THE d- AND f- BLOCK ELEMENTS

d- block elements: The d block elements are those elements in which the last electron enters
the d- subshell of penultimate shell.
Transition elements; the elements of d block are known as transition elements
First transition series or 3d series:​Scandium to Zinc
Second transition series or 4d series:​Yttrium to Cadmium
Third transition series or 5d series​: Lanthanum to Mercury
Fourth transition series​ ​or 6d series:​Begins with Actinium still incomplete
Zinc cadmium and mercury of group 12 have full diet and configuration in their ground state
hence they are not regarded as transition metals
General characteristics of transition elements
(i)Atomic and ionic radii:
In a transition series as the atomic number increases the atomic radii first decrease till the
middle, becomes almost constant and then increase towards the end of the period the decrease
in atomic radii in the beginning is due to increase in the effective nuclear charge with the
increase in atomic number.However, with the increase in the number of electrons in (n-1) d
subshell, the screening effect of these d electrons in the outermost and its electrons also
increases. This increased screening effect counterbalance is the effect of increased nuclear
charge, therefore the atomic radii remain almost constant in the middle of the series. Increase in
atomic radii towards the end may be attributed to the electron- electron repulsion
(ii) Enthalpies of Atomisation:
Transition elements exhibit higher enthalpies of atomisation because of large number of
unpaired electrons in their atoms. They have stronger interatomic interaction and have stronger
bond.
(iii) Ionisation Enthalpies:
In a series from left to right, ionisation enthalpy increases due to increase in nuclear charge.
The irregular trend in the first ionisation enthalpy of the 3d metals, though of little chemical
significance, can be accounted for by considering that the removal of one electron alter the
relative energies of 4s and 3d orbitals.
(iv) oxidation states:
Transition metals shows variable oxidation state due to incomplete outermost shells. The
transition elements in their lower oxidation state usually forms ionic compounds. In higher
oxidation state compounds are normally covalent.
(v) Standard electrode potentials:
There is irregular variation in electrode potential due to irregular variation in ionisation enthalpy,
sublimation energy and energy of hydration. The input value decreases from left to right across
the series.
Mn, Ni and Zn have higher values than expected because of their half filled or completely filled
3d orbital is in case of Mn2+ and Zn2+ and the highest negative enthalpy of hydration, Ni2+.
(vi)Melting and boiling point:
Except zinc, cadmium and mercury all the other transition elements generally have high melting
and boiling points. This is due to strong metallic bonds and presence of partially filled d-orbitals
in them.
Zn , Hg and Cd have fully filled d orbital therefore there is no covalent bonding amongst the
atoms of these element. This accounts for their low melting and boiling points.
(vii)Magnetic properties:
The magnetic moment of the electrons of first transition series can be calculated with the
unpaired electrons by the spin only formula.

(viii) complex formation:

The tendency to form complex ions is due to the higher charge on the transition metal ions and
the availability of d orbitals for accommodating electrons donated by the ligand atom.
(ix) Catalytic property:
Most of the transition metals and their compounds possess catalytic properties due to presence
of variable oxidation state and large surface area so that the reactants are adsorbed on the
surface and come close to each other facilitating the reaction process.
(x) colour​:
Most of the transition metal ions in solution as well as in solid state are coloured. This is due to
the partial absorption of visible light. The absorbed light promotes the electrons from one orbital
to another orbitals of the same d-subshell. It is because of these d-d transitions occurring in a
transition metal ion by absorption of visible light that they appear coloured.
(xi) Formation of interstitial compounds:
Interstitial compounds are those in which small atoms occupy the interstitial site in the crystal
lattice. Interstitial compounds are well known for transition metals because small sized atoms of
H, B, C, N, etc. can easily occupy positions in the voids present in the crystal lattice of transition
metals.
(x) Alloy formation:
The transition metals have similar radii and other characteristics. Therefore these metal can
mutually substitute their position in their crystal lattice and form alloys. The alloys so formed are
hard and often have high melting point.

Lanthanoid contraction
From La+3 to Lu+3 in lanthanoid series, overall decrease in atomic and ionic radii with an
increasing atomic number is known as lanthanoid contraction.
Consequences of lanthanoid contraction
(i) Similarity: the elements of second and third series of lanthanides have similar radii
(ii) Basicity - the size decreases from La+3 to Lu+3. Thus, the covalent character increases.
Hence, the basic character of hydroxides also decreases. Thus, La(OH)3 is most basic while
Lu(OH)3 is the least basic.
Presence of unpaired electrons makes a species paramagnetic. Each unpaired electron has a
magnetic moment associated with its spin angular momentum and orbital angular momentum.
For the compounds of the first series of transition metals, the contribution of the orbital angular
momentum is effectively quenched and hence is considerably important. For these, the
magnetic moment is determined by the number of unpaired electrons and is calculated by using
the spin only formula that is

Where n =number of unpaired electrons.

Q1 Among the transition metal iron given below the one with the lowest moment is:
(i) 3d7 (ii)3d9 (iii)3d2 (iv) 3d3
Q2 Which one of the following transition metal and is paramagnetic?
(i)Ag+ (ii) Zn2+ (iii) Cu2+ (iv) Au+
Q3 The magnetic moment of a transition metal and is found to be 3.87 B.M. The number of
unpaired electrons present in it is:
(i) 2 (ii) 3 (iii) 4 ( iv) 5

Q4 Assertion:Eo for Mn3+/Mn2+ is more positive than for Cr3+/Cr2+

Reason:The third ionisation energy of Mn is larger than that of Cr.
a) Both Assertion and Reason are true and Reason is correct explanation of the Assertion.
(b) Both Assertion and Reason are true and Reason is not the correct explanation of the
Assertion.
(c) Assertion is true but Reason is false.
(d) Both Assertion and Reason are false.

Q5 Assertion: Atomic size of silver is almost the same as that of gold

Reason: d sub shell has low penetration power and produces poor shielding.
a) Both Assertion and Reason are true and Reason is correct explanation of the Assertion.
(b) Both Assertion and Reason are true and Reason is not the correct explanation of the
Assertion.
(c) Assertion is true but Reason is false.
(d) Both Assertion and Reason are false.

Two marks questions

Q6why do the transition elements have higher enthalpies of atomisation? In 3d series which
element has the lowest enthalpy of atomisation and why?
Q7Give example and suggest reasons for the following features of the transition metal
chemistry:
(i)The lowest oxide of transition metal is basic, the highest is acidic.
(ii)The highest oxidation state is exhibited in oxo annoyance of a metal.
Q8Account for the following:
(i) Cobalt is stable in aqueous solution but in the presence of complexing agent, it is easily
oxidised.
(ii) The d1 configuration is very unstable in ions.
Q9 Why the ions Sm2+, Eu2+ and Yb2+ in solution are good reducing agent whereas Ce4+ is a
good oxidising agent?

Three marks questions

Q10 Explain the following observations:
(i) Transition elements and their compounds are known to act as catalyst.
(ii) The higher oxidation states are usually exhibited by the members in the middle of a series of
transition elements.
(iii)The metal metal bonding is more frequently found with the second and third series of
transition elements.
Q11Give reason for the following
(i)Scandium forms no coloured ions and yet it is regarded as transition elements.
(ii) The properties of third transition series are similar to second transition series.
(iii) La(OH)3 is more basic than Lu(OH)3.
Q12 Account for the following
(i) The separation of lanthanide elements difficult.
(ii)Chemistry of all the lanthanides is quite similar.
(iii)Size of trivalent lanthanide cations decreases with the increase in atomic number.