ST.

XAVIER’S INSTITUTION
ISC 2023
ISC 2024
INORGANIC CHEMISTRY
D BLOCK ELEMENTS

1. d-block: 3d, 4d and 5d series:

General electronic configuration: (n-1)d1-10 ns1-2 (where n is the last shell quantum no.)

➢ Exceptional electronic configuration or 24Cr and 29Cu are due to the stability of half-filled
and full-filled d-orbitals
For 24Cr:

For 29Cu:
 ➢ They are known as transition element as their properties are intermediate to that of
metals and non-metals. But the elements will full-filled d-orbitals are not considered as
transition elements which are Zn, Cd and Hg,
➢ Most abundant transition metal is iron(Fe).
➢ Technitium (Tc) is man-made transition element of 2nd transition series (4d series).
➢ Hg is the only liquid transition metal.
➢ Densest elements are osmium and iridium.
➢ 6d series elements are radioactive.
➢ In 6d series elements from atomic no.104 to 112 all are man-made.

A. Metallic character:
Due to the presence of very small no. of electrons in outer shell (ns1 or ns2) like other metals d-block
elements also exhibits metallic properties like –

• High mp and bp.

• Good conductor of heat and electricity
• Hard, malleable, ductile (except Hg)
• They have metallic luster, high density and high enthalpies of atomization
• They possess all 3 crystal structures like fcc, bcc, hcp
• Both metallic bonding (due to the presence of ns1 or ns2 electrons) and covalent bonding
(due to the presence of unpaired electrons in incomplete d-orbital) exist in transition
elements.

DO YOU KNOW:

*Cr, Mo, W are very hard metal and have strength of covalent bonding due to maximum no of
unpaired electrons (eg: Cr- 4s13d5). W (tungsten) has highest mp. (3410°C)

**Zn, Cd and Hg are soft and they have low mp and bp (as they do not have unpaired electrons in d-
orbitals).

***Metallic character increases down the group.

****At first mp. increases and reaches maximum at Cr. After that from Fe to Zn the mp. decreases. In
3d series Mn has the minimum melting point.

B. Atomic and ionic radii:

• Atomic radii of transition elements are smaller than s-block elements.
• In 3d series , radii increases from Sc to Cr and remains same from Cr to Cu. (reason : Sc to Cr
nuclear charge increases so radii decreases; in case of Cr to Cu as the no of d-electrons
increases a)the nuclear charge decreases and b) the screening effect decreases, due to these
two opposite factors the size remains almost same.
• At the end of each series the radius becomes highest due to inter electronic repulsions.
• For a particular group from 3d to 4d the size increases but the radii of 4d and 5d series
elements are almost same (except for La) due to the Lanthanide contraction.
 • Due to the inclusion of 14 electrons (in f orbitals with low shielding effect) between La and
Hf, the $d element Zr(zirconium) and Hf (hafnium) have almost same size.
• Ionic radii decrease gradually as atomic no increase in a particular group
• Ionic radii decrease with increase in charge of ion (eg: Fe3+<Fe2+, Ni3+<Ni2+)

C. Ionization enthalpy:
▪ Ionization energy lie between s block and p block elements.
▪ These elements are less electropositive than s-block elements and more electro-positive
than p-block elements. That is why s-block elements form ionic compounds whereas d-block
elements form covalent compounds.
▪ Ionisation energies increase (due to atomic size decreases from left to right which makes it
difficult to remove electrons from the last shell) but quite slowly. The reason is, the effect of
increased nuclear charge is neutralized by the additional screening effect of those electrons.
▪ Mn and Zn have very high IE values due to half filled and full filled configurations.
▪ IE3 of Mn is high as 3rd electron is to be removed from half-filled (3d5) orbital.
▪ IE2 of Cr and Cu are high due to their half-filled (Cr+ =3d5) and full-filled (Cu+=3d10)
configurations.
▪ In a same group , from 3d to 4d the IE decreases as size increases. But from 4d to 5d, the size
remains same while they differ by 32 units of nuclear charge. So IE value increases from 4d
to 5d.

D. Variable Oxidation state:

Oxidation state: The net numerical charge assigned to an atom of an element in its combined state is
known as its oxidation state.

