ISC CHEMISTRY

d-Block and f-Block Elements

Introduction:

D-block elements are the collective name for the groups 3 to 12, in which the d-orbitals are
progressively filled in each of the four long periods.
As the d-block elements lies between the s and p block elements, they are also referred to as the
transition elements.
There are mainly three series of transition elements. They are
3d series: This includes the elements from scandium to zinc.
4d series: This includes the elements from yttrium to cadmium
5d series: This includes the elements from lanthanum to mercury.
The fourth series, the 6d series, which begins with actinium, is still incomplete.
General electronic configuration:
(n-1) d1-10ns1-2.
The atoms of the d-block elements try to fill their available d-orbitals either partially with five
electrons, or completely with ten electrons whenever possible. This is due to the fact that half-
filled or completely filled orbitals impart greater stability to an atom.
Element Outer Electronic Configuration
Scandium (Sc) 3d1 4s2
Titanium (Ti) 3d2 4s2
Vanadium (V) 3d3 4s2
Chromium (Cr) 3d5 4s1
Manganese (Mn) 3d5 4s2
Iron (I) 3d6 4s2
Cobalt (Co) 3d7 4s2
Nickel (Ni) 3d8 4s2
Copper (Cu) 3d10 4s1
Zinc (Zn) 3d10 4s2

Configurations of chromium and copper in the 3d series:

Chromium, for example, has a configuration of 3d5 4s1 instead of the expected 3d4 4s2. Copper,
on the other hand, has an electronic configuration of 3d 10 4s1 instead of 3d9 4s2.

The properties of transition elements depend largely on their electronic -configurations. Thus,
with partly filled d orbitals.
The precious metals, like gold, platinum and silver, and industrially important metals like iron,
copper and titanium, form part of the transition elements.

Variation in atomic and ionic size

The atomic radii of elements of the 3d-series gradually decrease in radius with an increase in
atomic number.
Reason:
The d-orbitals offer poor shielding effect. Hence, the nuclear charge attracts all the electrons
more strongly, resulting in a contraction in size.

The same trend is observed in the ionic radii of a given series.

The atomic radii increase from 3d to 4d, the atomic radii of the 4d and 5d transition series are
very close. This is due to lanthanoid contraction.

The consequence of lanthanoid contraction:

The radii of the second and third transition series, that is, 4d and 5d are similar.
EX: Zirconium and Hafnium.

A decrease in the metallic radius along with an increase in the atomic mass results in a general
increase in the density of these elements. Thus, there is a significant increase in the density from
titanium to copper.

d-block: Oxidation states

One of the most striking features of the transition elements is their ability to exhibit several
oxidation states in their compounds. This unique ability is due to the small difference in energy
between the ns and (n -1) d orbitals. Thus addition to ns electrons (n -1)d electrons also
participate in bonding.
The table here lists the common oxidation states exhibited by the first row transition elements.
Sc Ti V Cr Mn Fe Co Ni Cu Zn
(+1) +1
+2 +2 +2 +2 +2 +2 +2 +2 +2
+3 +3 +3 +3 +3 +3 +3 +3
+4 +4 (+4) +4 (+4) (+4) +4
+5 (+5) (+5) (+5)
+6 +6 (+6)
+7
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.
The tendency to form ionic compounds decreases with an increase in the oxidation number of the
metal.
Higher oxidation states give rise to covalent compounds.
Ex: Mn(II) oxide is ionic, Mn(IV) oxide is intermediate between ionic and covalent and Mn(VII)
oxide is purely covalent. As the oxidation state of the transition metal increases, the charge
density on the metal also increases. This results in an increase in the polarisation of the anion
charge cloud by the metal and hence, the covalent character increases.
Oxidation Number
Oxide Nature of Compound
of Metal
MnO +2 Ionic
MnO2 +4 Covalent
Mn2O7 +7 Covalent
The acidic nature of the oxides increases with an increase in the oxidation state of the transition
element.
Ex: Mn(II) oxide is basic, Mn(IV) oxide is amphoteric while Mn(VII) oxide is acidic in nature.
In higher oxides, the acidic character is predominant. Thus, Mn(VII) oxide gives permanganic
acid, while Cr(VI) oxide gives chromic acid and dichromic acid.

