d-block elements: The elements in which last electron enters in the d - sub-shell i.e.

penultimate shell and lies in the middle of the periodic table belonging to groups 3-12.

Transition elements: The elements of d-block are known as transition elements as

they possess properties that are transitional between the s-block and p-block
elements. Transition elements are defined as the elements which have incompletely
filled d-orbitals in their ground states or in its most common oxidation state. Transition
elements have four series:
(i) First transition series: These elements have incomplete 3d-orbitals and they are from Sc
(21) to Zn (30).
(ii) Second transition series: These elements have incomplete 4d-orbitals and they are from
Y (39) to Cd (48).
(iii) Third transition series: These elements have incomplete 5d- orbitals and they are La
(57) and then from Hf (72) to Hg (80).
(iv) Fourth transition series: This series is yet incomplete and these elements have
incomplete 6d- orbitals. Known elements of this series are–actinium (89) and then from Rf
(104) and other elements.

General electronic configuration of transition elements: Valence shell electronic

configuration is (n–1)d¹⁻¹⁰, ns¹⁻² , where n is the outermost shell.

General characteristics of Transition Elements:

Physical Properties:
(i) All are metals.
(ii) All are malleable and ductile except mercury (liquid).
(iii) High thermal and electrical conductivity.
(iv) Metallic lustre and sonorous.
(v) Atomic radii: Smaller than atomic size of s-block elements, larger than atomic size of p-
block elements in a period.
In a transition series, as the atomic number increases, the atomic radii first decreases till the
middle, becomes constant and then increases towards end of the period.
It usually increase down the group. The size of 4d elements is almost of the same size as of
the 5d series elements.
The filling of 4f before 5d orbitals results in regular decrease in atomic radii which is called
as lanthanoid contraction.
(vi) Ionic radii: The ionic radii decrease with increase in oxidation state.
(vii) Density: From left to right in a period, density increases.
(viii) Ionisation enthalpy: Along the series from left to right, there is an increase in ionisation
enthalpy. Irregular trend in the first ionisation enthalpy of 3d metals is due to irregularity in
electronic configuration of 4s and 3d orbitals. In a group, IE decreases from 3d to 4d-series
but increases from 4d to 5d series due to lanthanoid contraction.
(ix) Metallic bonding: In metallic bonding, regular lattice of positive ions are held together by
a cloud of free electrons, which can move freely through the lattice. Transition metal atoms
are held together by strong metallic bonds.
(x) Enthalpy of atomisation: Enthalpy of atomisation is the heat required to convert 1 mole of
crystal lattice into free atoms. Transition elements have high enthalpy of atomisation. It first
increases, becomes maximum in the middle of the series and then decreases regularly.
(xi) Variable oxidation state: Since the energies of ns and (n–1) d electrons are almost equal,
therefore the electrons of both these orbitals take part in the reactions, due to which
transition elements show variable oxidation states. Transition metal ions show variable
oxidation states except the first and last member of the series.
(xii) Electrode potential: The electrode potential develops on a metal electrode when it is in
equilibrium with a solution of its ions, leaving electrons from the electrode. Transition metals