• Variable oxidation states in transition elements occurs due to involvement of both ns and (n-
1)d orbital electrons as they have nearly same energy.
• Lower oxidation states are shown when ns orbital electrons participate in bonding.
• Higher oxidation states are shown when both ns and (n-1)d orbital electrons participate in
bonding.
• Tendency to show variable oxidation state increases as atomic no. increases and reaches
maximum in middle and then starts decreasing.
• In 3d series Mn shows highest oxidation state= +7
 • Ru and Os show highest oxidation state= +8
• Sc(3d14s2) and Zn(3d104s2) do not show variable oxidation states and they show (+3) and (+2)
respectively.
• Except Sc all 3d elements shows stable +2 oxidation state but Cu(3d104s1) shows +1
oxidation state due to loss 4s electron.
• Oxidation state of metals in metal carbonyl compounds [such as Fe(CO)5 , Cr(CO)6 ] is zero.
• +2 and +3 oxidation states form ionic bonds and higher oxidation states form covalent bonds
which is attained with elements of high electronegativity ( such as F,O). The reason is as
oxidation state on cation increases, the size decreases so according to Fajan’s rule the
polarizing power increases and covalent nature increase.
• Oxidation states with d0 , d5 and d10 configuration have higher stability than others.
• Exception: Cu+ is less stable than Cu+2 (which has greater -ve Hohydration than Cu+)
• CuI2 is unstable but CuI is stable (due to the high reducing property of I-).

E. Magnetic properties:
Most of the transition metals are paramagnetic (attracted by magnetic field) due to presence of
unpaired electrons in them but some are diamagnetic (repelled by magnetic field) due to absence of
unpaired electrons.

Magnetic character is expressed as magnetic moment (μ)

μ = √𝑛(𝑛 + 2) BM where n is the no of unpaired electrons and BM=bohr magneton

As the no. of unpaired electron increase the μ value increase so the para-magnetism increase,

Fe, Co and Ni – In these metals the electron spins are more pronounced and they strongly attaracted
by magnetic field for which they are known as Ferromagnetic substances.

Calculation of μ value for the following complexes:

[MnCl4]2- : Mn +2 =[Ar]3d54s0 , n= 5 , μ=√5(5 + 2) = 5.91

[NiCl4]2- : Ni+2=[Ar] 3d84s0, n=3, μ=√2(2 + 2) = 2.82

F. Formation of colored compound:

Substances appear colored if they absorb certain wavelengths of light from the visible region (400-
800nm) and its complimentary color is shown by the object.
The main reason of coloured compounds is presence of unpaired electrons in d-orbital.
• Transition metals and their compounds show color in their solid state or in aqueous solution
due to excitation of electrons from d-orbitals of lower energy to d-obitals of higher energy
i.e. t2g to eg which is known as d-d transition.
• Exception: K2Cr2O7 (orange) and KMnO4 (violet) shows color due to charge transfer from O
atoms to Cr+6 and Mn+7 ions respectively.
 • Zn+2, Cd+2, Hg+2, Sc+3, Ti+4 are colorless as they don’t have any unpaired electrons.
• Brown colored complex formed in brown ring test [Fe(H2O)5NO]SO4 which also shows color
due to charge transfer from NO ligand to metal ion.

G. Formation of complexes:
D block elements form complexes due to-

1) Small size and high nuclear charge and charge density.

2) Presence of vacant orbitals where electrons can be given by ligands.

Eg: [Ni(CN)4]2-(coordination no =4), [Fe(CN)6]4- (coordination no =6)

H. Alloy formation:
Transition metals tend to form alloys as they have similar atomic radii so they substitute atoms of
other metals in its crystal lattice to form solid solution of smooth alloys. Such alloys are harder, more
resistant to corrosion and they have high melting point than parent metals.

• Alloys containing Hg are known as amalgams, such as Na-Hg (sodium amalagam)

• Purpose of making alloys is to develop more useful properties which are absent in the
original metal.

I. Interstitial compounds:
The transition metals form a large number of interstitial compounds in which small atoms such as
H,C,B and N occupy the empty spaces (interstitial sites) in their lattices (see figure below).

1) They are represented by formulae like TiC, TiH2, Mn4N, Fe3H etc. However, they are actually
non-stoichiometric materials.
2) They are very hard and rigid (eg: steel contain Fe and C)
3) They have high m.p than the pure metals.
4) They show conductivity like that of pure metals.
5) They exhibit chemical inertness.
 J. Catalytic properties:
Transition metals and their compounds show catalytic properties due to-

1) They possess variable oxidation states.

