Position in periodic Table

s-block p-block
1 18
IA Groups ‘Zero’
2 13 14 15 16 17
1
IIA IIIA IVA VA VIA VIIA

2
d-block
8 9 10
Periods
3 4 5 6 7 VIII 11 12
3
IIIB IVB VB VIB VIIB IB IIB
4

Lanthanoids

Actinoids

f-block
 Position in periodic Table

1. The d-block occupies the large middle section flanked by s and p-block
in the groups 3-12 of the periodic table .
2. There are 40 elements in four series of the d-block elements :

3 4 5 6 7 8 9 10 11 12
IIIB IVB VB VIB VIIB VIII IB IIB

3d-series

4d-series

5d-series

6d-series
General Characteristics of Transition Elements

Typical metallic character

Variety of oxidation states

High density and hardness

Both Boiling and Melting points are very high

Generally, ions and compounds are coloured

Complex formation
Why d-block elements are called transition elements
1. A transition element is defined as the one which has incompletely
filled d-orbitals in its ground state or in any one of its oxidation
state.
2. Zinc, Cadmium and Mercury of group 12 have full d10 configuration in
their ground state as well as in their common oxidation states and
hence, are not regarded as transition metals.
3. All transition elements are d-block elements, but all d-block elements
are not transition elements.
4. However, being the end members of the three-transition series,
chemistry of Zn, Cd and Hg is studied along with the chemistry of
the transition metals.
5. The very name ‘transition’ given to the elements of d-block is only
because of their position between s and p – block elements.
 Electronic configuration

(A) General Electronic Configurations

In general, the electronic configuration of these elements is

(n–1)d1–10 ns1–2

The (n–1) stands for the inner d-orbitals which may have one to
ten electrons.

The (n) stands for the outermost s-orbital which may have one
or two electrons (exceptionally 0 in case of Pd).
(B) Exceptions

1. Above generalization has several exceptions because

(i) The energy difference between (n–1)d and ns orbitals is very little.

(ii) Half and fully filled sets of orbitals are relatively more stable.

2. A consequence of this factor is reflected in the electronic

configuration of following elements.

(i) In 3d series — Cr and Cu

(ii) In 4d series — Nb, Mo, Tc, Ru, Rh, Pd, and Ag

(iii) In 5d series — Pt and Au

(iv) In 6d series — Rg
(C) Electronic configuration of all d-block elements.

(1) 3d–Series

Sc Scandium → 18[Ar] 3d1 4s2

Ti Titanium → 18[Ar] 3d2 4s2
V Vanadium → 18[Ar] 3d3 4s2
Cr Chromium → 18[Ar] 3d5 4s1
Mn Manganese → 18[Ar] 3d5 4s2
Fe Iron → 18[Ar] 3d6 4s2
Co Cobalt → 18[Ar] 3d7 4s2
Ni Nickel → 18[Ar] 3d8 4s2
Cu Copper → 18[Ar] 3d10 4s1
Zn Zinc → 18[Ar] 3d10 4s2
(2) 4d–Series

Y Yttrium → 36[Kr] 4d1 5s2

Zr Zirconium → 36[Kr] 4d2 5s2

Nb Niobium → 36[Kr] 4d4 5s1

Mo Molybdenum → 36[Kr] 4d5 5s1

Tc Technetium → 36[Kr] 4d6 5s1

Ru Ruthenium → 36[Kr] 4d7 5s1

Rh Rhodium → 36[Kr] 4d8 5s1

Pd Palladium → 36[Kr] 4d10 5s0

Ag Silver → 36[Kr] 4d10 5s1

Cd Cadmium → 36[Kr] 4d10 5s2

(3) 5d–Series

La Lanthanum → 54[Xe] 5d1 6s2

Hf Hafnium → 54[Xe] 5d2 6s2

Ta Tantalum → 54[Xe] 5d3 6s2

W Tungsten → 54[Xe] 5d4 6s2

Re Rhenium → 54[Xe] 5d5 6s2

Os Osmium → 54[Xe] 5d6 6s2

Ir Iridium → 54[Xe] 5d7 6s2

Pt Platinum → 54[Xe] 5d9 6s1

Au Gold → 54[Xe] 5d10 6s1

Hg Mercury → 54[Xe] 5d10 6s2

(4) 6d–Series

Ac Actinium → 86[Rn] 6d1 7s2

Rf Rutherfordium → 86[Rn] 6d2 7s2

Db Dubnium → 86[Rn] 6d3 7s2

Sg Seaborgium → 86[Rn] 6d4 7s2

Bh Bohrium → 86[Rn] 6d5 7s2

Hs Hassium → 86[Rn] 6d6 7s2

Mt Meitnerium → 86[Rn] 6d7 7s2

Ds Darmstadtium → 86[Rn] 6d8 7s2

Rg Roentgenium → 86[Rn] 6d10 7s1

Cn Copernicium → 86[Rn] 6d10 7s2

 3 4 5 6 7 8 9 10 11 12

3d-series

4d-series

5d-series

6d-series
Atomic Radii 19
18
5d-series
4d-series 17

Radius (nm)
3d-series 16
15
14

13
12
Trends in atomic radii of transition elements
3d-series Sc Ti V Cr Mn Fe Co Ni Cu Zn
4d-series Y Zr Nb Mo Tc Ru Rh Pd Ag Cd
5d-series La Hf Ta W Re Os Ir Pt Au Hg
In a period

> > ⋜
> > > > > ⋜

Smallest ⎯→ Ni
Largest ⎯→ Sc

In initial five elements attraction between nucleus and valence shell

remains more as compared to repulsion between valence shell and
penultimate shell that’s why atomic radius decreases from Sc to
Mn.
In a period

> > ⋜
> > > > > ⋜

Smallest ⎯→ Ni
Largest ⎯→ Sc

In next three elements attraction between nucleus and valence shell

becomes equal to repulsion between valence shell and penultimate
shell that’s why atomic radius of Fe, Co and Ni remains almost equal
(slightly larger for Fe).

In last two elements attraction between nucleus and valence shell

remains less as compared to repulsion between valence shell and
penultimate shell that’s why atomic radius from Cu to Zn increases.
 In a group

The atomic radius of elements increases on moving down the first

transition series (3d) to second transition series (4d). This is due to
the increase in number of shells with the increase in atomic number.
The atomic radii of second (4d) and third (5d) transition series in a
group is almost same except Y(39) and La(57)

3d–series
         
4d–series
         
4f series
5d–series
f-contraction
or Lanthanoid 3d series < 4d series  5d series
Contraction For Group 4-12
density

The decrease in metallic radius coupled with increase in atomic

mass results in a general increase in the density of these elements.
Thus, from Scandium to Copper the significant increase in the
density may be noted.

