UNIT-8

d and f block elements

Periodic table
d –Block elements and transition metals:-

The elements lying in the middle of periodic table belonging to groups 3

to 12 are known as d – block elements.

Transition Elements:-
Elements having partially filled d-orbitals in ground state or in excited
state, are known as transition elements.
They have been placed in the centre of the Periodic Table between s-
block and p-block elements.
General Electronic Configuration of Transition Elements:-

(n −1)d1─10 ns1─2, where (n −1) stands for the inner d orbitals.

The d-block elements having incompletely filled d-subshell are called
transition metals.

General electronic configuration of Zinc, cadmium, mercury :

(n –1)d10 ns2, they are not regarded as transition metals due to completely
filled d – orbital.

Four transition series:

a) 3d – transition series:-
Atomic number 21(Sc) to 30(Zn) and have incomplete 3d orbitals is called
the first transition series.
b) 4d – transition series:-
Atomic number 39(Y) to 48 (Cd) and have incomplete 4d orbitals. It is
called second transition series.
c) 5d – transition series:-
Atomic number 57(La), 72(Hf) to 80(Hg) have incomplete 5d orbitals. It is
called third transition series.
d) 6d – transition series:-
Atomic number 89(Ac), 104(Rf) to 112(Uub) having incomplete 6d
orbitals. It is called fourth transition series.
 Atomic Electronic
Element
number configuration
Scandium 21 [Ar]3d-452
Titanium 22 [Ar]30-452
Vanadium 23 [Ar]3d3452
Chromium 24 [Ar]3d5451
Manganese 25 [Ar]305452
Iron 26 [Ar]346452
Cobalt 27 [Ar]3d452
Nickel 28 [Ar]3d8452
Copper 29 [Ar]3d104s1
Zinc 30 [Ar]3d104.52
 General Characteristics of transition elements
1. Atomic and ionic radii :-

• Atomic size decreases left to right.

• Increases at the end of series.

• 4d & 5d series have almost same

size.(due to lanthanoid contraction)

*The atomic radii decrease from Sc to Cr because the effective nuclear charge
increases.
*The atomic size of Fe, Co, Ni is almost same because the attraction due to
increase in nuclear charge is cancelled by the repulsion because of increase in
shielding effect.
*Cu and Zn have bigger size because the shielding effect increases and
electron - electron repulsions repulsion increases.

2. Metallic character : -
All transition elements are metallic in nature, i.e. they have strong metallic
bonds. It is because of presence of unpaired electrons.
3.Ionization enthalpy :-
*There is an increase in ionization enthalpy from left to right
which is due to the increase in effective nuclear charge along a series.
*But the trend is not very regular.
Exceptions :- Chromium and copper have notably larger ionization
enthalpy due to the extra stability associated with the half-filled and
fully-filled set of d-orbitals.
* Although the first ionization enthalpy increases, the magnitude of
2nd and 3rd ionization enthalpies for the successive elements is much
higher.
IE1 < IE2 < IE3
4. Oxidation state:

Transition metals show variable oxidation states due to tendency of

(n-1)d as well as ns electrons to take part in bond formation.
For example:- Oxidation states of the first row transition metals are:
5. Enthalpy of atomization :-
Transition elements exhibit higher enthalpies of atomization. Because of
the presence of a large number of unpaired electrons in their atoms, they
have stronger interatomic interactions and hence, stronger bond.
The elements of 4d and 5d series have greater enthalpies of atomization
than the elements of 3d series. That’s why the elements of 4d and
5d series have more frequent metal-metal bonding in their compounds.

6.Density :-
d-block elements have high density because of their small atomic size
and strong metallic bonding.

7.Melting and boiling point :-

*Due to strong metallic bond, they have high m.p. and b.p.
*Tungsten has the highest m.p. (3410oC).
*Mercury is liquid at room temperature (m.p. – 38.9°C) due to absence
of unpaired electrons, and weak metallic bonding.

8. Complex formation:-
They are well known to form a large number of complex compounds
mainly due to
(a) small atomic size and high nuclear charge
(b) presence of partly filled or vacant d-orbitals. Ex.:-K4[Fe(CN)6]
 9. Coloured ions :-
Colour exhibited by transition metal ions is due to absorption of some
radiation from visible light to cause d-d transition of electrons in
transition metal atom.

10.Catalytic properties :-
The transition metals and their compounds behave like catalyst due to
presence of incomplete or empty d – orbitals,
(ii) large surface area,
(iii) variable oxidation state,
(iv) ability to form complexes,
Ex., Fe, Ni, V2O3, Pt, Mo, Co are used as catalyst.
11.Interstitial compounds:
Transition metals have voids or interstitials in which C, H, N, B etc. can fit into
resulting in formation of interstitial compounds. They are non – stoichiometric,
i.e., their composition is not fixed.
Ex., Steel. They are harder and less malleable and ductile.
12. Alloys formation:
They form alloys due to similar ionic size. Metals can replace each other in
crystal lattice, Ex., brass, bronze, steel etc.

