atomic size: Size of the atom of third transition series is nearly the same as that of the atom of the
second transition series. For example: radius of Zr = radius of Hf & radius of Nb = radius of Ta etc.
2. Difficulty in the separation of lanthanides: As there is an only small change in the ionic radii of
Lanthanides, their chemical properties are similar. This makes the separation of elements in the pure state
difficult.
3. Effect on the basic strength of hydroxides: As the size of lanthanides decreases from La to Lu,
the covalent character of the hydroxides increases and hence their basic strength decreases. Thus, La (OH)3
is more basic and Lu(OH)3 is the least basic.
4. Complex formation: Because of the smaller size but higher nuclear charge, tendency to form coordinate.
Complexes increases from La3+ to Lu3+.
5. Electronegativity: It increases from La to Lu.
6. Ionization energy: Attraction of electrons by the nuclear charge is much higher and hence Ionization
energy of 5d elements are much larger than 4d and 3d. In 5d series, all elements except Pt and Au have
filled s-shell.
Elements from Hafnium to rhenium have same Ionization Energy and after Ionization Energy increases
with the number of shared d-electrons such that Iridium and Gold have the maximum Ionization Energy.
Mercury – the liquid metal: Mercury is the only metal that exists in its liquid state at room
temperature. 6s valence electrons of Mercury are more closely pulled by the nucleus
(lanthanide contraction) such that outer s-electrons are less involved in metallic bonding.
7. Formation of Complex: Lanthanides exhibiting 3+ oxidation state is the larger and hence
low charge to radius ratio. This reduces the complex-forming ability of lanthanides
compared to d-block elements. Still they, form complexes with strong chelating agents like
EDTA, β-diketones, oxime etc. They do not form Pπ-complexes.
OXIDATION STATES

MOST COMMON OXIDATION STATE

MOST STABLE OXIDATION STATE
OTHER OXIDATION STATES
USES
ACTINIDES
Properties of Actinides
• The Actinide elements appear to be silvery.
• These elements have a radioactive nature.
• These metals are highly reactive and their reactivity
increases when they are finely divided.
• A decrease in atomic and ionic radii from Actinium
to Lawrencium is observed. This is called the actinoid
contraction.
• They generally exhibit an oxidation state of +3. However,
elements belonging to the first half of the series are known
to exhibit higher oxidation states quite frequently.
ELECTRONIC CONFIGURATION AND OXIDATION STATES
• ACTINOIDS HAVE MORE COMPOUNDS IN +3 STATE JUST LIKE LANTHANOIDS
• +3 AND +4 HYDROLYSE IN AQ SOLUTIONS UNLIKE LANTHANOIDS