The Transition Elements (d-Block)

Position in the Periodic Table

 Their position is in between s- and p- block elements.
 There are four rows of transition elements − 3d, 4d, 5d, and 6d. The fourth row of 6d is still
incomplete.
Electronic Configuration
 General outer electronic configuration is (n −1)d1−10 ns1−2.
o But this generalization has several exceptions as there is very little difference in
energy between (n − 1)d and ns orbitals. For example, Cr has electronic configuration
3d5 4s1 instead of 3d4 4s2. Cu has electronic configuration 3d10 4s1 instead of 3d9 4s2.
 Outer electronic configurations of the transition elements in the ground state are listed in the
following tables:

1st series 2nd series

Atomic Outer electronic Atomic Outer electronic

Element Element
number configuration number configuration

Sc 21 3d14s2 Y 2 4d15s2

Ti 22 3d24s2 Zr 2 4d25s2

V 23 3d34s2 Nb 1 4d45s1

Cr 24 3d54s1 Mo 1 4d55s1

Mn 25 3d54s2 Tc 1 4d65s1

Fe 26 3d64s2 Ru 1 4d75s1

Co 27 3d74s2 Rh 1 4d85s1

Ni 28 3d84s2 Pd 0 4d105s0

Cu 29 3d104s1 Ag 1 4d105s1

Zn 30 3d104s2 Cd 2 4d105s2

3rd series 4th series

Element Atomic Outer electronic Element Atomic Outer electronic

 number configuration number configuration

La 57 5d16s2 Ac 89 6d17s2

Hf 72 5d26s2 Rf 104 6d27s2

Ta 73 5d36s2 Db 105 6d37s2

W 74 5d46s2 Sg 106 6d47s2

Re 75 5d56s2 Bh 107 6d57s2

Os 76 5d66s2 Hs 108 6d67s2

Ir 77 5d76s2 Mt 109 6d77s2

Pt 78 5d96s1 Ds 1010 6d87s2

Au 79 5d106s1 Rg 111 6d107s1

Hg 80 5d106s2 Uub 112 6d107s2

 Zn, Cd, and Hg are not regarded as transition elements.

o Reason − The orbitals of these elements are completely-filled. [Electronic
configuration is (n − 1) d10 ns2]
 Ions of configuration d1−9 have similar magnetic and electronic properties.
 Elements with partially-filled d-orbitals exhibit certain characteristic properties such as
showing a variety of oxidation states, formation of coloured ions, and formation of complex
with a variety of ligands.
 They and their compounds have catalytic property and are paramagnetic in nature.

General Properties of Transition Metals : I

Physical Properties
 Nearly all transition metals display metallic properties such as high tensile strength, ductility,
malleability, high thermal and electrical conductivity and metallic lustre.
 Very hard and have low volatility (Exception: Zn, Cd and Hg)
 The melting and boiling points of the first transition series are lower than those of the heavier
 transition elements.
Reason: Occurrence of stronger metallic bonding (M−M bonding) in heavier metals
 Trends in melting points of transition metals are shown in the given figure.

 Transition elements have high effective nuclear charge and a large number of valence
electrons. Therefore, they form very strong metallic bonds. As a result, the enthalpy of
atomisation of transition metals is high.
 Trends in enthalpies of atomisation of transition elements are shown in the given figure.

 The enthalpies of atomisation of the elements in the first transition series are lower than those
of the corresponding elements in the second and third transition series.
Variation in Atomic and Ionic Sizes of Transition Metals
 Atomic size generally decreases from left to right across a period.
 The atomic sizes of the elements of the first transition series are smaller than those of the
corresponding heavier elements (elements of the 2nd and 3rd transition series).
 However, the atomic sizes of the elements in the third transition series are virtually the same
as those of the corresponding members in the second transition series. This is due to
lanthanoid contraction.
 Trends in atomic radii of transition elements are shown in the given figure.
Ionisation Enthalpies
 In each of the three transition series, the first ionisation enthalpy increases from left to right.
However, there are some exceptions.
 The first ionisation enthalpies of the third transition series are higher than those of the first
and second transition series.
Reason: Poor shielding effect of 4f electrons in the third transition series
 Certain elements in the second transition series have higher first ionisation enthalpies than the
elements corresponding to the same vertical column in the first transition series.
 There are also elements in the 2nd transition series whose first ionisation enthalpies are lower
than those of the elements corresponding to the same vertical column in the 1 st transition
series.