Colour and magnetic properties

Most d-block metal compounds are coloured in their solid or liquid states.
In the case of transition metal ions, under the influence of ligands, the degeneracy of the 5 d-
orbitals is lost and they separate into two distinct energy levels.

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.
Magnetic properties:
Substances, depending on their behaviour in an external magnetic field, are classified into 2
types
Paramagnetic substances: These are weakly attracted to a magnetic field
Reason: presence of unpaired electrons in the atom
Diamagnetic: These are repelled to a magnetic field.
Reason: absence of unpaired electrons in the atom.

f-block

Physical properties of the actinoids:

 They are all silvery metals.
 These are highly reactive metals.
 They tarnish in air due to the formation of an oxide coating.

Chemical properties of the actinoids:

 They react with hot water to give a mixture of an oxide and a hydride.
6An + 8O2 → 2An3O8
Actinoid Oxygen Actinoid oxide
 An + 2X2 → AnX4
Actinoid Halogens Actinoid halide

2An + 3H2 → 2AnH3

Actinoid Hydrogen Actinoid hydride
 They react readily with HCl, but its reaction with other acids is slower than expected.
 These are basic and do not react with sodium hydroxide.
 They react with oxygen, halogens and with hydrogen.

Applications of the d- block elements:

Iron and its alloy, steel, are used extensively in the construction industry.
Titanium is used in aircraft and spaceship manufacture.
Tungsten is used to make electrical filaments.
Manganese dioxide is used in dry battery cells.
Zinc is used as the negative electrode in sealed dry batteries.
Niobium alloys are used in jet engines.
Tantalum is used to make analytical weights.
Silver bromide is used in photography.
Many transition metals and their compounds are used as catalysts in the chemical industry.
Ex:
Ziegler-Natta, a complex of titanium tetrachloride and trimethyl aluminium used in the
polymerisation of ethene to polythene.

Iron used in Haber's process for the production of ammonia.

Palladium chloride used in the Wacker process of oxidation of ethane to ethanal.
PdCl2
CH2 = CH2 + H2O + ½O2 → CH3CHO + H2O
CuCl
Ethene 2 Ehanal
Applications of f-block elements:
Alloys of lanthanides (misch-metals) used for the production of heat-resistant and instrumental
steels.
Borides, carbides and nitrides of lanthanides are used as refractories.
Lanthanide oxides are used as abrasives for polishing glass.
Thorium is used in the treatment of cancer and in incandescent gas mantles.
Uranium is used as a nuclear fuel.
Plutonium is used in atomic reactors and in atomic bombs.

Physical properties of lanthanoids:

All lanthanoids are soft and silvery white metals.
 They are electropositive.
 They rapidly tarnish in air due to the formation of an oxide coating on their surface.
4Ln + 3O2 → 2Ln2O3
Lanthanoid oxygen lanthanoid oxide
 They are good conductors of heat and electricity.
 Their M.P and density change gradually, except in the case of europium, ytterbium,
samarium and thulium.
Element Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
Melting
1068 1208 1297 1315 1345 1099 1585 1629 1680 1734 1802 1818 1097 1925
Point(K)
 Element Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
Density (g
6.77 6.77 7.01 7.26 7.52 5.26 7.90 8.23 8.54 8.79 9.07 9.32 6.90 9.84
cm-3)
 Many of the trivalent lanthanoid ions are coloured, both in their crystalline state and
in aqueous
solutions.

 Lanthanoid ions that have empty f orbitals, like La (III), half-filled f-orbitals, like Gd
(III), or completely filled 4f orbitals, like Lu (III) ions, are colourless.

 Due to the presence of unpaired electrons in the 4f orbitals, all lanthanoid ions show
paramagnetic behaviour.

