Chapter 4- The d and f Block Elements

Elements from 3rd group to 12th group in the Modern Periodic table are called d-block elements. In
these elements their last electron enters in the penultimate d- sub shell. They are placed in between s-block and
p-block elements. They show a regular transition from the highly electropositive metals of s- block elements to
the less electropositive p-block elements. So they are called transition elements.
Transition elements can be defined as elements which contain partially filled d orbitals in their atomic
state or in any of their oxidation state. The elements Zn, Cd and Hg contain only completely filled d-orbitals. So
they are not regarded as transition elements. Or, they are called pseudo transition elements.
There are four series of transition elements.
1) 3d series [from Scandium (Sc, z = 21) to zinc (Zn, z = 30)]
2) 4d series [from Yttrium(Y, z = 39) to cadmium, (Cd, z = 48)]
3) 5d series [from Lanthanum, (La, z =57), Hafnium, (Hf, z = 72) to Mercury, (Hg, z=80)]
4) 6d series [from Actinium, (Ac, z=89), Rutherfordium, (Rf, z=104) to copernicium, (Cn, z=112)]
Electronic Configuration
General outer electronic configuration of d-block elements is (n-1) d1-10 ns1-2. There is only a small
difference in energy between (n-1)d orbital and ns orbital. So in some cases ns electrons are also transferred to
(n-1)d level.
The electronic configurations of Cr and Cu in the 3d series show some exceptions.
24Cr – [Ar] 3d 4s
5 1

29Cu – [Ar] 3d 4s
10 1

This is due to the extra stability of half-filled (d5) and completely-filled electronic configurations (d10).
The electronic configurations of Zn, Cd and Hg are represented by the general formula (n-1)d10 ns2.
The orbitals in these elements are completely filled in the ground state as well as in their common oxidation
states. So they are not regarded as transition elements.

Electronic configuration of first row transition series elements:

