CHAPTER 4

D AND F BLOCK ELEMENTS

Introduction to d-block elements

• In the periodic table the d block consists of the elements of group 3 to

12.
• The d orbital of the d-block elements in four periods are filled.
• The three series of the transition metals are 3d series from Sc to Zn, 4d
series from Y to Cd and 5dseries from La to Hg.
• The fourth 6dseries begins from Ac and is incomplete till now.
Position of d-block in periodic table
 • The d-block elements are found in the middle section of s- and p- block
elements in the periodic elements.
• This lead to its name ‘transition’ due to its position between s- and p-
block elements.
Electronic Configurations of the d-Block Elements

• The electronic configuration of d-block elements is(n-1) d1–10 ns1–2. They

have two incomplete outer shells.
• Where (n–1) = Inner d orbitals having electrons from 1-10.
• ns = Outermost orbital may have one or two
• (n-1) d10 n s2 represents the electronic configurations of Zn, Cd and Hg.
• They exhibit variable valency that differ by units of one.
Physical Properties
• The transition metals are hard and tough. They have low volatility but Zn,
Cd and Hg are an exception.

• They have high melting and boiling points due to the greater quantity of
electrons from (n-1) d along with the ns electrons metallic
Fig. The trends in melting point of d-block elements.
• Metals possessing high boiling point are noble in their.
• The metals belonging to second and third series have greater enthalpies
of atomisation than the elements belonging to first series.

Fig. Enthalpies of atomisation

Metallic characteristics:
• All transition metals exhibit metallic character.

• They are good conductors of heat and electricity.

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

Fig. Aluminium is beaten into thin sheets to make aluminium foil used to pack
food (Malleability)

Fig. bells in temples are made of metal that when struck against hard surface
produces sound (Sonorousity)

Fig. Metals are drawn into wires (Ductility)

• They form alloys by combining with some other metals.
 • They are found to exist in face-centered cubic (fcc) structure, hexagonal
close-packed (hcp) structure and body-centered cubic (bcc) structure.
• The transition elements exhibit covalent as well as metallic bonding
within the atoms.
Atomic radii
• The atomic radii of the elements of 3d-series decreases as the atomic
number increases.
• The atomic radii increase from 3d to 4d, the atomic radii of the 4d and
5d transition series are very close due to lanthanoid contraction. For
example, Zirconium and Hafnium.
• This decrease in the metallic radius due to increase in the atomic mass
leads to an increase in the density of elements. Consequently the density
increases from titanium to copper.

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

Oxidation States
• The number allotted to an element in a compound representing the
number of electrons lost or gained by an atom of the element of the
compound is called oxidation state.
For example, the electron configuration of copper is [Ar] 3d10 4s1. It attains
noble gas configuration by losing one electron. The energy required to lose one
more electron is very less and hence copper loses 2 electrons and forms
Cu2+ ion. Therefore copper exhibits +1 and +2 oxidation state. But +2 oxidation
states are more common.
It forms compounds like CuCl2 and also with oxygen like CuO. In both the cases
the oxidation state of Cu is +2.
• Transition elements exhibit varying oxidation states due to the minor
energy difference between ns and (n -1) d orbitals.
• Along with ns electrons, (n -1) d electrons takes part in bonding. But due
to the availability of few electrons for bonding Scandium does not show
variable oxidation states.
 • Due to presence of more d electrons, zinc has less orbital available for
bonding and hence does not exhibit varying oxidation state.
• Among d-block elements the elements belonging to 8th group exhibit
maximum oxidation state.
• Among the elements of 3d –series Manganese belonging to 7th group
exhibits maximum oxidation state.
• Among the elements of 4d-Series Ruthenium belonging to 8th group
exhibits maximum oxidation state.
• Among the elements of 5d-Series Osmium belonging to 8th group
exhibits maximum oxidation state.
• The oxidation number of a free element is always 0.
• Oxidation number of (group I) elements like Li, Na, K, Rb, Cs is +1.
• Oxidation number of (group II) elements like Be, Mg, Ca, Sr, Ba is +2.
• Oxidation number of oxygen is -2.
• For example, oxidation state of Phosphorous in the compound HPO32-
can be calculated by the following method:
Oxidation state of H = +1
Oxidation state of O = -2
Oxidation state of O3 = 3(-2) [Since it has 3 atoms of oxygen.]
Overall oxidation state of the compound = -2
Let P represent the oxidation state of Phosphorous.
Therefore,
HPO32- = +1+P+3(-2) = -2
• P = +3
Standard hydrogen electrode
• The electrode is connected to a standard hydrogen electrode (SHE) to
constitute a cell
• It consists of a platinum electrode coated with a layer of platinum black.
 • The electrode is immersed in an acidic solution and the pure hydrogen
gas is bubbled through it.
• The concentration of the reduced form and the oxidized form of
hydrogen is sustained at unity with following conditions:
• Pressure of hydrogen gas = 1 bar
• Concentration of hydrogen ion in the solution = 1 molar
Ecell = Ecathode – Eanode
Ecell = Ecathode – 0 = Ecathode
• The measured Emf of the cell:
Pt| H2 (1 bar)| H+ (1M) || Cu2+ (1M)| Cu is 0.34 V.
The positive value of the standard electrode potential signifies the easy
reduction of Cu2+ ions than H+ ions.
• The measured Emf of the cell
Pt| H2 (1 bar)| H+ (1M) || Zn2+ (1M)| Zn is -0.76 V.
The negative value of the standard electrode potential signifies that the
hydrogen ions oxidizes the zinc (or it can be said that zinc can reduce hydrogen
ions).
• An electrode with standard electrode potential greater than zero is
stable in its reduced form compared to hydrogen gas.
 • Whereas an electrode with negative standard electrode potential is less
stable in its reduced form compared to hydrogen gas.
• This decreases the standard electrode potential which in turn decreases
the oxidizing power of the specific electrode on the left and increases
the reducing power of the electrode to the right of the reaction.
Magnetic Properties
Substances, depending on their behaviour in an external magnetic field, are
classified into 2 types:
Paramagnetic
• They are weakly attracted on application of magnetic field due to
presence of one or more unpaired electrons that gets attracted by the
magnetic field.
• Application of a magnetic field magnetizes the paramagnetic substances
in the same direction but lose their magnetism in the absence of
magnetic field.
• O2, Cu2+, Fe3+, Cr3+ are some examples of such substances.