General Properties of Transition Metals : II

Oxidation States
 All transition metals exhibit a variety of oxidation states.
 The oxidation states of the first row transition metals are listed in the given table.

Sc Ti V Cr Mn Fe Co Ni Cu Zn

- +2 +2 +2 +2 +2 +2 +2 +1 +2

+3 +3 +3 +3 +3 +3 +3 +3 +2 -

- +4 +4 +4 +4 +4 +4 +4 - -

- - +5 +5 +5 - - - - -
 - - - +6 +6 +6 - - - -

- - - - +7 - - - - -

(The most common ones are in bold types)

 The variable oxidation states of transition elements are due to the participation of ns and
(n−1)d-electrons in bonding.
 Lower oxidation state is exhibited when ns-electrons take part in bonding.
 Higher oxidation states are exhibited when (n − 1)d-electrons take part in bonding.
 In each group, the highest oxidation state increases with the increase in atomic number;
reaches the maximum in the middle, and then starts decreasing.
Example: In the first transition series, manganese has the maximum oxidation state (+7).
 For the elements of the first transition series, the most common oxidation state is +2.
(Exception: Scandium)
 The highest oxidation state shown by any transition metal is +8. (Example: osmium and
ruthenium)
 Some transition elements show zero oxidation state in their compounds.
Trends in the M2+/M Standard Electrode Potentials
 The observed and calculated values of standard electrode potential (Eθ) for the elements Ti to
Zn are shown in the given figure.

 Copper has a high energy of atomisation and low hydration energy. Hence, the Eθ(M2+/M)
value for copper is positive.
 The values of Eθ for Mn, Ni, Zn are more negative than the expected trend.
o
Reason: The stability of the half-filled d-subshell in Mn2+ and the completely filled d10
configuration in Zn2+
Negative value of Eθ for Ni is due to the highest negative hydration energy.
Trends in the M3+/M2+ Standard Electrode Potentials
 The given table lists the values of Eθ for M2+/M and M3+/M2+.

Element - Sc Ti V Cr Mn Fe Co Ni Cu Zn
 Standard
M2+/M - -1.63 -1.18 -0.90 -1.18 -0.44 -0.28 -0.25 +0.34 -0.76
electrode

Potential
M3+/M2+ - -0.37 -0.26 -0.41 +1.57 +0.77 +1.97 - - -
E Θ/ V

 The highest value for Zn is due to the formation of the stable d10 configuration of Zn2+.
 Similarly, comparatively higher value for Mn is due to the formation of the stable d5
configuration of Mn2+.
Chemical Reactivity
 Many of the transition metals are electropositive. Hence, they dissolve in mineral acids.
 Few of them are ‘noble’, and are unaffected by simple acids.
 Metals of the first series are relatively more reactive and are oxidised by 1M H +.
 The Eθ values for M2+/M indicate the decreasing tendency to form divalent ions across the
series.
 The Eθ values for M3+/M2+ show that Mn3+ and Co3+ ions are the strongest oxidising agents in
aqueous solution.
 Ti2+, V2+ and Cr2+ are strong reducing agents, and will liberate hydrogen gas from dilute acids.

General Properties of Transition Metals : III

Magnetic Properties
 Diamagnetic substance − Repelled by the applied field
Paramagnetic substance − Attracted by the applied field
 Ferromagnetic substance − Attracted very strongly
 Paramagnetism arises due to the presence of unpaired electrons.
 Magnetic moment can be calculated by using ‘spin-only’ formula, i.e.,

Where,
n = Number of unpaired electrons
μ = Magnetic moment in Bohr magneton (BM)
 Magnetic moment increases with the increase in the number of unpaired electrons.
 Magnetic moments (calculated from ‘spin-only’ formula) for some ions of the first row transition
elements are listed in the given table.

Magnetic moment (BM)

Unpaired
Ion Configuration
electron(s)
Calculated Observed
 Sc3+ 3d0 0 0 0

Ti3+ 3d1 1 1.73 1.75

Tl2+ 3d2 2 2.84 2.76

V2+ 3d3 3 3.87 3.86

Cr2+ 3d4 4 4.90 4.80

Mn2+ 3d5 5 5.92 5.96

Fe2+ 3d6 4 4.90 5.3 − 5.5

Co2+ 3d7 3 3.87 4.4 − 5.2

Ni2+ 3d8 2 2.84 2.9 − 3, 4

Cu2+ 3d9 1 1.73 1.8 − 2.2

Zn2+ 3d10 0 0 -

Formation of Coloured Ions

 An electron from a lower energy d-orbital is excited to a higher energy d-orbital when the
energy of excitation corresponds to the frequency of light absorbed.
 This frequency of light generally lies in the visible region.
 The colour observed is the colour of the light absorbed.
 Colours of some of the first row transition metal ions (aquated) are listed in the given table
Configuration Example Colour