Atomic volume of d-block elements is less when compared with s-

block elements because of high Zeff and as density = mass/volume
so, density of d-block elements is higher than that of respective
s-block elements in the period.
 density

Trends of density in 3d-series

< < < < < < < < ≤

3.43 4.1 6.07 7.1 7.19 7.21 7.8 8.7 8.9 8.9

Lowest ⎯→ Sc
Highest ⎯→ Cu

Elements with highest densities among all transition elements are

Iridium (Ir) = 22.61 g/cm3
Osmium (Os) = 22.51 g/cm3
 Ionisation energy

In a period

In a period highly irregular pattern of IE is observed

< < < < < < < < <

Lowest IE1 ⎯→ Sc
Highest IE1 ⎯→ Zn

Cr < Mn < Zn (due to extra stability of 3d5 4s2 and 3d10 4s2 config. in
Mn and Zn respectively)

V ≤ Cr ≤ Ti and Co ≤ Fe : IE1 order

IE1 Trend for 3d-series elements

1100

1000
906
Zn
900
762 745
800 717 Fe Cu
Mn
656 652 758
700 Ti Cr Co 736
Ni

600 631
650
V
Sc

500
 Ionisation enthalpy / ΔiH⊝ / kJ mol–1 for 3d-series elements

Element Sc Ti V Cr Mn Fe Co Ni Cu Zn

ΔiH⊝I 631 656 650 653 717 762 758 736 745 906

ΔiH⊝II 1235 1309 1414 1592 1509 1561 1644 1752 1958 1734

ΔiH⊝III 2393 2657 2833 2990 3260 2962 3243 3402 3556 3829
 Ionisation energy

In a period

For 2nd IE Cr > Fe > Mn, Cu > Zn and Zn has highest

Sc < Ti < V < Mn < Fe < Cr < Co < Ni < Zn < Cu

For 3rd IE Mn > Cr > Fe and Zn has highest

Sc < Ti < V < Fe < Cr < Mn < Co < Ni < Cu < Zn

 In a group

3d–series
         

4d–series
 
 
 
 
 
 
 
 
 

4f series
5d–series
f-contraction
or Lanthanoid
Contraction 3d series < 4d series < 5d series
For Group 4, 5, 6 & 10

4d series < 3d series < 5d series

For Group 7, 8, 9, 11 & 12
Ionisation enthalpy / ΔiH⊝ I / kJ mol–1 for 3d, 4d and 5d-series elements

Element Sc Ti V Cr Mn Fe Co Ni Cu Zn

ΔiH⊝I 631 656 650 652 717 762 758 736 745 906

Element Y Zr Nb Mo Tc Ru Rh Pd Ag Cd

ΔiH⊝I 616 674 664 685 703 711 720 736 731 876

Element La Hf Ta W Re Os Ir Pt Au Hg

ΔiH⊝I 541 760 760 770 759 840 900 870 889 1007
 Oxidation-State

1. d-block element shows variable oxidation state due to partially

filled configuration.

2. It has two types of oxidation states -

(a) Minimum oxidation states

(b) Maximum oxidation states

3. The variability of oxidation states, a characteristic of transition

elements arises out of incomplete filling of d–orbitals in such a way
that their oxidation states differ from each other by 1 unit.

Example

VII VIII VIV VV

 Physical Properties

1. Nearly all the transition elements display typical metallic properties

such as high tensile strength, ductility, malleability, high thermal and
electrical conductivity and metallic lustre.

2. With the exceptions of Zn, Cd, Hg and Mn, they have one or more
typical metallic structures at normal temperatures.
 Lattice Structure

Lattice Structures of Transition Metals

Sc Ti V Cr Mn Fe Co Ni Cu Zn
3d-Series bcc
hcp hcp X bcc X
bcc (bcc, ccp ccp ccp
(bcc) (bcc) (hcp) (hcp) (hcp)
ccp)

Y Zr Nb Mo Tc Ru Rh Pd Ag Cd
4d-Series
hcp hcp X
bcc bcc hcp hcp ccp ccp ccp
(bcc) (bcc) (hcp)

La Hf Ta W Re Os Ir Pt Au Hg
5d-Series hcp
hcp
(ccp, bcc bcc hcp hcp ccp ccp ccp X
(bcc)
bcc)
 Melting Point

01  The high melting points of these metals attributed to the

involvement of great number of electrons from (n–1) d in
addition the ns electrons in the inter atoms metallic bonding.

02 (i) In any series the melting points of these metals rise to
a maximum at d5 and fall regularly as the atomic number
increases.

(ii) Mn and Tc show anomalous behavior in above trend.

 4
W
Re
Ta
3 Mo Os
Nb Ru

M.P. (103 K)
Ir

Hf Tc
Cr
V Rh Pt
Zr
2 Fe Co Pd
Ti
Ni
Mn Cu
Au
Ag
1
Atomic number

Trends in melting points of transition elements

Melting point  number of unpaired electrons

Mn and Tc have low melting point

▪ Due to typical exceptional crystal structure of Mn and Tc

▪ Due to stable electronic configuration

3d5 4s2 for Mn

Due to low Enthalpy of atomisation.

Highest M.P. among all d-block elements is of W(Tungsten) - 3380°C

In general, M.P. order : 3d < 4d < 5d

Melting Point order in Group 12 : Zn > Cd > Hg

Enthalpy of Atomisation

900
800 5d-series
4d-series
700 3d-series

600

\ kJ mol
500

400

300

⊝
aH
200
100

0
Atomic number

Trends in enthalpies of atomisation of transition elements

 Enthalpy of Atomisation

1. Enthalpy of atomisation means the energy required to break the

metallic bond.

2. Enthalpy of atomisation  no. of unpaired electrons

 interaction b/w atoms

 strength of metallic bonding

3. More is number of unpaired electrons more will be the interaction

b/w atom that will favor the formation of strong metallic bond.

4. Stronger is the metallic bond more will be the heat of atomisation.

5. In case of Mn and Zn due to stable 3d5 4s2 and 3d10 4s2 configuration,
respectively, electrons present in 3d-orbitals do not involve in metallic
bond formation so, metallic bond is weak and hence, they have low
Enthalpy of atomisation.

6. Zn has the lowest Enthalpy of atomisation among all 3d-series

elements.

7. In general, order of Enthalpy of Atomisation : 3d < 4d < 5d

Electrode potential

The oxidizing and reducing power of an element is measured in

terms of the standard electrode potentials.

There is no regular trend in electrode potential values.