Atomic number Element Symbol Electronic configuration
21 Scandium Sc [Ar] 3d1 4s2
22 Titanium Ti [Ar] 3d2 4s2
23 Vanadium V [Ar] 3d3 4s2
24 Chromium Cr [Ar] 3d5 4s1
25 Manganese Mn [Ar] 3d5 4s2
26 Iron Fe [Ar] 3d6 4s2
27 Cobalt Co [Ar] 3d7 4s2
28 Nickel Ni [Ar] 3d8 4s2
29 Copper Cu [Ar] 3d10 4s1
30 Zinc Zn [Ar] 3d10 4s2
 General characteristics of transition elements
1. Atomic and ionic radii
In a transition series, the atomic and ionic radii first decrease, then become constant and increase
towards the end of the series. This is because in transition elements, the new electron enters in a penultimate
d-orbital. Initially, since there is a few numbers of d electrons, the shielding effect is very poor. As the atomic
number increases, the nuclear charge also increases, so the atomic radius decreases. Towards the middle of the
series, the increase in nuclear charge is balanced by the shielding effect and so the atomic radius becomes
constant. Towards the end of the series, as the e- - e- repulsion increases the atomic radius also increases.
The atomic and ionic radii of 2nd and 3rd row transition metals are quite similar. This is due to the Lanthanide
contraction. In between the 2nd and 3rd row transition elements, 4f electrons are present. The 4f electrons have
very poor shielding effect and as a result the atomic and ionic radii of Lanthanides decrease from left to right
(Lanthanide contraction).
2. Melting and boiling points
Transition elements are generally very hard and have
high melting and boiling points. This is due to the participation
of (n-1)d electrons (penultimate d electrons) in addition to the
ns electrons (valence s electrons) in metallic bonding.
In a transition series, the melting and boiling points 1st
increases up to the middle and then decreases. This can be
explained in terms of metallic bond strength and heat of
atomization which depend on the number of unpaired
electrons. As the number of unpaired electrons increases, the
metallic bond strength increases and hence the heat of
atomization increases. In a transition series, the number of
unpaired electrons increases up to the middle and then
decreases. Hence the melting point also increases first and then decreases.
Manganese (Mn) and Technetium (Tc) have low melting point even though they have d5 configuration. This is
because of their low heat of atomization. The m.ps of second and third row transition series are higher than that of
the first row due to their higher enthalpies of atomization.
3. Ionisation enthalpy
The ionisation enthalpy of transition elements generally increases from left to right. This is due to
increase in the nuclear charge from left to right. But the increase is not regular. This can be explained as
follows.
After the removal of one electron, the relative energies of 4s and 3d orbitals get changed. Hence the
remaining electron in the 4s level is transferred to 3d level. So the unipositive ions have dn configuration with
no 4s electrons. During this reorganisation of electrons, some energy is released and it is known as exchange
energy. So the net energy required to remove the 1st electron is equal to the sum of ionisation enthalpy and
exchange energy.
 The first ionisation enthalpies of Cr and Cu are low. This is because the removal of one electron
does not change their d configuration. Similarly first ionisation enthalpy of Zn is high because after the
removal of one electron there is no change in the d configuration.
Zn → Zn+ +
e- 3d104s2 3d104s1
The 2nd I.E of Cr and Cu are very high. This is because the removal of one more e- from these
metals disrupted their stable configuration (d5 or d10)
The 2nd ionisation enthalpies of Mn and Zn are low, this is because after the removal of one more
electron, they attain the stable half filled or completely filled electronic configuration.
4. Oxidation State
Transition metals show variable oxidation states. This is because in these elements d and s electrons have
comparable energies. So in chemical reaction along with s-electrons, d-electrons also participate.
In a given transition series, the maximum oxidation state increases up to the middle and then decreases.
This is due to the half-filled or fully filled electronic configuration (noble gas configuration). The common
oxidation state of 1st row transition elements is +2. The maximum oxidation state increases from top to bottom
in a group. In lower oxidation state, the transition elements mainly form ionic compounds.
Scandium generally shows +3 oxidation state because after the removal of 3 electrons, it gets a stable noble
gas configuration (d0). The oxidation state of Zinc is +2, because of the completely filled configuration of Zn2+.
5. Electrode Potential
The electrode potential values of first row transition series elements generally increases from left to right
with some exceptions. The E0(Cu 2+| Cu) is positive (+0.34V), while the E0 values of all the other first row
transition elements are –ve. This is because the electrode potential depends on heat of atomization,
ionization enthalpies and hydration enthalpy. For copper, the high energy to transform solid Cu to aqueous Cu2+
is not balanced by its hydration enthalpy. So, copper does not easily react with acid and liberate H2. Only
oxidizing acids [e.g. HNO3 and hot conc. H2SO4] react with Cu and the acid get reduced.
Along the series the E0 values become less –ve due to the increase in the sum of 1st and 2nd ionisation
enthalpies. The E0 values of Mn2+ and Zn2+ are more –ve, this is because of the half-filled configuration of
Mn2+ (d5) and completely filled configuration of Zn2+ (d10). E(M 0 3+ 2+
|M ) value of scandium (Sc) is very low and
that for zinc (Zn) is very high. This is because of their stable electronic configuration.
3+ 2+ 2+ 0 |Fe )
0 e
E (Mn |Mn ) is high because of the stable half-filled configuration of Mn . Similarly E (F 2+ 3+ is low, this
is because after the removal of one electron from Fe2+, it gets a stable electronic configuration.
Fe2+ → Fe3+ +
e- 3d6 3d5
Q. Cu2+ is more stable than Cu+ in aqueous solution. Why?
This is due to the greater –ve hydration enthalpy of Cu2+ than Cu+ . In the case of Cu2+, the
(aq) (aq)
hydration enthalpy is compensated by second ionisation enthalpy.
6. Magnetic Properties
Transition metals show mainly two types of magnetic properties - paramagnetism and diamagnetism.
Some transition metals also show ferromagnetism which is an extreme case of paramagnetism. Paramagnetic
substances are weakly attracted by an external magnetic field, while diamagnetic substances are repelled by an
external magnetic field. Ferromagnetic substances are strongly attracted by an external magnetic field.
Paramagnetism arises from the presence of unpaired electrons. Each unpaired e- is associated with a spin
magnetic moment and an orbital magnetic moment. For the compounds of 1st row transition elements, the
contribution of orbital magnetic moment is effectively cancelled and so only spin magnetic moment is
considered. It is determined by the no. of unpaired e-s and is calculated by the spin only formula:
µs = √n(n + 2) where n is the no. of unpaired electrons and µs is the spin only magnetic moment in the unit
of Bohr Magneton (B.M).
The magnetic moment increases with increase in no. of unpaired e-s. Thus the observed magnetic moment
gives an idea about the no. of unpaired e-s present in the atom or ion.