3d0 Sc3+ Colourless

3d0 Ti4+ Colourless

3d1 Ti3+ Purple

3d1 V4+ Blue

3d2 V3+ Green

3d3 V2+ Violet

 3d3 Cr3+ Violet

3d4 Mn3+ Violet

3d4 Cr2+ Blue

3d5 Mn2+ Pink

3d5 Fe3+ Yellow

3d6 Fe2+ Green

3d6, 3d7 Co3+, Co2+ Blue, pink

3d8 Ni2+ Green

3d9 Cu2+ Blue

3d10 Zn2+ Colourless

Formation of Complex Compounds

 Transition metals form a large number of complex compounds.
o Reason: Comparatively smaller size of metal ions, high ionic charges and availability of
d-orbitals for bond formation

 Example: , etc.
Catalytic Properties
 Transition metals and their compounds are known for their catalytic activity.
 Example: Vanadium (V) oxide (in Contact Process), nickel (in Catalytic Hydrogenation), etc.
 Iron (III) catalyses the reaction of iodide with persulphate ions.

 Mechanism:

Formation of Interstitial Compounds

 Interstitialcompounds
o Formed when small atoms like H, C, N are trapped inside the crystal lattices of metals
o Usually non-stoichiometric
o Neither typically ionic nor covalent
o Example: TiC, Mn4N, Fe3H, etc.
  Characteristics of interstitial compounds
o Higher melting points than pure metals
o Very hard
o Retain metallic conductivity
o Chemically inert
Alloy Formation
 Alloys are readily formed by these metals.
o Reason: Because of similar radii and other characteristics of transition metals
 Alloys, so formed, are hard and have high melting points.
 Ferrous alloys − Cr, V, W, Mo and Mn are used for the production of a variety of steels and
stainless steel.
 Alloys of transition metals with non-transition metals: Brass (Cu − Zn) and bronze (Cu − Sn)

Some Important Compounds of Transition Elements

Oxides and Oxoanions of Metals
 Oxides are generally formed by the reaction of metals with oxygen at higher temperatures.
 All the metals (except scandium) form MO oxides, which are ionic in nature.
 As the oxidation number of a metal increases, ionic character decreases.

Potassium Dichromate ( )

 Prepared from chromite ore in the following steps:

o Preparation of sodium chromate

o Conversion of sodium chromate into sodium dichromate

o Conversion of sodium dichromate to potassium dichromate

 Potassium dichromate being less soluble than sodium dichromate can be obtained in the form
of orange coloured crystals by treating sodium dichromate with potassium chloride and can be
removed by filtration.

 The dichromate ion exists in equilibrium with chromate ion at pH = 4.

However, by changing the pH, they can be inter-converted.
  acts as a very strong oxidising agent in the acidic medium.

 takes up electrons to get reduced and acts as an oxidising agent.

 Examples:
o Oxidises iodide to iodine

o Oxidises iron (II) solution to iron (III) solution i.e., ferrous ions to ferric ions

o Oxidises H2S to sulphur

Potassium Permanganate
 It can be prepared from pyrolusite (MnO2). The ore is fused with KOH in the presence of either
atmospheric oxygen or an oxidising agent such as KNO 3 or KClO4 to give K2MnO4.

 The green mass can be extracted with water and then oxidised either electrolytically or by
passing chlorine/ozone into the solution.
 Electrolytic oxidation:

 At anode, manganate ions are oxidised to permanganate ions.

 Oxidation by chlorine:

 Oxidation by ozone:

 Acidified KMnO4 solution oxidises Fe (II) ions to Fe (III) ions i.e., ferrous ions to ferric ions.

 Acidified potassium permanganate oxidises SO2 to sulphuric acid.

  Acidified potassium permanganate oxidises oxalic acid to carbon dioxide.