This is due to the irregular variation of below parameters in the

period-

➢ Ionisation enthalpies (IE1 + IE2)

➢ Hydration energies

➢ Sublimation energies
Trends in the E°(M2+/ M) Standard Electrode Potentials

0.5 E°(M2+/ M)

Standard electrode potential in V

0

–0.5

–1

–1.5

Calculated values
–2
Observed values Ti V Cr Mn Fe Co Ni Cu Zn

Copper has a positive reduction potential. i.e., elemental copper is

more stable than Cu2+.
Trend of Standard Electrode Potential in 3d-series

E°(M2+/ M) − −1.63 −1.18 −0.90 −1.18 −0.44 −0.28 −0.25 +0.34 −0.76

E°(M3+/M2+) −2.08 −0.37 −0.26 −0.41 +1.57 +0.77 +1.97 − − −

Negative value of E°(M2+/ M) and E°(M3+/M2+) indicates inability to get

converted from M2+ to M and from M3+ to M2+ respectively.

Positive value of E°(M2+/ M) and E°(M3+/M2+) indicates ability to get

converted from M2+ to M and from M3+ to M2+ respectively.

Note

Compounds of Sc, exist only in +3 oxidation states due to very highly

negative value of E°(M3+/M2+) .
Memory warning : No need to memorize the table but remember
the comments.

° °
Element (M) 𝐄(𝐌 𝟑+ /𝐌 𝟐+
)
𝐄 (𝐌 𝟐+ /𝐌
)
Comments
+2 Oxidation state does not exist for Sc
Sc –2.08 –
Only +3 Oxidation state is stable
Ti –0.37 –1.63 +3 Oxidation state is more stable
V –0.26 –1.18 +3 Oxidation state is more stable
Cr –0.41 –0.90 +3 Oxidation state is more stable
Mn +1.57 –1.18 +2 Oxidation state is more stable
Fe +0.77 –0.44 +2 Oxidation state is more stable
Co +1.97 –0.28 +2 Oxidation state is more stable
Ni – –0.25 +3 Oxidation state does not exist for Ni
+3 Oxidation state does not exist for Cu. 0
Cu – +0.34
Oxidation state is more stable than +2
+3 Oxidation state does not exist for Zn
Zn – - 0.76
Only +2 Oxidation state is stable
 Example

Why is Cr2+ reducing and Mn3+ oxidizing when both have d4 configuration ?
Hint : Eo(Cr2+/ Cr3+) → + 0.41
Eo(Mn3+/ Mn2+) → + 1.57
Magnetic character

Metals, which have unpaired electrons show Para-magnetism.

Spin only magnetic moment  = n(n + 2)

here, n = no. of unpaired electron.
unit of  is B.M. (Bohr-Magneton)
Magnetic character

When a magnetic field is applied to substances, mainly two types

of magnetic behaviour are observed:
▪ Diamagnetism
▪ Paramagnetism

A diamagnetic substance is one which is slightly repelled by an

external magnetic field.

A paramagnetic substance is one which is attracted towards an

external magnetic field.
Ferromagnetism

Substances which get attracted very strongly towards an external

magnetic field are said to be ferromagnetic.

Ferromagnetism is an extreme form of paramagnetism.

Ferromagnetic materials  Fe, Co, Ni etc.

colour

Due to d-d transition of unpaired electron, d-block elements show

characteristic colours.

𝐸 = ℎ𝜈2
↿ eg R
O V/I

↿
Y B
𝐸 = ℎ𝜈1 ↿ G
t2g

d-block elements during the formation of coordination compounds,

loose their degeneracy of orbitals and orbitals get separated into
two levels t2g and eg.
Ionic and covalent compounds of many transition elements are
coloured.

They form different coloured compounds.

The compounds in which metal ion has an unpaired electron that

compound may be coloured.
When an electron from a lower energy d-orbital is excited to a
higher energy d-orbital, if the energy of excitation lies in visible
range, complimentary colour is observed.

MnO4⊝ is coloured, despite of d0 configuration of Mn.

It is not due to d-d transition, but it occurs due to charge transfer

between Mn and O and the phenomenon called Ligand to Metal
charge transfer spectra (LMCT spectra).
 Memory warning : Memorize the table completely.

Oxidation
Sc Ti V Cr Mn Fe Co Ni Cu Zn
State

Colour
1+ less
Colour
2+ Violet Blue Pink Green Pink Green Blue
less
Colour
3+ less
Purple Green Violet Violet Yellow Blue

Colour
4+ less
Blue
 𝜈minimum
𝝀maximum
Eminimum 𝜈maximum
R 𝝀minimum
Emaximum
O V/I

Y B

Complementary Colour Wheel

Formation of complex compound

The transition elements have an unparalleled tendency to bind

several anions or neutral molecules (Lewis bases, which can donate
electron pair; known as Ligands) to form complex species also
known as coordination compounds.

Transition Elements for Complex compounds because of

▪ Small size

▪ High charge density

▪ Availability of vacant ‘d’ orbital

 In general, the smaller the positive ions and larger the charge, the
greater will be the stability of complexes formed. Thus, the
relatively large ions of the Group IA and Group IIA elements do not
have as great tendency to form stable complex ions as do the
smaller, more highly charged ions of the transition elements.

The ability of transition metals to form complexes is more than the

s- and p- block elements which only form few complexes.

Example

[SiF6]2⊝, [SnCl6]2⊝, [Al(H20)6]3⊕ etc.

Cobalt forms more complexes than any other elements among all the
transition series.
 Example
KCN
+2 KCN (excess)
FeSO4 + 2KCN

+2
Fe(CN)2 + K2SO4
 KCN (excess)
+2
K4 [Fe(CN)6]
(Potassium ferrocyanide)
+2 +2
Fe(CN)2 + K2SO4 K4[Fe(CN)6]
Colourless
complex

Example

[Fe(CN)6]3–, [HgI4]2–, [Cu(NH3)4]2+, [PtCl4]2–

Catalytic Properties

The transition metals and their compounds are known for their
catalytic activity because of

▪ Variability of oxidation states

▪ Ability to form complex compounds

On the solid surface of catalyst, catalytic action involves the

formation of bonds between reactant molecules and the surface
atoms of the catalyst.

This increases the concentration of the reactants at the catalyst

surface and decreases the interaction among reactant molecules
that leads to weakening of the bonds in the reacting molecules
(thus, the activation energy is lowered).
Also, because the transition metal ions can change their oxidation
states, they become more effective as catalysts.

A catalytic substance is capable in forming an unstable intermediate

compound which readily decomposes yielding the product and
regenerating the Catalyst.

A + B + catalyst → [AB] → C + catalyst

reactants Intermediate product
compound

Example

2Fe3+ + 2I– → I2 + 2Fe2+

2Fe2+ + S2O2−
8 – → 2Fe3+ + 2SO2−
4

Fe3+
2I– + S2O2−
8 2SO2−
4 +I2
 Several d-block metals and their compounds are known to catalyze
various reactions of industrial importance.