have lower value of reduction potential. Variation in E° value is irregular due to the regular
variation in ionisation enthalpies (I.E₁ + I.E₂), sublimation and hydration enthalpies.
(xiii) Catalytic properties: Many of the transition metals and their compounds, particularly
oxides act as catalysts for a number of chemical reactions. Iron, cobalt, nickel, platinum,
chromium, manganese and their compounds are the commonly used catalysts.
All transitional metals show multiple oxidation states and have large surface area so, all
metals work as a catalyst.
(xiv) Magnetic properties: On the basis of the behaviour of substances in magnetic field, they
are of two types :
(i) Diamagnetic, (ii) Paramagnetic.
Diamagnetic substances have paired electrons only. e.g., Zn has no (zero) paired electrons.
In paramagnetic substances, it is necessary to have at least one unpaired electron.
Paramagnetism increases
with the increase in number of unpaired electrons.
Paramagnetism may be measured by magnetic moment.
Magnetic moment, (µ) = under-root n(n+2) B.M.
where n = number of unpaired electrons in atom or ion and B.M. = Bohr Magnetron (unit of
magnetic moment). Diamagnetic and paramagnetic substances are repelled and attracted in
the magnetic field respectively (Magnetic properties of transition elements).
(xv) Melting and boiling points: Except zinc, cadmium and mercury, all other transition
elements have high melting and boiling points. This is due to strong metallic bonds and
presence of partially filled d-orbitals in the shell of the atom of element.
(xvi) Complex formation: They have tendency to form complex ions due to high charge on the
transition metal ions and the availability of d-orbitals for accommodating electrons donated
by the ligand atoms.
(xvii) Formation of coloured compounds: Transition metals form coloured ions due to the
presence of unpaired d-electrons. As a result, light is absorbed in the visible region to cause
excitation of unpaired d-electrons (d – d transition) and colour observed corresponds to the
complementary colour of the light absorbed. Cu⁺, Zn²⁺ and Cd²⁺ are colourless due to the
absence of unpaired d-electron (d¹⁰).
(xviii) Formation of alloys: Alloy formation is due to almost similar size of the metal ions, their
high ionic charges and the availability of d-orbitals for bond formation. Therefore, these
metals can mutually substitute their position in their crystal lattice to form alloys. e.g., steel,
brass.
(xix) Formation of interstitial compounds: Interstitial compounds are known for transition
metals as small-sized atoms of H, B, C, N, etc. can easily occupy positions in the voids
present in the crystal lattices of transition metals. Characteristics of interstitial compounds:
l High melting points
l Hard
l Chemically inert
l Retain metallic conductivity
l Non-stoichiometric
Oxides of Transition metals: They form oxides of the general composition MO, MO₃, MO₂,
M₂O₅ and MO₆.
Oxides in the lower oxidation states are generally basic while those in the higher oxidation
states are amphoteric
or acidic. For example,
+2, +3 ,+8, +3 ,+4 ,+7
MnO, Mn₂O₅, Mn₃O₄, MnO₂, Mn₂O₇
Basic, Amphoteric, Amphoteric, Amphoteric, Acidic
Potassium Dichromate (K₂Cr₂O₇):
Preparation: It is prepared from chromate ore in the following steps:
(i) Chromite ore is fused with sodium carbonate in the presence of air to give sodium
chromate.
4FeCr2O4 + 8Na2CO3 +7O2 → 2Fe2O3 + 8Na2CrO4 + 8CO2
(ii) Na2CrO4 is filtered and acidified with conc. H2SO4 to give Na2Cr2O7.