Fig. A trickle of liquid oxygen is deflected by a magnetic field, illustrating its

para magnetism.

Diamagnetic
• They are weakly repelled by a magnetic field due to the absence of
unpaired electrons.
• They are weakly magnetized on application of magnetic field in opposite
direction.
 • Pairing of electrons cancels out their magnetic moments and they lose
their magnetic character.
• For example, H2O, NaCl and C6H6 are some examples of such substances.

In 3d series the orbital angular momentum of the electrons of the elements is

less due to which they exhibit less contribution.

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

PROBLEM: Calculate the 'spin only' magnetic moment of M2+(aq) ion (Z = 27).
SOLUTION: Z = 27 = [Ar] 3d7 4s2
M2+ = [Ar] 3d7

This means that it has 3 unpaired electrons.

n=3

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

• [Fe(CN)6]4–
 • [Cu(NH3)4]2+

• [PtCl4]2–

Formation of Interstitial Compounds

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

Alloy Formation
• Alloys are homogeneous mixtures of more than one metal that can
displace another metal from the crystal lattice due to their comparable
sizes. This leads to the formation of alloys.
• The alloys so formed are hard with high melting points. For example,
chromium, vanadium, tungsten, manganese, molybdenum are the
ferrous alloys.
• Some other examples are brass (alloy of copper + zinc), stainless steel,
bronze (alloy of copper + tin), etc.
Non-stoichiometric Compounds
• The compounds in which the there is no conformity in chemical
composition with the ideal chemical formula are called non-
stoichiometric compounds.
• These compounds are formed due to variable valency in transition
metals and also due to the defects arising in solid state.
 • The compounds formed with O, S, Se, Te, Fe, Zn etc. are the examples
of such compounds.

Preparation of K2Cr2O7
Potassium dichromate, (K2Cr2O7) is an orange-ish inorganic
chemical reagent. In different laboratory or industry it is
basically used as an oxidizing agent usually for alcohols.
It can be prepared through the following process:
• At first the fusion of chromite ore FeCr2O4 with sodium
or potassium carbonate in the presence of access of air.
4FeCr2O4 + 8Na2CO3 + 7O2 --> 8Na2CrO4 + 2FeO3 + 8CO2
• Solution of sodium chromate is first filtered and then
acidified with a solution of sulfuric acid which results in
an orange sodium dichromate solution Na2Cr2O7 2H2O
can be crystallized.
2Na2CrO4 + 2H+ --> Na2Cr2O7 + 2Na+ + H2O
• Sodium dichromate is more soluble than potassium
dichromate and therefore it is fused with KCl that leads
to the formation of orange crystals of potassium
dichromate.
Na2Cr2O7 + 2KCl --> K2Cr2O7 + 2NaCl
 • At pH equal to 4 the dichromates and chromates exists
in equilibrium and can be inter convertible.
2CrO4 2- + 2H2+ --> Cr2O72- + H2O
Cr2O7 2- + 2OH- --> 2CrO42- + H2O