Catalyst Used
Fe Promoted Iron is used in Haber-Bosch process for manufacture of NH3
Converts SO2 to SO3 in Contact process for manufacture of H2SO4
V2O5
(formerly Pt was used)
Pt/Rh as gauze catalyst in making of HNO3 by Ostwald's process
Pd Used for hydrogenation of hydrocarbons
Ni Raney Nickel is used in numerous reduction processes
Pt/PtO2.H2O Used as Adam’s Catalyst for reduction
FeSO4 + H2O2 Used as Fenton’s reagent for oxidizing alcohols to aldehydes
TiCl4 Used as the Ziegler-Natta Catalyst in the production of polythene
CuCl2 Deacon’s process for making Cl2 from HCl
Used in Direct process for production of (CH3)2SiCl2 used to make
Cu silicones
MnO2 Used as a catalyst to decompose KClO3 to give O2
Formation of Interstitial Compounds

B, H, C, N trapped inside interstices of Crystal lattices of metals

Usually, non-stoichiometric and neither typically ionic nor covalent

TiC, Mn4N, Fe3H, VH0.56, TiH1.7

High melting point than the pure metal

Very harder than pure metal

(some borides have diamond like hardness)

Retain metallic conductivity

Chemically inert
Formation of Alloys

What is Alloy ?

When two or more metallic elements are combined the new mixture
formed is called as “Alloy”.

Alloys may be homogeneous solid solutions in which the atoms of one

metal are distributed randomly among the atoms of the other.

Such alloys are formed by atoms with metallic radii that are within
about 15 percent of each other.

In the alloys, ratio of component metals is fixed.

Alloys can not be decomposed into its components by physical

methods.
Properties of Alloys

Alloys of d-block metals retain the properties of parent metals like

ductility, malleability, conductivity, hardness and strength.

Alloys, often have more desirable colour, improved lustre and higher
melting point than parent metal elements.

They are more corrosion protective i.e. in these compounds, corrosion

does not take place easily.
Transition metals form alloy because :

1. Similarity of Radii

2. Low reactivity

The transition elements have almost similar sizes and very low
reactivity, due to this a transition metal atom in the lattice can
be replaced easily by the other transition metal atoms hence,
they have maximum tendency to form alloys.
Transition metals form alloy because :

3. High strength

4. hardness

Due to high strength and hardness of d-block metal elements, alloys

are readily formed by these metals..

Alloys of transition metals with non transition metals such as brass

(copper-zinc) and bronze (copper-tin), have considerable industrial
importance.
 Some Important alloys

(a)* Bronze Cu (75 - 90 %) +Sn ( 10 - 25 %)

(b)* Brass Cu ( 60 - 80 %) +Zn (20 - 40 %)
(c) Gun metal (Cu + Zn + Sn) (87 : 3 : 10)
(d) German Silver Cu + Zn + Ni ( 3 : 1 : 1)
(d) Sterling Silver Ag (92.5%) + Cu (7.5%)
(e) Red Gold (Orange Gold) Au + Cu
(f) White Gold Au + Ag
(g) Mild Steel Fe + C + Si

(h) Stainless Steel Fe + C + Cr

Note Memorize the ‘ * ’ marked alloys

 Oxidation-State

1. d-block element shows variable oxidation state due to partially

filled configuration.

2. It has two types of oxidation states -

(a) Minimum oxidation states

(b) Maximum oxidation states

3. The variability of oxidation states, a characteristic of transition

elements arises out of incomplete filling of d–orbitals in such a way
that their oxidation states differ from each other by 1 unit.

Example

VII VIII VIV VV

 Oxidation-State

4. In d-block elements the higher oxidation states are favored by the

heavier members

Example

In group – 6 Mo (VI) and W(VI) are found to be more stable than

Cr(VI).

Thus Cr (VI) in form of dichromate (Cr2 O2−

7 ) in acidic medium is a
strong oxidizing agent, whereas MoO3 and WO3 are not.

5. Low oxidation states are found when a complex compound has ligand
capable of p – acceptor character in addition to the s-bonding.

Example

In Ni (CO)4 and Fe(CO)5, the oxidation state of nickel and iron is zero.
 Oxidation-State

Variable oxidation states of Transition Elements

Sc Ti V Cr Mn Fe Co Ni Cu Zn
+1
+2 +2 +2 +2(a) +2 +2 +2 +2 +2
+3 +3 +3 +3 +3 +3 +3 +3
+4 +4 +4 +4(b) +4 +4 +4
+5 +5 +5
+6 +6 +6
+7
(a) Acidic medium (b) Basic medium

Shaded states are popular ones.

Underlined states are the most stable ones.
Catalytic Properties

The transition metals and their compounds are known for their
catalytic activity because of

▪ Variability of oxidation states

▪ Ability to form complex compounds

On the solid surface of catalyst, catalytic action involves the

formation of bonds between reactant molecules and the surface
atoms of the catalyst.

This increases the concentration of the reactants at the catalyst

surface and decreases the interaction among reactant molecules
that leads to weakening of the bonds in the reacting molecules
(thus, the activation energy is lowered).
Also, because the transition metal ions can change their oxidation
states, they become more effective as catalysts.

A catalytic substance is capable in forming an unstable intermediate

compound which readily decomposes yielding the product and
regenerating the Catalyst.

A + B + catalyst → [AB] → C + catalyst

reactants Intermediate product
compound

Example

2Fe3+ + 2I– → I2 + 2Fe2+

2Fe2+ + S2O2−
8 – → 2Fe3+ + 2SO2−
4

Fe3+
2I– + S2O2−
8 2SO2−
4 +I2
 Several d-block metals and their compounds are known to catalyze
various reactions of industrial importance.

Catalyst Used
Fe Promoted Iron is used in Haber-Bosch process for manufacture of NH3
Converts SO2 to SO3 in Contact process for manufacture of H2SO4
V2O5
(formerly Pt was used)
Pt/Rh as gauze catalyst in making of HNO3 by Ostwald's process
Pd Used for hydrogenation of hydrocarbons
Ni Raney Nickel is used in numerous reduction processes
Pt/PtO2.H2O Used as Adam’s Catalyst for reduction
FeSO4 + H2O2 Used as Fenton’s reagent for oxidizing alcohols to aldehydes
TiCl4 Used as the Ziegler-Natta Catalyst in the production of polythene
CuCl2 Deacon’s process for making Cl2 from HCl
Used in Direct process for production of (CH3)2SiCl2 used to make
Cu silicones
MnO2 Used as a catalyst to decompose KClO3 to give O2
Formation of Interstitial Compounds

B, H, C, N trapped inside interstices of Crystal lattices of metals

Usually, non-stoichiometric and neither typically ionic nor covalent

TiC, Mn4N, Fe3H, VH0.56, TiH1.7

High melting point than the pure metal

Very harder than pure metal

(some borides have diamond like hardness)

Retain metallic conductivity

Chemically inert
Formation of Alloys

What is Alloy ?