2Na2CrO4 + 2H+ → Na2Cr2O7 + 2Na+ + H2O.
(iii) Sodium dichromate solution is treated with KCl to give K2Cr2O7.
Na2Cr2O7 + 2KCl → K2Cr2O7 + 2NaCl
Properties:
(a) It is an orange, crystalline solid.
(b) With alkali:
Cr2O72– + 2OH– → 2CrO42– + H2O
Chromate ion
(Yellow)
(c) With acid:
2CrO42– + 2H+ → Cr2O72– + H2O
Dichromate ion
(orange red)
In acidic solutions, oxidising action is
Cr2O72–+ 14H++ 6e– → 2Cr3+ + 7H2O
(d) It is a powerful oxidising agent. For example,
(i) It oxidises ferrous to ferric.
Cr2 O72– + 14H+ + 6e– → 2Cr3+ + 7H2O
[Fe2+ → Fe3+ + e–] × 6
Cr2O72– + 6Fe2+ 14H+ → 2Cr3++ 6Fe3+ + 7H2O
(ii) It oxidises stannous to stannic.
Cr2O72– + 14H+ + 6e– → 2Cr3+ + 7H2O
[Sn2+ → Sn4+ + 2e–] × 3
Cr2O72– + 3Sn2+ 14H+ → 2Cr3+ + 7H2O + 3Sn4+
(iii) It oxidises sulphur dioxide to sulphate.
Cr2O72– + 14H++ 6e– → 2Cr3+ + 7H2O
[SO2 + 2H2O → SO42– + 4H+ + 2e–] × 3
Cr2O72– + 3SO2 + 2H+ → 2Cr3+ + 3SO42– + H2O
(iv) It oxidises hydrogen sulphide to sulphur.
Cr2O72– + 14H++ 6e– → 2Cr3+ + 7H2O
[H2S → 2H+ + S + 2e–] × 3
Cr2O72– + 3H2S + 8H+ → 2Cr3+ + 3S + 7H2O
(v) It oxidises iodides to iodine.
Cr2O72– + 14H+ + 6e–→ 2Cr3+ + 7H2O
[2I–→ I2 + 2e–] × 3
Cr2O72– + 6I– +14H+ → 2Cr3+ + 3I2 + 7H2O
Uses:
(i) In leather industry for chrome tanning.
(ii) Preparation of azo compounds.
(iii) As a primary standard in volumetric analysis for the estimation of reducing agent.
Structure : From NCERT
Potassium permanganate (KMnO4)
Preparation:
(i) It is prepared from pyrolusite ore with KOH in the presence of oxidising agent like KNO3.
The dark green potassium manganate undergoes electrolytic oxidation to produce potassium
permanganate.
2MnO2 + 4KOH + O2 → 2K2MnO4+ 2H2O
3MnO42– + 4H+ → 2MnO4– + MnO2 + 2H2O
(ii) Commercially, it is prepared by alkaline oxidative fusion of MnO2 followed by electrolytic
oxidation of manganate (VI).
MnO2+2e– → MnO42-
MnO42– → MnO4– +1e–
(iii) In laboratory, by oxidation of manganese (II) ion salt by peroxodisulphate.
2Mn2+ + 5S2O82– + 8H2O → 2MnO4– + 10SO42– + 16H+
Properties:
(i) Dark purple crystalline solid.
(ii) Sparingly soluble in water.
(iii)Decomposes on heating at 513 K.
2KMnO4 → K2MnO4 + MnO2 + O2
(iv) Acts as a powerful oxidising agent in acidic, alkaline and neutral medium. For example
1. In acidic medium oxidises:
(i) Iodide to iodine
[MnO4– + 8H+ +5e–→ Mn2+ + 4H2O] × 2
[2I–→ I2 + 2e–] × 5
2MnO4– + 10I– + 16H+→ 2Mn2+ + 5I2 + 8H2O
(ii) Ferrous to ferric
MnO4– + 8H++ 5e–→Mn2+ + 4H2O
[Fe2+ → Fe3+ + e–] × 5
MnO4– + 5Fe2+ + 8H+→ Mn2+ + 5Fe3+ + 4H2O
(iii) Oxalate to carbon dioxide :
[MnO4– + 8H + 5e–→ Mn2+ + 4H2O] × 2
[C2O42–→ 2CO2 + 2e–] × 5
2MnO4– + 5C2O42–+ 16H+ → 2Mn2+ + 10CO2 + 8H2O
(iv) Hydrogen sulphide to sulphur
[MnO4– + 8H+ + 5e–→ Mn2+ + 4H2O ] × 2
[S2–→ S + 2e–] × 5
2MnO4– + 5S2– + 16H+ → 2Mn2+ + 5S + 8H2O
(v) Sulphite to sulphate
[MnO4– + 8H+ + 5e–→ Mn2+ + 4H2O] × 2
[SO32– + H2O → SO42– + 2H+ + 2e–] × 5
5SO32– + 2MnO4– + 6H+ → 2Mn2++5SO42– + 3H2O
(vi) Nitrite to nitrate
[MnO4– + 8H+ + 5e–→ Mn2+ + 4H2O] × 2
[NO2– + H2O → NO3– + 2H+ + 2e–] × 5
2MnO4– + 5NO2– +6H+ → 2Mn2+ + 5NO3– +3H2O
2. In neutral alkaline medium:
(i) Iodide to iodate
[MnO4– + 2H2O + 3e–→ MnO2 + 4OH–] × 2
I– + 6OH–→ IO3– + 3H2 O + 6e–
2MnO4– + I– + H2O → IO3– + 2MnO2 + 2OH–
(ii) Manganous to manganese dioxide
2MnO4– + 3Mn2⁺ + 2H2O → 5MnO2 + 4H⁺
(iii) Thiosulphate to sulphate
8MnO4– + 3 S2O32– + H2O → 8MnO2 +6SO42– + 2OH⁻
Uses:
(i) Bleaching of wool, silk, cotton and other textile fibres, etc.
(ii) Decolourisation of oils.
(iii) In analytical chemistry (titration).
(iv) In organic synthesis.