7. Formation of coloured ions or compounds

Most of the Transition metals ions or compounds are coloured. This is because of the presence of partially
filled d orbitals. When an electron from a lower energy d orbital is exited to higher d level, it absorbs energy
and this is equal to the energy of certain colours in visible region. So the colour observed is the
complementary colour of the light absorbed.
In aqueous solution most of the transition metal ions are coloured since water molecules act as the ligands.
Among Ti2+ and Ti4+, Ti2+ is coloured while Ti4+ is colourless. This is because Ti4+ has no partially filled
d orbitals.
Ti2+ - [Ar] 3d2 Ti4+ - [Ar] 3d0
Similarly among Cu+ and Cu2+, Cu2+ is coloured while Cu+ is colorless. This is due to the lack
(absence) of partially filled d orbitals in Cu+.
8. Formation of Complexes
Transition metals form a large no. of complexes. This is due to:
1. Comparatively smaller size
2. High ionic charge
3. Presence of partially filled d orbitals
4. Ability to show variable oxidation state
Eg: K4[Fe(CN)6], K3[Fe(CN)6], [Ni(CO)4] etc.
9. Catalytic Property
Transition metals act as catalysts in a large no. of chemical reactions. This is due to their large surface area and their
ability to show variable oxidation state.
10. Interstitial Compound Formation
These are formed when smaller atoms like H, N, C, B etc. are trapped inside the crystal lattice of the
metal. They are usually non-stoichiometric and neither typically ionic nor covalent.
E.g.: Fe3H, Mn4N, TiC, VH0.56, TiH1.7 etc.
Some the properties of these compounds are:
1) They have high melting point.
2) They are very hard.
 3) They retain metallic conductivity.
4) They are chemically inert.
11. Alloy Formation
Alloys are homogeneous solid solutions of elements in which at least one element is a metal. They are
formed by atoms with metallic radii within about 15% of each other. Because of similar radii and other
characteristics of transition metals, they readily form alloys. The alloys formed are hard and have high melting point.
E.g.: Bronze (Cu and Sn), Brass (Cu and Zn), Stainless steel (Fe, C, Ni, Mn and Cr) etc.