AlloyFormation
•Alloysarehomogeneousmixturesofmorethanone
metalthatcandisplaceanothermetalfromthe
crystallatticeduetotheircomparablesizes.This
leadstotheformationofalloys.
©Thealloyssoformedarehard,highmeltingpoint,
resistanttocorrosion.

©Someotherexamplesarebrass(alloyofcopper+
zinc),stainlesssteel,bronze(alloyofcopper+tin),
etc.

Transitionelementsmakesalloyveryeasilydueto:-
(1)Similaratomicradii(Thediff,inatomicradiiis
notverylargesotheycaneasilysubstituteinone
another'scrystallattice)
13. Magnetic properties :-

(a) Paramagnetic nature is due to the presence of unpaired electrons in d-orbitals.

Paramagnetic character increases with increase in the number of unpaired electrons
and highest for Mn(II) [among 3d-series].

(b) Diamagnetic substances are repelled by applied magnetic field and have no
unpaired electron.

(c) In ferromagnetism, permanent magnetic character is acquired by substance

e.g., Fe.
Magnetic moment is given by
µ = √n (n + 2) BM,
Where, n = number of unpaired electrons and BM = Bohr magneton (unit of
magnetic moment).
 TRENDS IN THE M2+⁄ M STANDARD ELECTRODE
POTENTIAL

*The irregularity in the variation of electrode potentials is due to the irregular

variation of the ionisation enthalpies and also the hydration energies.

*All those elements with negative reduction potentials act as strong reducing agents
and liberate hydrogen from dilute acids.

*Copper does not liberate hydrogen from dilute acids because of its positive
electrode potential.
*The electrode potential values of manganese and zinc can be explained on the
basis of the stability of the half-filled d sub-shell in Mn+2, and the completely filled
d10 configuration in Zn+2.

*Ni is related to the highest negative hydration enthalpy corresponding to its

smaller radius.
 TRENDS IN THE M3+ /M2+STANDARD ELECTRODE
POTENTIAL

• The low value for Sc reflects the stability of Sc3+ which has a
noble gas configuration.

• The highest value for Zn is due to the removal of an electron from

the stable d10 configuration of Zn2+ .

• The comparatively high value for Mn shows that Mn2+ is stable ,

whereas comparatively low value for Fe shows the extra stability
of Fe3+ .
Trends in stability of the higher oxidation states:

#From the table, TiX4, VF5 and CrF6 have the highest oxidation numbers.
#The highest oxidation state +7, for manganese is not seen in simple halides, but
MnO3F is known.
#VF5 is stable, while the other halides undergo hydrolysis to give oxohalides of the
type VOX3.
#Fluorine stabilises higher oxidation states either because of its higher lattice energy
or higher bond enthalpy.
#Fluorides are unstable in their lower oxidation states, and, therefore, chlorides,
bromides and iodides exist in +2 oxidation state, while fluorides do not.
#Copper in +2 oxidation state forms all the halides, except iodides, because cupric
ion oxidises iodide to iodine.
2 Cu2+ + 4I- Cu2I2 + I2
*The highest oxidation number in an oxide coincides with the group number.
*No higher oxides are seen beyond manganese.
*Oxygen also stabilises higher oxidation states in the form of oxocations.
Ex: V (V) is stabilised as dioxovanadium (V) ion, vanadium (IV)as Oxo- vanadium (IV) ion
*Oxygen exceeds fluorine in its ability to stabilise higher oxidation states. Thus, the highest
manganese fluoride is MnF4, while the highest oxide is MnO7.
 F BLOCK ELEMENTS

The elements constituting the f -block are those in which the 4 f and 5 f orbitals are
progressively filled in the latter two long periods.
These consist of two series of elements placed at the bottom of the periodic table.
a)Lanthanoids or Lanthanides or rare earth metals: The first series follows
lanthanum, La (Z= 57) and the elements present in this series from cerium to lutetium
(58Ce – 71Lu) are called lanthaniods or lanthanides. These are also called rare earth
elements.
b)Actinoids or Actinides: The second series follows actinium, Ac (Z = 89) and the
elements present in this series from thorium to lawrencium (90Th - 103Lr) are
called actionoids or actinides. These are of radioactive elements.

1.Electronic configuration
The general electronic configuration of these elements is (n-2) 4f0 – 14 (n-1)d0-1 ns2.

2. Atomic and Ionic size: Lanthanoid contraction

Steady decrease in the atomic and ionic (Ln3+) radii as the atomic number of the
lanthanide elements increases is called lanthanoid contraction. This is because the
additional electron goes to 4f-subshell and 4f-orbitals being large and diffuse, have
poor shielding effect. The effective nuclear charge increases which causes the
contraction in the size of electron charge cloud. This contraction in size is quite
regular and is known as lanthanoid contraction.