When two or more metallic elements are combined the new mixture
formed is called as “Alloy”.

Alloys may be homogeneous solid solutions in which the atoms of one

metal are distributed randomly among the atoms of the other.

Such alloys are formed by atoms with metallic radii that are within
about 15 percent of each other.

In the alloys, ratio of component metals is fixed.

Alloys can not be decomposed into its components by physical

methods.
Properties of Alloys

Alloys of d-block metals retain the properties of parent metals like

ductility, malleability, conductivity, hardness and strength.

Alloys, often have more desirable colour, improved lustre and higher
melting point than parent metal elements.

They are more corrosion protective i.e. in these compounds, corrosion

does not take place easily.
Transition metals form alloy because :

1. Similarity of Radii

2. Low reactivity

The transition elements have almost similar sizes and very low
reactivity, due to this a transition metal atom in the lattice can
be replaced easily by the other transition metal atoms hence,
they have maximum tendency to form alloys.
Transition metals form alloy because :

3. High strength

4. hardness

Due to high strength and hardness of d-block metal elements, alloys

are readily formed by these metals..

Alloys of transition metals with non transition metals such as brass

(copper-zinc) and bronze (copper-tin), have considerable industrial
importance.
 Some Important alloys

(a)* Bronze Cu (75 - 90 %) +Sn ( 10 - 25 %)

(b)* Brass Cu ( 60 - 80 %) +Zn (20 - 40 %)
(c) Gun metal (Cu + Zn + Sn) (87 : 3 : 10)
(d) German Silver Cu + Zn + Ni ( 3 : 1 : 1)
(d) Sterling Silver Ag (92.5%) + Cu (7.5%)
(e) Red Gold (Orange Gold) Au + Cu
(f) White Gold Au + Ag
(g) Mild Steel Fe + C + Si

(h) Stainless Steel Fe + C + Cr

Note Memorize the ‘ * ’ marked alloys

Potassium dichromate K2Cr2O7

Preparation

Dichromats are generally prepared from chromate, which are

obtained by the fusion of Chromite ore (FeCr2O4 or FeO.Cr2O3) with
sodium or potassium carbonate in free access of air.

The yellow solution of sodium chromate is filtered and acidified with

sulphuric acid to give a solution from which orange sodium
dichromate, Na2Cr2O7 . 2H2O can be crystallised.

Lime (CaO) is added with Na2CO3 to keep the mass porous so that
air can attack throughout the solution.
Sodium dichromate is more soluble than potassium dichromate. The
latter is therefore, prepared by treating the solution of sodium
dichromate with potassium chloride.

Na2Cr2O7 + 2KCl ⎯→ K2Cr2O7 + 2NaCl

Orange crystals of potassium dichromate crystallise out.

2CrO42⊝ + 2H ⎯→ Cr2O72⊝ + H2O

Cr2O72⊝ + 2OH⊝ ⎯→ 2CrO42⊝ + H2O

The complete preparation reaction is as follows :

 The complete preparation reaction is as follows :

1000 – 1300°C
4 FeCr2O4 + 8 Na2CO3 + 7 O2 ⎯⎯⎯⎯⎯→ 8 Na2CrO4 + 8 CO2 + 2 Fe2O3
Red hot temp.
(Chromite ore) (Alkaline air Sodium chromate Insoluble
soln) (yellow colour) in water
(residue)
Filter
(Fe2O3 removed)

H2O + Na2SO4 + Na2Cr2O7 ⎯ H2SO4 (Conc.) + 2Na2CrO4

Sodium dichromate (In filtrate)
(orange colour)

Na2Cr2O7 + 2KCl ⎯⎯→ K2Cr2O7 + 2NaCl

Potassium dichromate
Hot concentrated
(orange colour)
soln
 Chromates and dichromats are interconvertible in aqueous solution
depending upon pH of the solution.

OH (pH )
⊝

Cr2O7 2⊝ CrO42⊝
H (pH )
dichromate ion chromate ion
(orange colour) (yellow colour)

Note

Oxidation state of chromium remains same.

 The structures of chromate ion, CrO42⊝ and the dichromate ion,
Cr2O72⊝ are shown below. The chromate ion is tetrahedral whereas
the dichromate ion consists of two tetrahedra sharing one corner
with Cr—O—Cr bond angle of 126°.

Structure

2–
O
2–
O O O
Cr O Cr Cr O
126°
O O O O
O
Chromate ion Dichromate ion
Structure of Potassium Dichromate
Structure of Potassium Dichromate
Oxidising Property

Both Sodium and Potassium dichromats are strong oxidising agents;

but K2Cr2O7 is preferred over Na2Cr2O7 for standardising of primary
standard solutions in volumetric analysis or titration because the
sodium salt has a greater solubility in water due to its hygroscopic
nature.

In acidic solution, its oxidising action can be represented as follows :

Cr2O72⊝ + 14H + 6e⊝ ⎯→ 2Cr3 + 7H2O (E = 1.33V)

⊝
Acidified Potassium dichromate oxidises :

⊝ ⊝
Iodides to iodine : 6I ⎯→ 3I2 + 6e

⊝
Sulphides to sulphur : 3H2S ⎯→ 3S + 6e + 6H

⊝
Tin (ll) to Tin (lV) : 3Sn2 ⎯→ 3Sn4 + 6e

⊝
Iron (ll) to Iron (lll) : 6Fe2 ⎯→ 6Fe3 + 6e

The full ionic equation may be obtained by adding the half-reaction

for potassium dichromate (oxidising agent) to the half-reaction for
the reducing agent -

Cr2O72⊝ + 14H + 6Fe2 ⎯→ 2Cr3 + 6Fe3 + 7H2O

 Chemical reaction of K2Cr2O7

Reaction of acidified K2Cr2O7 with H2O2

When H2O2 reacts with acidified K2Cr2O7 then deep blue colour
solution is obtained.

This deep blue colour is due to formation of CrO5 which fades away
and CrO5 decomposed to Cr3 (green Cr2O3) and O2 (g) in the aqueous
solution readily.

2 2 H O
K2Cr2O7 + H ⎯⎯⎯→ CrO5 ⎯⎯⎯→ Cr2O3 + O2 (g)
Deep blue Green
Blue colour can be retained by adding pyridine in the solution of
acidified K2Cr2O7 with H2O2.

pyridine
.
CrO5 Py
H2O2 Deep blue
K2Cr2O7 + H ⎯⎯⎯→ CrO5
O
O O Cr2O3 + O2 (g)
exposure
Cr Green
O O
d-block
 Chemical reaction of K2Cr2O7

Chromyl chloride test

On reacting K2Cr2O7 with sulphuric acid CrO3 (reddish brown) is

formed.