Note: refer the book to clear subscript and superscript in chemical reactions of K₂Cr₂O₇ &
KMnO₄.

f-block elements: The elements in which filling of electrons takes place in (n–2) f-subshell
which belongs to anti-penultimate (third to the outermost) energy shell. This block consists
of two series of elements known as Lanthanoids and Actinoids. These elements are also
known as inner transition elements. The general electronic configuration of the f - block
elements is:
(n–2)f¹⁻¹⁴(n–1)d⁰⁻¹ ns²
For lanthanoids, n is 6 while its value is 7, for actinoids. There are many exceptions in the
electronic configuration.
Lanthanoids: The series involves the filling of 4f-orbitals following lanthanum La (Z = 57) is
called the lanthanoid series. There are 14 elements in this series starting with Ce (Z = 58) to
Lu (Z = 71).

Physical properties:
(i) Highly dense metals, soft, malleable and ductile.
(ii) High melting point.
(iii) Forms alloys easily with other metals.
(iv) Magnetic properties: Among lanthanoids, La3+ and Lu3+ which have 4f⁰ or 4f¹⁴
electronic configurations are diamagnetic and all other trivalent lanthanoid ions are
paramagnetic due to the presence of unpaired electrons.
(v) Atomic and ionic sizes: With increasing atomic number, the atomic and ionic radii
decreases from one element to the other but the decrease is very small.
A steady decrease in the size of lanthanoids with increase in atomic number is known as
lanthanoid contraction.
Consequences of Lanthanoid contraction:
(a) It leads to similar physical and chemical properties among lanthanoids.
(b) Zr and Hf have same properties, due to similar atomic radii.
(c) Chemical separation of lanthanoids become difficult.
(vi) Oxidation state: They mainly give +3 oxidation state. Some elements show +2 and +4
oxidation states.
(vii) Colour: Some of the trivalent ions are coloured. This happens due to the absorption in
visible region of the spectrum resulting in f-f transitions.
Chemical properties: All lanthanoids are highly electropositive metals and have almost
similar chemical reactivity.
Uses:
(i) Misch metal is the alloy of cerium (about 55%) and various other Lanthanoid elements
(40-43%). It also contains iron upto 5% and traces of sulphur, carbon, silicon calcium and
aluminium. It is a pyrophoric material, hence it is used in lighter flints.
(ii) Lanthanoid oxides are used for polishing glass.
(iii) Cerium salts are used in dyeing cotton and also as catalysts.
(iv) Lanthanoid compounds are used as catalyst for hydrogenated dehydrogenation and
petroleum cracking.
(v) Pyrophoric alloys are used for making tracer bullets and shells.
Actinoids: The series involving the filling of 5f orbitals from actinium, Ac (Z = 89) upto
lawrencium, Lr (Z = 103) comprises of actinoids.
All the elements beyond uranium are known as transuranic or man-made elements. These
elements do not occur in nature because their half-life periods are so short.
Electronic configuration: [Rn] 5f ¹⁻¹⁴ 6d ⁰⁻¹ 7s²
Physical properties:
(i) Highly dense metals and form alloys with other metals.
(ii) Silvery white metals.
(iii) Highly electropositive.
(iv) High melting point.
(v) Ionic and atomic radii: The atomic and ionic size decreases with an increase in atomic
number due to actinoid contraction. The electrons are added to 5f shell resulting in an
increase in the nuclear charge causing the shell to shrink inwards. This is known as actinoid
contraction.
(vi) Colour: Many actinoid ions are coloured.
(vii) Magnetic properties: Many actinoid ions are paramagnetic.
(viii) Oxidation State: The common oxidation state exhibited is +3. They also exhibit oxidation
state of +4,
+5, +6 and +7.
(ix) Many elements are radioactive.
Chemical reactivity: Less reactive towards acids.
Uses:
(i) Thorium is used in the treatment of cancer and in incandescent gas mantles.
(ii) Uranium is used in the glass industry, in medicines and as nuclear fuel.
(iii) Plutonium is used in atomic reactors and in atomic bombs.

Difference between Lanthanoids and Actinoids:

Lanthanoids
(i) 4f orbital is progressively filled.
(ii) +3 oxidation state is most common along with
+2 and +4.
(iii) Except promethium, all are non-radioactive.
(iv) Less tendency of complex formation.
(v) Chemically less reactive than actinoids.
Actinoids:
(i) 5f orbital is progressively filled.
(ii)+3 oxidation state is most common, but exhibit
higher oxidation state of +4, +5, +6, +7.
(iii)All are radioactive.
(iv)Strong tendency of complex formation.
(v)More reactive than lanthanoids.