Some Important Compounds of Transition Elements

1. Potassium dichromate ( K2Cr2O7)
Potassium dichromate is generally prepared from chromite ore (FeCr2O4). The preparation involves three steps.
1. Conversion of chromite ore to sodium chromate
Chromite ore is first fused with sodium carbonate in presence of air to form sodium chromate.
4 FeCr2O4 + 8 Na2CO3 + 7 O2 →−−−→ 8 Na2CrO4 + 2 Fe2O3 + 8 CO2
2. Acidification of sodium chromate to sodium dichromate
The yellow solution of sodium chromate is filtered and acidified with sulphuric acid to orange sodium dichromate.
2Na2CrO4 + 2 H+ →−−−→ Na2Cr2O7 + 2 Na+ + H2O
3. Conversion of sodium dichromate to potassium dichromate
The solution of sodium dichromate is treated with potassium chloride so that orange crystals of potassium
dichromate crystallise out.
Na2Cr2O7 + 2 KCl →−−−→ K2Cr2O7 + 2 NaCl
Properties: The chromate and dichromate are inter convertible in aqueous solution depending upon pH of the
solution. Chromate on acidification gives dichromate and the dichromate on treating with alkali gives chromate.
2 CrO42– + 2H+ →−−−→ Cr2O72– +
H2O Cr2O72– + 2OH- →−−−→ 2 CrO42–
+ H2O
The oxidation state of chromium in chromate and dichromate is
+6.
Structure
The chromate ion is tetrahedral while, the dichromate
ion consists of two tetrahedra sharing one corner with
Cr–O–Cr bond angle of 126°.
Sodium and potassium dichromates are strong oxidising agents. Sodium dichromate is most commonly
used as oxidizing agent, due to its greater solubility in water. Potassium dichromate is used as a primary
standard in volumetric analysis.
Oxidising Property
K2Cr2O7 is a good oxidising agent in acidic medium. Its oxidising action can be represented as follows:
Cr2O72– + 14H+ + 6e– →−−−→ 2Cr3+ + 7H2O
Thus, acidified potassium dichromate will oxidise:
1) Iodide to iodine
6 I – →−−−→ 3I2 + 6 e-
Cr2O72– + 14H+ + 6e– →−−−→ 2Cr3+ + 7H2O
6I – + Cr2O72– + 14H+ →−−−→ 3I2 + 2Cr3+ + 7H2O
2) Sulphide to sulphur
3S2- →−−−→ 3 S + 6e-
Cr2O72– + 14H+ + 6e– →−−−→ 2Cr3+ + 7H2O
3S2- + Cr2O72– + 14H+ →−−−→ 3S + 2Cr3+ + 7H2O
3) Tin(II) to tin(IV)
3 Sn2+ →−−−→ 3Sn4+ + 6 e-
Cr2O72– + 14H+ + 6e– →−−−→ 2Cr3+ + 7H2O
3Sn2+ + Cr2O72– + 14H+ →−−−→ 3 Sn4+ + 2Cr3+ + 7H2O
4) Iron(II) to iron(III) OR, Ferrous ion to ferric
ion 6 Fe2+ →−−−→ 6Fe3+ + 6 e-
Cr2O72– + 14H+ + 6e– →−−−→ 2Cr3+ + 7H2O
Cr2O72– + 14 H+ + 6 Fe2+ →−−−→ 2 Cr3+ + 6 Fe3+ + 7 H2O
USES: It is used as a primary standard in volumetric analysis, as an oxidising agent in many reactions, in
leather industry etc.
2. Potassium permanganate ( KMnO4)
Potassium permanganate is commercially prepared from MnO2 (Pyrolusite). The preparation involves two steps:
i) Conversion of MnO2 to potassium manganate (K2MnO4) by fusing with KOH in presence of air (or an
oxidizing agent like KNO3).
2MnO2 + 4KOH + O2 →−−−→ 2K2MnO4 + 2H2O
ii) Potassium manganate is oxidised to potassium permanganate either by electrolysis or by acidification.

Or, 3MnO 2- + 4H+ →−−−→ 2MnO - + MnO2 + 2H2O

4 4

Properties:
Potassium permanganate forms dark purple crystals which are iso-structural with those of potassium
perchlorate (KClO4).
When heated it decomposes and liberate O2.
2KMnO4 →−−−→ K2MnO4 + MnO2 + O2
Note: In permanganate ion, Mn is in +7 oxidation state with no d-electrons. So the colour of permanganate is
due to ligand to metal charge transfer. i.e. an electron is transferred from oxygen atom to the vacant d-orbital of
Mn.
Structure: The manganate and permanganate ions are tetrahedral. The green manganate is paramagnetic with
one unpaired electron but the permanganate is diamagnetic.

Oxidising Property of KMnO4

KMnO4 is a good oxidizing agent in acidic, basic and neutral media. The oxidizing action in acidic
medium is due to the reaction:
MnO 4- + 8H++ 5e-→−−−→ Mn2+ + 4H 2 O
Acidified permanganate solution oxidises:
1) Oxalate to carbon dioxide
5 x (C2O42-→−−−→2 CO2 + 2e–
)
2 x (MnO 4- + 8H++ 5e-→−−−→ Mn2+ + 4H 2 O)
5 C2O4 +2 MnO4 + 16H →−−−→ 10 CO2 +2 Mn2+ + 8H2O
2- - +

2) Iron(II) to iron(III)
5 Fe2+ →−−−→ 5 Fe3+ + 5e–
MnO 4- + 8H++ 5e-→−−−→ Mn2+ + 4H 2 O
5Fe + MnO4 + 8H →−−−→ 5Fe + Mn2+ + 4H2O
2+ - + 3+