Lanthanoids
 Lanthanoids are the fourteen elements from lanthanum (La) to lutetium (Lu).
Electronic Configuration
 In general, the outermost electronic configuration is 4f1−146s2.
 Electronic configurations of lanthanum and lanthanoids are listed in the table

Electronic configurations Radii/pm

Atomic
Name Symbol
Number
Ln Ln2+ Ln3+ Ln4+ Ln Ln3+

57 Lanthanum La 5d16s2 5d1 4f0 - 187 106

58 Cerium Ce 4f15d16s2 4f2 4f1 4f0 183 103

59 Praseodymium Pr 4f36s2 4f3 4f2 4f1 182 101

60 Neodymium Nd 4f46s2 4f4 4f3 4f2 181 99

61 Promethium Pm 4f56s2 4f5 4f4 - 181 98

62 Samarium Sm 4f66s2 4f6 4f5 - 180 96

63 Europium Eu 4f76s2 4f7 4f6 - 199 95

64 Gadolinium Gd 4f75d16s2 4f35d1 4f7 - 180 94

65 Terbium Tb 4f96s2 4f9 4f8 4f7 178 92

66 Dysprosium Dy 4f106s2 4f10 4f9 4f8 177 91

67 Holmium Ho 4f116s2 4f11 4f10 - 176 89

68 Erbium Er 4f126s2 4f12 4f11 - 175 88

69 Thulium Tm 4f136s2 4f13 4f12 - 174 87

 70 Ytterbium Yb 4f146s2 4f14 4f13 - 173 86

71 Lutetium Lu 4f145d16s2 4f145d1 4f14 - - -

Atomic and ionic sizes

 There is a gradual decrease in atomic and ionic radii of Lanthanoids with an increase in atomic
number. This is known as lanthanoid contraction.
 Due to lanthanoid contraction, the radii of the elements of the 3 rd transition series are very
similar to those of the corresponding elements of the 2 nd series.
Oxidation states
 The lanthanoids exhibit mainly +3 oxidation state. However, sometimes, +2 and +4 oxidation
states are also exhibited.
General Characteristics
 Silvery-white, soft metals; tarnish rapidly in air
 Hardness increases with increasing atomic number
 Good conductors of heat and electricity
 1st and 2nd ionisation enthalpies around 600 kJ mol−1 and 1200 kJmol−1 respectively
 Chemical reactions:

Uses
 In the production of alloy steels for plates and pipes
 Mixed oxides of lanthanoids are used as catalysts in petroleum cracking.
 Some lanthanum oxides are used as phosphors in television screens and other fluorescing
surfaces.
The Actinoids & Some Applications of d-and f-block
Elements
Actinoids
 These include fourteen elements after actinium (from thorium to lawrencium).
 These are the radioactive elements.
Electronic Configuration:
 They have the electronic configuration of 7s2 with variation of occupancy in 5f and 6d orbitals.
 There is a gradual decrease in atomic and ionic radii of actinoids with increase in atomic
number.
This is known as actinoid contraction.
Oxidation States:
 Greater range of oxidation states
 Reason: 5f, 6d, and 7s subshells are of comparable energies.
 Exhibit mainly +3 oxidation state. However, +4, +5, +6, and +7 oxidation states are also
exhibited.
 Oxidation states of actinium and actinoids are given in the following table.

Ac Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr

3 3 3 3 3 3 3 3 3 3 3 3 3 3

4 4 4 4 4 4 4 4

5 5 5 5 5

6 6 6 6

7 7

General Characteristics and Comparison with Lanthanoids

 Silvery metals
 Have a variety of structures
 Highly reactive (especially when finely divided)
 Give a mixture of oxide and hydride when treated with boiling water
 Combine with most non-metals at moderate temperatures
 React readily with hydrochloric acid, but slowly with nitric acid due to the formation of
protective oxide film
 Do not react with alkalies
 Paramagnetic in nature
Their magnetic properties are complex in comparison to lanthanoids.
  Lower ionisation enthalpies than lanthanoids
 Reason − 5f electrons are less effectively shielded than 4f electrons.
Some Applications of d-and f-block Elements
 Iron is used in the construction materials.
 Fe, Cr, Ni, and Mn are used in the manufacture of steel, which is used in construction.
 TiO is used in pigment industry whereas MnO 2, Zn, and Ni/Cd are used in battery industry.
 Ag, Au, Cu, and Ni are used in making coins.
 Some metals and/or their compounds (V, Ti, Al, Fe, Ni, and Pd) are used as catalysts.
 AgBr is used in photographic industry as it has special light sensitive properties.

MAZHAR SIR
(M.Sc. ORGANIC CHEMISTRY)
CONTACT NO. 7878114456