K2Cr2O7 + H2SO4 ⎯⎯⎯→ CrO3 + H2O

Reddish brown

CrO3 reacts with HCl obtained in the solution by reaction of NaCl

and H2SO4.

NaCl + H2SO4 ⎯⎯⎯→ HCl + NaHSO4

 warm gently
HCl + CrO3 ⎯⎯⎯⎯⎯→ CrO2Cl2
Chromyl chloride
(red fumes)

Passed through
conc. NaOH Soln

2H2O + 2NaCl + 2Na2CrO4

(Yellow color soln)

CH3COOH CrO42⊝
+ +
(CH3COO)2Pb 2H2O2 + 2H

alcohol
CH3COONa CrO5 + 3H2O ⎯⎯⎯→ blue colour soln
+
2PbCrO4 
(Yellow ppt)
d-block
Chemical reaction of K2Cr2O7

Heating

D 3
2K2Cr2O7 ⎯⎯⎯→ 2K2CrO4 + Cr2O3 + O2
2
(Orange) (Yellow) (Green)

Uses

Very important chemical used in leather industry

As an oxidant for preparation of many azo compounds.

Potassium permanganate KMnO4

Preparation

Potassium permanganate (KMnO4) is prepared by fusion of MnO2

(pyrolusite ore) with an alkali metal hydroxide and an oxidising
agent like KNO3.

This produces the dark green K2MnO4 which disproportionate in a

neutral or acidic solution to give permanganate (MnO4⊖).

∆ (high temp.)
2MnO2 + 4KOH + O2 ⎯⎯⎯⎯→ 2K2MnO4 + 2H2O + KNO2
Green melt

3K2MnO4 + 4H ⎯→ 2KMnO4 + MnO2 ↓ + 2H2O

Green melt Purple Dark
brown ppt
Lab Preparation

Permanganate ion is stable in high alkaline medium or when pH of

solution is high and as we start decreasing the pH of the solution,
manganate ion disproportionate in permanganate and MnO2

3K2MnO4 + 2H2SO4 ⎯→ 2KMnO4 + MnO2 ↓ + 2K2SO4 + 2H2O

1rd
In this process of Mn is lost as MnO2
3

In the laboratory, a manganese (II) ion salt is oxidised by peroxodi-

sulphate to permanganate.

2Mn2 + 5S2O82⊝ + 8H2O ⎯→ 2MnO4⊝ + 10SO42⊝ + 16H

Commercial Preparation

Commercially it is prepared by the alkaline oxidative fusion of MnO2

followed by the electrolytic oxidation of manganate (Vl) in alkaline
solution.

Fused with KOH, oxidised

with air or KNO3
MnO2 MnO2−
4
Manganate ion

Electrolytic oxidation in
alkaline solution
MnO2−
4 MnO−
4
manganate ion Permanganate ion
Physical Property
The manganate and permanganate ions are tetrahedral; the π-bonding
takes place by overlap of p orbitals of oxygen with d orbitals of
manganese.

The green manganate is paramagnetic because of one unpaired

electron but the purple permanganate is diamagnetic due to the
absence of unpaired electron.
Oxidising Property

Acidified permanganate solution oxidises oxalates to carbon dioxide,

iron(II) to iron(III), nitrites to nitrates and iodides to free iodine.
The half-reactions of reductants are:

5C2O42⊝ ⎯→ 10 CO2 + 10e⊝

5 Fe2 ⎯→ 5 Fe3 + 5e⊝

5 NO2⊝ + 5H2O ⎯→ 5NO3⊝ + 10H + 10e⊝

10I⊝ ⎯→ 5I2 + 10e⊝

 A few important reactions of KMnO4 as oxidising agent are given below:

In acid solutions

(a) Iodine is liberated from potassium iodide :

10 I⊝ + 2 MnO4⊝ + 16 H ⎯→ 2 Mn2 + 8 H2O + 5 I2

(b) Fe2 ion is converted to Fe3 :

5 Fe2 + MnO4⊝ + 8 H ⎯→ Mn2 + 4 H2O + 5 Fe3

(Green) (Yellow)
(c) Oxalate ion or oxalic acid is oxidised at 333 K:
5C2O42⊝ + 2MnO4⊝ + 16H ⎯→ 2Mn2 + 8H2O + 10CO2

(d) Hydrogen sulphide is oxidised, sulphur being precipitated:

H2S ⎯→ 2H+ + S2⊝
5S2⊝ + 2MnO4⊝ + 16H ⎯→ 2Mn2 + 8H2O + 5S

(e) Sulphurous acid or sulphite is oxidised to a sulphate or sulphuric acid:

5SO32⊝ + 2MnO4⊝ + 6H ⎯→ 2Mn2 + 3H2O + 5SO42⊝

(f) Nitrite is oxidised to nitrate :

5NO2⊝ + 2MnO4⊝ + 6H ⎯→ 2Mn2 + 5NO3⊝ + 3H2O
In weak acidic solutions

(a) Thiosulphate is oxidised almost quantitatively to sulphate:

8MnO4⊝ + 3S2O32⊝ + H2O ⎯⎯→ 8MnO2 + 6SO42⊝ + 2OH⊝

In faintly / slightly alkaline solutions

(a) A notable reaction is the oxidation of iodide to iodate:

2MnO4⊝ + H2O + I⊝ ⎯⎯→ 2MnO2 + 2OH⊝ + IO3⊝

Heating of KMnO4

Potassium permanganate forms dark purple (almost black) crystals

which are isostructural with those of KClO4. The salt is not very
soluble in water (6.4 g/100 g of water at 293 K), but when heated it
decomposes at 513 K.

∆ (513 K)
2KMnO4 ⎯⎯⎯⎯⎯⎯→ K2MnO4 + MnO2 ↓ + O2 ↑
Purple Green Black

Note

Potassium permanganate (KMnO4) on suspension in open air decomposes

that’s why it is stored in dark bottles in lab to stop its decomposition in
presence of light.
The Inner Transition Elements (f-block) :

Introduction

1. The elements constituting the f – block are those in which the 4f

and 5f orbitals are progressively filled.

2. These elements are formal members of group 3 from which they

have been taken out to form a separate f – block of the periodic
table.

3. All f–block elements are called Inner Transition Elements because

their valence shell, penultimate shell and ante-penultimate shell are
partially filled.

4. Mostly of the f – block elements are found in the Earth’s crust in

very less abundance, so they are also termed as Rare Earth
elements.
5. The f-block consists of the two series

(i) Lanthanoids or 4f- series elements (At. No. - 58-71)

The fourteen elements following Lanthanum.