3) Nitrite to nitrate
5NO2– + 5H2O →−−−→ 5NO 3
-
+ 10H+ + l0e–
2 x (MnO 4- + 8H++ 5e-→−−−→ Mn2+ + 4H 2 O)

5NO2– +2 MnO4- + 6H+ →−−−→ 5NO3- + 2 Mn2+ + 3H2O

4) Iodide to free iodine.
10 I– →−−−→ 5I2 + 10e–
2 x (MnO 4- + 8H++ 5e-→−−−→ Mn2+ + 4H 2 O)
10 I + 2 MnO +416H →−−−→ 5 I2 + 2 Mn2+ + 8 H2O
- - +

5) Sulphite to sulphate
2 x (MnO 4- + 8H++ 5e-→−−−→ Mn2+ + 4H 2 O)
5 x (SO3 + H2O →−−−→ SO4 + 2 H + 2e-)
2- 2- +

5SO32- +2 MnO 4- + 6H+ →−−−→ 5SO42- + 2 Mn2+ + 3H2O

In alkaline or neutral medium, permanganate ion is reduced to MnO2
MnO 4- + 2H 2O + 3e-→−−−→ MnO 2 + 4OH
-

In alkaline medium it oxidises

1) Iodide to iodate
(MnO4- + 2H2O + 3e-→−−−→ MnO2 + 4OH-) x
2 I- + 6OH- →−−−→ IO3- + 3 H2O + 6 e–
2 MnO - 4+ H2O + I - →−−−→ 2 MnO2 + 2 OH-+ IO - 3
 2) Thiosulphate to sulphate
(MnO4- + 2H2O + 3e-→−−−→ MnO2 + 4OH-) x
8 (S2O32- + 10OH- →−−−→ 2SO42- + 5 H2O + 8e-
)x3
8MnO4- + H2O +3 S 2O 32- →−−−→ 8MnO 2 + 2OH-+ 6SO
4
2-

Note: For acidification of permanganate, hydrochloric acid (HCl) is not used, since it is oxidised to chlorine.
Uses: It is used as an oxidising agent in acidic, basic and neutral medium. It is used as a primary standard in
volumetric analysis. It is used for the bleaching of wool, cotton, silk and other textile fibres and also for the
decolourisation of oils.
THE INNER TRANSITION ELEMENTS ( f-BLOCK)
The elements in which the last electron enters in the anti-penultimate f-subshell are called f-block
elements. They include lanthanides of the 6th period and actinides of the 7th period. They are also called inner
transition elements. Since lanthanum (57La) closely resembles lanthanides, it is also included along with them.
Similarly, actinium (89Ac) is included along with actinoids because of its close resemblance with them.