2) They provide larger surface area for the reactants to be absorbed.

Potassium dichromate(K2Cr2O7)
• K2Cr2O7 is orange red crystals with melting point 669K
• By the action of heat, it decomposes into potassium chromate, chromic oxide and oxygen.

• When reacted with alkali it changes into yellow potassium chromate and water.

• Chromate and dichromate exist in equilibrium and are interconvertible with change in pH.
STRUCTURE OF DICHROMATE AND CHROMATE :

[Tetrahedral structure]

(Chromate ion CrO42-)

(DICHROMATE ION Cr2O72-)

Each (CrO4) subunit is tetrahedral and these two subunits share one common ‘O’ atom.

PREPARATION:
It is prepared from the ore called chromite (FeO.Cr2O3)

Step 1: Chromite to sodium chromate

finely powdered ore is mixed with sodium carbonate and quicklime and then roasted in a furnace by
which yellow colored sodium chromate is formed along with evolution of CO2 . Quick lime keeps the
mass porous and facilitates the oxidation.

Step 2: coversion of chromate to dichromate

The filtrate containing sodium chromate is treated with conc. H2SO4 and it is gets converted to
orange colored sodium dichromate after cooling and the byproduct sodium sulphate is removed as
crystals.

Step 3: conversion of sodium dichromate to potassium dichromate

Hot conc solution of sodium di9chromate is treated with calculated amount of potassium chloride
when potassium dichromate (much less soluble then sodium dichromate) crystallizes on cooling as
orange-red crystals.

REACTIONS:
1) ACTION OF ACID:
 2) Oxidation of ferrous salts to ferric salts:

3) Oxidation of I2 to KI

4) Oxidation of H2S to S

5) Reaction with SO2:

6) Reaction with hydrogen peroxide:

This is the structure of CrO5. It is also expressed as CrO(O2)2 which is a peroxo

compound.

USES:
In volumetric analysis, K2Cr2O7 is used as a primary standard for the estimation of Fe2+ and I- (iodide)in
redox titrations. (Na2Cr2O7 is not used as it is a deliquescent substance)

In industry it is used for chrome tanning, dyeing, painting, photography and preparation of other
compounds of chromium.

In organic chemistry, it is used as an oxidising agent.

KMnO4 (POTASSIUM PERMANGANATE):

1. PREPARATION:
On a large scale KMnO4 is prepared from its ore Pyrolusite (MnO2) in the following two steps:

Step 1: conversion of MnO2 to potassium manganate

Finely powdered pyrolusite mineral is fused with potassium hydroxide in the presence of air (or
other oxidizing agents) to form green color potassium manganate (K2MnO4).

Step 2: oxidation of potassium manganate to potassium permanganate:

The fused mass obtained from the first step is with water and after filtration it is oxidsied by chlorine
gas (or CO2 or O3) bubbling through the green solution to form potassium manganate.
 2. PROPERTIES AND REACTIONS:
I. Potassium permanganate exists as deep purple black prisms with a greenish lusture.
II. It is moderately soluble in water at room temperature and more soluble in hot water.
III. When heated to 513K it decomposes readily t give potassium manganate, manganese
dioxide and oxygen.
IV. Oxidizing property : it is a powerful oxidizing agent and its course of reaction depends on the
nature of medium
a) Acidic medium: (5 electrons transfer reaction so eqv. wt.= Mol. Wt/3)

1. With KI:

[Link] oxalic acid:

[Link] ferrous salt:

[Link] hydrogen sulphide:

b) neutral medium:

potassium permanganate acts as a mild oxidizing agent in neutral medium due to the following
reason: (3 Electrons are associated with this reaction so equivalent wt. = molecular wt./ 3)

1. oxidation of H2S

a) alkaline medium: (1 electron transfer reaction so [Link]. =mol. Wt.)

STRUCTURES OF MANGANATE AND PERMANGANATE IONS:

Tetrahedral manganate ion [MnO42-]

 tetrahedral permanganate ion [MnO4-]

Uses of potassium permanganate:

1. It is used in quantitative analysis for the estimation of ferrous salts, oxalates, iodides and
hydrogen peroxide.

2. It is used as strong oxidising agent in industry and also in laboratory. Alkaline KMnO4 is known as
Baeyer’s reagent.

3. It is a disinfectant and germicide and used for cleaning water.

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