• The yellow colour of chromate changes to orange

coloured dichromate in the presence of acidic medium
whereas the dichromate changes into chromate in the
presence of basic medium.
2CrO42- + 2H+ --> 2HCrO4- (Hydrogen chromate)

2HCrO4- --> Cr2O72- + H2O Dichromate (orange)

• The chromate ion is tetrahedral and the dichromate ion
consists of two tetrahedral sharing at one corner, with
Cr-O-Cr bond angle 126 degree.
Properties of Potassium dichromate (K2Cr2O7)
• Oxidizing properties

Potassium dichromate is a powerful oxidizing-agent in an acidic

medium.
• Cr2O7 2- + 14H+ + 6 electron --> 2Cr3+ + 7H2O
•
It oxidizes iodides to iodine.
• Cr2O7 2- + 14H+ + 6I- --> 2Cr 3+ + 7H2O + 3I2
•
It oxidizes ferrous salts to ferric salts.
• Cr2O7 2- + 14H+ + 6 Fe2+ --> 2Cr 3++ 7H2O + 6Fe3+
•
It oxidizes stannous salts to stannic salts.
• Cr2O7 2- + 14H+ + 3Sn 2+ --> 2Cr 3+ + 7H2O + 3Sn 4+
•
It oxidizes H2S to sulphur.
• Cr2O7 2- + 8H+ + 3H2S --> 2Cr 3+ + 7H2O + 3S
•
• Action of heat

Application of heat leads to the decomposition of Potassium

dichromate leading to the formation of potassium chromate,
chromic oxide and oxygen.
• 4K2Cr2O7 -Heat-> 4K2CrO4 + 2CrO3 + 3O2
Preparation of Potassium Permanganate (KMnO4)
Potassium Permanganate (KMnO4) is a dark purple solid consisting
of two ions: a potassium ion (K⁺) and a permanganate ion (MnO−
4
). It is a strong oxidizing agent and also possess medication
properties due to which it is extensively used to clean wounds and
in dermatitis.
• Fusion of powdered Pyrolusite ore (MnO2) with an alkali metal
hydroxide like KOH in the presence of air or an oxidizing agent
like KNO3 leads to the formation of dark green potassium
Manganate (K2MnO4) which disproportionate either in a
neutral or acidic medium and results in the formation
of potassium permanganate.
2 MnO2 + 4 KOH + O2 --> 2K2MnO4 + 2H2O
3 MnO42- + 4H+ --> 2MnO4- + MnO2 + 2H2O
• Potassium permanganate is commercially prepared by an
alkaline oxidative fusion of Pyrolusite ore (MnO2) and again by
the electrolytic oxidation of manganate (4) ion.
2 MnO2 + 4KOH + O2 --> 2K2MnO4 + 2H2O
MnO42- + (electrolytic oxidation) --> MnO4- + e-
 Introduction to F-block elements
• 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.

Problem: Actinoid contraction is greater from element to element

than lanthanoid contraction. Why?
Solution: In actinoids, 5f orbitals are filled having poorer shielding
effect than 4f orbitals (in lanthanoids) due to which the effective
nuclear charge experienced by the electrons in valence shells of
actinoids is more than what is experienced by lanthanoids. Therefore,
the size of contraction in actinoids is greater as compared to that in
lanthanoids. They are termed as inner transition elements due to their
occurrence inside the series of transition elements.
Lanthanoid:
 • The electronic Configuration of lanthanoid is [Xe] 4fn+1 5d°
6s2 or [Xe] 4fn 5d1 6s2 with their valence shell electronic
configuration as 4f1−14 6s2.
• They exhibit the oxidation state of +3, +2 and +4.
• The initial members of this series are somewhat reactive
towards calcium which resembles their behaviour to that of
aluminium with the gradual increasing atomic number.
• On application of gentle heat Lanthanides combine with
hydrogen.
• Heating them with carbon leads to the formation of carbides and
halides (in presence of halogens while burning).
• Reaction of Lanthanides with dilute acids releases hydrogen gas.
• They form basic alkaline earth metal oxides and hydroxides like
N2O3 and M(OH)3.
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
• As a result of lanthanoid contraction there is a similarity in the
properties of second and third transition series.
Oxidation States of lanthanoids
• The elements belonging to lanthanide series exhibit an oxidation
state of +3. For example, Praseodymium (Pr) shows +3
oxidation state.
• Some elements exhibit +2 oxidation states in their complexes in
solutions. For example, Samarium (Sm), Europium (Eu),
Thulium (Tm) and Ytterbium (Yb) show +2 oxidation state.
• Some elements exhibit +4 oxidation states due to high stability
of empty, half-filled or fully filled f-subshells.
• Praseodymium (Pr), Neodymium (Nd), Terbium (Tb) and
Dysprosium (Dy) exhibits +4 oxidation state in their oxides.
• Cerium (Ce) shows both +3 as well as +4 state.
Actinoids

• The elements from Th to Lr belong to the series of Actinoids i.e.