The Lanthanoids or lanthanides

The 14 elements after lanthanum of the 6th period are called lanthanides or lanthanoids or lanthanones
or rare earths. They include elements from 58Ce to 71Lu. They are generally represented as Ln. Atomic and
ionic radii - Lanthanide Contraction
In lanthanides, the atomic and ionic radii decrease regularly from lanthanum to lutetium. This regular decrease in
the atomic and ionic radii along lanthanide series (though very slightly) is called lanthanide contraction.
Reason: In lanthanides, as the atomic number increases, the nuclear charge increases one by one and the
electrons are added to the anti-penultimate f subshell. Due to its diffused shape, f orbitals have poor shielding
effect. So the nucleus can attract the outer most electrons strongly and as a result the radii decreases.
Consequences of Lanthanide contraction:
1) Due to Lanthanide Contraction the 2nd and 3rd row transition series elements have similar radii.
E.g. Zr – 160pm and Hf -159pm
2) Lanthanides have similar physical properties and they occur together in nature. So their isolation is
difficult.
3) The basic character of their hydroxides decreases from lanthanum to lutetium. i.e, La(OH)3 is more basic
than Lu(OH)3.
Oxidation number
In lanthanoids, the most common oxidation state is +3. However, +2 and +4 ions in solution or in
solid compounds are also obtained. This irregularity arises mainly from the extra stability of empty, half-filled
or filled f subshells. Cerium shows the oxidation state +4 due to its noble gas configuration. Praseodymium
(Pr), neodymium (Nd), terbium (Tb) and dysprosium (Dy) also exhibit +4 state but only in oxides, MO2.
Europium (Eu) and ytterbium (Yb) shows +2 oxidation state because of the stable f7 or f14 configuration.
Samarium (Sm) shows +2 oxidation state also.
General properties of Lanthanoids
All the lanthanoids are silvery white soft metals and tarnish rapidly in air. Their hardness increases
with increasing atomic number. They have typical metallic structure and are good conductors of heat and
electricity.
Most of the lanthanoid ions are coloured both in the solid state and in aqueous solutions. Colour of
these ions is due to the presence of f electrons. But La3+ or Lu3+ ion are colourless. The lanthanoid ions other
than the f 0 type (La3+ and Ce4+) and the f 14 type (Yb2+ and Lu3+) are all paramagnetic. The paramagnetism
rises to maximum in neodymium.
Chemical properties
Some of the chemical reactions of lanthanides are:
Δ
4 Ln + 3 O2 →−−−−→2 Ln2O3
Δ
2 Ln + 3 S →−−−−→ Ln2S3
Δ
Ln + ½ N2 →−−−−→ LnN
2773 K
Ln + 2 C →−−−−−−−→ LnC2
Ln + 3 H2O →−−−→ Ln(OH)3 + 3
H2 2 Ln + 3 X2 →−−−→ 2 LnX3
2 Ln + 6 HCl →−−−→ 2 LnCl3 + 3 H2
Uses of Lanthanides
The main use of the lanthanoids is for the production of alloy steels. An important alloy is mischmetall
which consists of a lanthanoid metal (~ 95%) and iron (~ 5%) and traces of S, C, Ca and Al. It is mainly used in
Magnesium based alloy to produce bullets, shell and lighter flint.
Mixed oxides of lanthanoids are used as catalysts in petroleum cracking. Some lanthanide oxides are
used as phosphors in television screens and similar fluorescing surfaces.

The Actinoids or Actinones

The 14 elements after actinium in the 7th period of modern periodic table are called actinides or
actinoids or actinones. They include elements from 90Th to 103Lr. Most of them are artificially prepared and are
short lived. They are radioactive. The elements after Uranium are artificially prepared and so they are called
trans-uranium elements or trans-uranic elements.
Atomic and ionic radii
In actinoid series the atomic and ionic radii decrease regularly from left to right. This is known as
Actinoid contraction.
Oxidation state
Common oxidation state of actinoids is +3. The elements in the first half of the series show higher
oxidation states. The maximum oxidation state increases from +4 in thorium (Th) to +5, +6 and +7
respectively in protactinium (Pa), uranium (U) and neptunium (Np) but decreases in succeeding elements.
The actinoids resemble the lanthanoids in having more compounds in +3 state than in the +4 state.
 Comparison between lanthanoids and actinoids
1. Most of the actinoids are artificially prepared and are radioactive.
2. The first ionisation enthalpy of early actinoids is lower than those of lanthanoids.
3. Actinoid contraction is greater from elements to elements than lanthanoid contraction. This is due to
the poor shielding effect of 5f electrons.
USES OF d AND f BLOCK ELEMENTS
I. d and f block elements and their compounds are used as catalysts in many chemical reactions.
II. In the Wacker process, the oxidation of ethyne to ethanal is catalysed by PdCl2.
III. Iron and steels are the most important construction materials.
IV. Alloys of d and f block elements are used in various fields.
V. Copper (Cu), Silver (Ag), Gold (Au) and some alloys are used for making coins.
VI. TiO is used in pigment industry.
VII. Zn, Ni, cadmium (Cd), MnO2 etc are used in making batteries.
VIII. Compounds of Ag are used in photography.
IX. Nickel complexes are useful in the polymerisation of alkynes and other organic compounds such as
benzene.
X. An alloy of lanthanoids known as mischmetall is used in Magnesium based alloy to produce bullets,
shell and lighter flint.
XI. Uranium is used as fuel in nuclear reactors.