Because Lanthanum (La) closely resembles the lanthanoids, it is

usually included in any discussion of the lanthanoids. General symbol
“Ln” is often used for Lanthanoids.

(ii) Actinoids or 5f- series elements (At. No. - 90-103)

The fourteen elements following Actinium.

Because actinium closely resembles the actinoids, it is usually included

in any discussion of the actinoids.
The Lanthanoids :

Name

Ce ⎯→ Cerium

Pr ⎯→ Praseodymium

Nd ⎯→ Neodymium

Pm ⎯→ Promethium

Sm ⎯→ Samarium
The Lanthanoids :

Name

Eu ⎯→ Europium

Gd ⎯→ Gadolinium

Tb ⎯→ Terbium

Dy ⎯→ Dysprosium

Ho ⎯→ Holmium
The Lanthanoids :

Name

Er ⎯→ Erbium

Tm ⎯→ Thulium

Yb ⎯→ Ytterbium

Lu ⎯→ Lutetium
 Electronic Configurations of Lanthanoids

58Ce Cerium ⎯→ 54[Xe] 4f1 5d1 6s2

59Pr Praseodymium ⎯→ 54[Xe] 4f3 5d0 6s2

60Nd Neodymium ⎯→ 54[Xe] 4f4 5d0 6s2

61Pm Promethium ⎯→ 54[Xe] 4f5 5d0 6s2

62Sm Samarium ⎯→ 54[Xe] 4f6 5d0 6s2

63Eu Europium ⎯→ 54[Xe] 4f7 5d0 6s2

64Gd Gadolinium ⎯→ 54[Xe] 4f7 5d1 6s2

 Electronic Configurations of Lanthanoids

65Tb Terbium ⎯→ 54[Xe] 4f9 5d0 6s2

66Dy Dysprosium ⎯→ 54[Xe] 4f10 5d0 6s2

67Ho Holmium ⎯→ 54[Xe] 4f11 5d0 6s2

68Er Erbium ⎯→ 54[Xe] 4f12 5d0 6s2

69Tm Thulium ⎯→ 54[Xe] 4f13 5d0 6s2

70Yb Ytterbium ⎯→ 54[Xe] 4f14 5d0 6s2

71Lu Lutetium ⎯→ 54[Xe] 4f14 5d1 6s2

 Electronic Configuration

lanthanoid series: 58Ce – 71Lu

4f-series

5f-series

actinoid series : 90Th– 103Lr

It may be noted that atoms of these elements have electronic

configuration with 6s2 common but variable occupancy of 4f level.

The irregularities in the electronic configuration of lanthanoids are

related to the stabilities of the f 0 f 7 f 14 occupancies of the 4f
orbitals.
Some information regarding lanthanides

1. Position in periodic table – 6th period and 3rd group.

2. In Lanthanoids except Pm (Promethium) all elements are naturally

occurring substances.

3. Due to high reactivity, Pm (Promethium) is found in combined form

or compound form.

4. Pm is a lab synthesized radioactive metal substance.

5. In lanthanoids, 4f orbital electrons doesn’t participate in Bonding

that leads to variable oxidation states in a very few elements.
 Atomic and Ionic Size

1. The decrease in atomic radii is not quite regular in the Lanthanoids.

2. The overall decrease in atomic and ionic radii from Lanthanum to

Lutetium is a unique feature in the chemistry of the lanthanoids.

3. This is due to poor shielding of nucleus by electrons present in the

inner ante-penultimate 4f-orbitals.

4. The cumulative effect of the contraction of the lanthanoid series,

known as Lanthanoid Contraction or f-contraction.
Lanthanoid Contraction or f-contraction

6s

5d

4f
 Atomic and Ionic Size
Sm2+
110
Eu2+
5. The decrease in ionic radii of La3+

M3⊕ ions is comparatively more Ce3+

Pr3+
regular than the atomic radii. 100 Nd3+
Pm3+
Sm3+

Ionic radii in pm
Eu3+ Tm2+
Gd3+
Ce4+ Tb3 Yb2+
+
Dy 3+

90 Pr 4+ Ho3+
Er3+
Tm3+
Yb3+
Tb4+ Lu3+

57 59 61 63 65 67 69 71
Atomic number

Trends in ionic radii of lanthanoids

Consequences of lanthanoid contraction

Small difference between size of 4d and 5d series of transition

element.

Effect of basic strength: Basic strength decreases on moving from

left to right.

Steady decrease in size.

Electrode potential E° ⎯→ –2.2 to -2.4 (except Eu i.e. E° is –2.0)

Increased tendency to get hydrolysed.

Thermal decomposition of oxysalts decreases on moving left to right.

 Oxidation States

1. The common oxidation state for lanthanoids is +3 but some elements

show +2 and +4 states also.

2. (i) Ce → +3 most stable but in some solutions +4 is also observed.

(ii) Pr, Nd, Tb and Dy also exhibit +4 state but only in oxides, MO2.

(iii) Eu2+ is a strong reducing agent changing to the common +3 state,

and Samarium is very much like Europium exhibiting both +2 and
+3 oxidation states.

(iv) Yb2+ has f14 configuration is a reductant changing to the common

+3 state.

(v) TbIV has f7 configuration is an oxidant changing to the common

+3 state.
 Oxidation States

Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu

+2 +2 +2 +2 +2 +2

+3 +3 +3 +3 +3 +3 +3 +3 +3 +3 +3 +3 +3 +3

+4 +4 +4 +4 +4
 General characteristics

1. Reactivity very high.

2. All lanthanoids are Silvery white soft metals.

3. Tarnish rapidly in air.

4. They have typical metallic structure; due to that they are good
conductor of heat and electricity.

5. The hardness increases with increasing atomic number as metallic

bonding strength increases generally.

6. Basic nature : Ca(OH)2 > hydroxides of Ln > Al(OH)3

Melting Point

No regular trend of melting point.

Melting points ranging from 1000 to 1200 K.

M. P. of Samarium is 1623 K.

Samarium is also called steel hard due to high M.P. similar as steel.
Density

Lanthanoids have high density due to low volume and large atomic mass.

(density = mass/volume)

Density change smoothly except for Eu and Yb.

As in Eu and Yb due to stability of half and fully filled f-orbital only

s-orbital electrons participate in metallic bonding, hence, size
increases and density decreases.
 COLOUR

1. (i) Many trivalent lanthanoid ions are coloured both in the solid state
and in aqueous solutions.

(ii) Colour of these ions may be attributed to the presence of

unpaired electrons present in f-orbitals. However, absorption
bands are narrow, probably because of the excitation within f-
level, called f-f transition.

(iii) La3+ and Lu3+ both ions do not show any colour, but the rest do so.

2. (i) The lanthanoid ions other than the f 0 type (La3+ and Ce4+) and the
f14 type (Yb2+ and Lu3+) are all paramagnetic.