Actinoids contain 14 elements.
• They are radioactive elements.
• The former elements have long half-lives whereas the latter
elements have a half-life value ranging from1 day to 3 minutes
for lawrencium with atomic number 103.
• Actinoids have the electronic configuration of 7s2 and inconstant
occupancy of the 5f and 6d subshells.
• Electronic configuration of Thorium is 5f1 6d1 7s2, Am is [Rn]
5f77s2 and Cm
is [Rn] 5f 76d17s2
 • The ionic radii gradually decrease across the series due to the
poor screening effect of nuclear charge exerted by
the f electrons. This is called Actinoid contraction.

Oxidation state in Actinoids

• In general the oxidation state of these elements is +3 (similar to
lanthanides).
• They also exhibit +4 oxidation states.
• Some of the elements also exhibit higher oxidation states.
• The oxidation state initially rises to the middle of the series (+4
for Th to +5, +6 and +7 for Pa, V and Np) and then descends in
the succeeding elements.
General Characteristics and Comparison of Actinoids with
Lanthanoids
(i) Electronic configuration
• The general electronic configuration for actinoids is [Rn]86 5f1-
14
6d0-1 7s2 and for lanthanoids is [Xe]54 4f0-14 5d0-1 6s2.
(ii) Atomic and ionic sizes
• Like lanthanoids the ionic radii of actinoids gradually decrease
across the series due to the poor screening effect of nuclear
charge exerted by the f electrons.
(iii) Oxidation states
• The lanthanoids exhibit +3 oxidation states. Some elements may
exhibit + 2 and + 4 oxidation states due to extra stability of
fully-filled and half-filled orbitals.
 • On the other hand Actinoids also exhibit + 3 oxidation state.
They also exhibit varying oxidation states due to the comparable
energies of 5f, 6d, and 7s.
(iv) Chemical reactivity
• Earlier members of the lanthanide series are more reactive and
are comparable to solution: They resemble Al with increasing
atomic number.
• Finely divided Actinoids are highly reactive metals and when
added to boiling water gives a mixture of oxide and hydride.
• At moderate temperatures Actinoids combine with most of the
non-metallic elements.
• Actinoids remain unaffected by the action of alkalies but gets
slightly affected by nitric acid due to the formation of a
protective oxide layer.
Applications of d- and f-Block elements
• Iron and steels are used for making tools, utensils, vehicles,
bridges and much more.

• TiO for the pigment industry and MnO2 for use in dry battery
cells.

• Zn and Ni/Cd is also used for battery industry.

 • Elements of Group 11 called the coinage metals.

• V2O5 catalyses the oxidation of SO2 in the manufacture of

sulphuric acid.
• TiCl4 with A1(CH3)3 forms the basis of the Ziegler catalysts
used to manufacture polyethylene (polythene).
• Iron catalysts are used in the Haber process for the production of
ammonia from N2/H2 mixtures.
• Nickel catalysts enable the hydrogenation of fats
• Wacker process the oxidation of ethyne to ethanal is catalysed
by PdCl2.
• Nickel 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.
Problem: Write down the electronic configuration of:
(i) Cr3+ (iii) Cu+ (v) Co2+ (vii) Mn2+
(ii) Pm3+ (iv) Ce4+ (vi) Lu2+ (viii) Th4+
Solution:
(i) Cr3+: 1s2 2s2 2p6 3s2 3p6 3d3
Or, [Ar]183d3
(ii) Pm3+: 1s2 2s2 2p6 3s2 3p6 3d10 4s2 4p6 4d105s2 5p6 4f4
Or, [Xe]54 3d3
(iii) Cu+: 1s2 2s2 2p6 3s2 3p6 3d10
Or, [Ar]18 3d10
(iv) Ce4+: 1s2 2s2 2p6 3s2 3p6 3d10 4s2 4p6 4d10 5s2 5p6
Or, [Xe]54
(v) Co2+: 1s2 2s2 2p6 3s2 3p6 3d7
Or, [Ar]183d7
(vi) Lu2+: 1s2 2s2 2p6 3s2 3p6 3d10 4s2 4p6 4d10 5s2 5p6 4f14 5d1
Or, [Xe]542f143d3
(vii) Mn2+: 1s2 2s2 2p6 3s2 3p6 3d5
Or, [Ar]18 3d5