Exceptions:
La (III), Ce (IV) ions with fO configuration, & Yb (II) & Lu ( III) ions with f14 configuration
show diamagnetic nature.
Paramagnetism is the maximum in Dysprosium.
The value of the first ionisation energy of the lanthanides is about
600 K J/mole and of the second ionisation energy is about 1200 K /mole

Chemical reactivity:
The first few members of the lanthanoids are quite reactive and show chemical behaviour similar
to that of calcium. The standard electrode potentials of the Ln+3/Ln couple indicate that all the
lanthanides are more reactive than aluminium.
These metals combine with hydrogen when heated gently in the gas, and form hydrides of the
type LnH2 and LnH3.
lanthanoids (Ln)
Ln + H2 → LnH2
lanthanoid Hydrogen Lanthanoid hydride

Ln + O2 → LnO2
lanthanoid Oxygen Lanthanoid Oxide

Calcium (Ca)
Ca + H2 → CaH2
Calcium Hydrogen Calcium hydrogen

Ca + O2 → CaO2
Calcium oxygen Calcium peroxide

On being heated, these elements combine directly with non-metals, and form carbides with
carbon, nitrides with nitrogen, sulphides with sulphur, and halides with halogens.
2773K
Ln + 2C → 2LnC2
lanthanoid carbon Carbide
Δ
2Ln + N2 → 2LnN
lanthanoid Nitrogen Nitride

Δ
2Ln + 3S → 2Ln2S3
lanthanoid Sulphur Sulphide

Δ
2Ln + 3X2 → 2LnX3
lanthanoid Halogen Halide

They liberate hydrogen from dilute acids.

Δ
2Ln + 6HX → 2LnX3 + 3H2↑
lanthanoid Nitrogen Halide hydrogen

They burn in oxygen to form oxides of the type Ln 2O3.

They react slowly with cold water, but more rapidly with hot water, and liberate hydrogen gas.
The lanthanoid oxides and hydroxides are basic in nature.
Uses:
 Lanthanoids are widely used for the production of alloy steels for pipes and plates.
 A well-known alloy, mischmetal, which is used in a magnesium-based alloy to
produce bullets, shells and lighter flint.
 Mixed oxides of lanthanoids are used as catalysts in petroleum cracking.
 EuO2 and YbO 2 are used to produce the red colours on television screens.
 The oxides of praseodymium and neodymium are used in glass, such as in television
screens.

Properties of F block Elements

 Have electrons added to the ‘f’ sub-orbitals of (n-2) level
 Are placed between (n-1)d and ns block elements in the periodic table.
 Properties are similar to d-block elements.

Properties of Lanthanides
 Lanthanides are soft metals with a silvery white colour.
  Their colour dulls and their brightness reduces rapidly when exposed to air.
 They have melting points ranging from 1000K to 1200K (Except Samarium, 1623K).
 Lanthanides are good conductors of heat and electricity.
 They are non-radioactive in nature except Promethium
 A decrease in atomic and ionic radii from lanthanum to lutetium is observed. This is called the
lanthanoid contraction.

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.

Difference between Lanthanides and Actinides

 Lanthanoids are involved in the filling of 4f- orbitals whereas actinoids are involved in the filling of
5f-orbitals. The binding energy of 4f electrons is comparatively less than that of 5f-electrons. The
shielding effect of 5f-electrons is less effective as compared to that of 4f-electrons.
 The paramagnetic properties of lanthanoids can be easily explained but this explanation is difficult in
the case of actinoids.
 Lanthanides are non-radioactive in nature except promethium whereas all actinide series elements are
radioactive.
 Lanthanides do not have a tendency to form oxo-cations, but several oxo-cations of actinide series
exist. The compounds formed by lanthanides are less basic on the other hand the compounds of
actinides are highly basic.

Similarities between Lanthanides and Actinides

The elements of lanthanide and actinide series are characterized by filling of (n-2) f subshell. They possess
almost similar outermost electronic configuration hence have similar properties. Following are the significant
similarities:

1. Both have a prominent oxidation state of +3.

2. They are involved in the filling of (n-2) f orbitals.
3. They are highly electropositive and very reactive in nature.
4. With an increase in atomic number, there is a decrease in atomic and ionic size.
5. Both show magnetic properties.