(ii) The paramagnetism rises to maximum in Nd.

Ionisation Enthalpy

The first ionisation enthalpies of the lanthanoids is less than the

alkaline earth metal elements of their respective period.

Magnetic Property

The lanthanoid ions other than the f0 type (La3+ and Ce4+ ) and the f14
type (Yb2+ and Lu3+) are all paramagnetic.

Neodymium is the maximum paramagnetic exceptionally.

Chemical Properties
H2 
Ln2O3

Ln
Ln2S3

LnN Ln(OH)3 +H2 

(hydroxide)

LnC2 ⎯⎯⎯→ Ln3C/ Ln2C3

Small amount/fraction
Alloy Formation

A well-known alloy is Misch-metal which consists of a lanthanoid

metal (~95%) and iron (~5%) and some traces of S, C, Ca and Al.

Misch-metal is used in Mg-based alloy to produce bullet shells and

lighter flints.

Mixed oxides of lanthanoids are employed as catalysts in petroleum

cracking.

Some individual Ln oxides are used as phosphors in television screens

and similar fluorescent surfaces.

The best single use of the lanthanoids is to produce alloy steels for
manufacturing of plates and pipes.
 Radioactivity

All lanthanoids are naturally occurring except Promethium (pm) which

is a lab synthesized radioactive substance.

Complex Formation

Due to low charge density, they have poor tendency to form complexes.
However, Lu3+ forms several complexes due to its small size.
Uses of LanthAnoids

CeO2 is used to polish glass. CeO2, La2O3, Nd2O3 and Pr2O3 are used
as decolourizing agents for glasses.

Cerium molybdate and cerium tungstate are used in paints and dyes.

CeS is used for making crucibles that can withstand temperatures up

to 1950 °C (as M.P. of the crucibles is 2000 °C) and used as
refractory material..
The actinoids :

Name

Th ⎯→ Thorium

Pa ⎯→ Protactinium

U ⎯→ Uranium

Np ⎯→ Neptunium

Pu ⎯→ Plutonium
The actinoids :

Name

Am ⎯→ Americium

Cm ⎯→ Curium

Bk ⎯→ Berkelium

Cf ⎯→ Californium

Es ⎯→ Einstenium
The actinoids :

Name

Fm ⎯→ Fermium

Md ⎯→ Mendelevium

No ⎯→ Nobelium

Lr ⎯→ Lawrencium
 Electronic Configuration

90Th Thorium ⎯→ 86[Rn] 5f0 6d2 7s2

91Pa Protactinium ⎯→ 86[Rn] 5f2 6d1 7s2

92U Uranium ⎯→ 86[Rn] 5f3 6d1 7s2

93Np Neptunium ⎯→ 86[Rn] 5f4 6d1 7s2

94Pu Plutonium ⎯→ 86[Rn] 5f6 6d0 7s2

95Am Americium ⎯→ 86[Rn] 5f7 6d0 7s2

96Cm Curium ⎯→ 86[Rn] 5f7 6d1 7s2

 Electronic Configuration

97Bk Berkelium ⎯→ 86[Rn] 5f9 6d0 7s2

98Cf Californium ⎯→ 86[Rn] 5f10 6d0 7s2

99Es Einsteinium ⎯→ 86[Rn] 5f11 6d0 7s2

100Fm Fermium ⎯→ 86[Rn] 5f12 6d0 7s2

101Md Mendelevium ⎯→ 86[Rn] 5f13 6d0 7s2

102No Nobelium ⎯→ 86[Rn] 5f14 6d0 7s2

103Lr Lawrencium ⎯→ 86[Rn] 5f14 6d1 7s2

 Electronic Configuration

lanthanoid series: 58Ce – 71Lu

4f-series

5f-series

actinoid series : 90Th– 103Lr

It may be noted that atoms of these elements have electronic

configuration with 7s2 common but variable occupancy of 5f and 6d
sub shell.

The irregularities in the electronic configuration of actinoids are

related to the stabilities of the f0, f 7, f 14 occupancies of the 5f
orbitals.
 General characteristics

1. Silvery white soft metals.

2. Show variety of structures due to irregularities in metallic radii.

3. Uranium is the heaviest naturally occurring element.

4. After Uranium (92), 11 elements of f-block are artificially

synthesized called Transuranium elements.

5. All actinoids are highly radioactive in nature so study of their

properties becomes difficult.

6. Electrons of 5f-orbitals participate in bonding leads to large range

of oxidation states in some elements.
Atomic and Ionic Sizes

The general trend like lanthanoids is observable for atomic radii in

the actinoids as well.

There is a gradual decrease in the size of M3⊕ ions across the series.

This may be referred to as the actinoid contraction (like lanthanoid

contraction).

Actinoid contraction is resulting from poor shielding done by 5f

electrons over electrons present in the outer shells.

The contraction is, however, greater from element to element in this

series as compared to the lanthanoid series.
 Oxidation State

Most common oxidation state is +3 but they show +4, +5, +6, +7
oxidation state in certain elements.

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
+4 4 +4 +4 +4 +4 +4 +4
+5 +5 +5 +5 +5
+6 +6 +6 +6
+7 +7
Oxidation State

Highest oxidation state shown is +7 by Np and Pu.

Uranium has +6 stable oxidation state and forms UF6.

Density

Except Thorium and Americium all actinoids have high densities.

Colour

Actinoids are generally coloured.

The colour of actinoids depends upon the number of unpaired 5f

electrons.

If there is no unpaired electrons it will be colourless.

Colour

Actinoids are generally coloured.

The colour of actinoids depends upon the number of unpaired 5f

electrons.

If there is no unpaired electrons in 5f orbitals, then it will be

colourless.
Magnetic Property

The magnetic properties of the actinoids are more complex than

those of the lanthanoids.

Although the variation in the magnetic susceptibility of the actinoids

with the number of unpaired 5f electrons is roughly parallel to the
corresponding results for the lanthanoids, the latter have higher
values.

Actinoid are paramagnetic due to unpaired electrons except

Nobelium (No).

102No ⎯→ 86[Rn] 5f14 6d0 7s2

Complex Formation

Actinoids have stronger tendency towards complex formation.

Radioactivity

All actinoids are radioactive while lanthanoids are non-radioactive

[except Promethium (Pm)].

Basic Nature of Oxides and hydroxides

Oxides and hydroxides of actinoids are more basic than lanthanoid.

 Uses of actinoids

1. Thorium is used in nuclear reactors as fuel rod and in treatment of

cancer.

2. Uranium is used as nuclear fuel.

3. Compounds of uranium are used to impart green color to glass and

also for medicinal purposes.

4. Plutonium is used as fuel for atomic reactors and also used to make
atomic bombs or explosives.