CHEMISTRY CLASSES

D BLOCK ELEMENTS Calculate the number of

unpaired electrons in the
Q- TRANSITION VS NON TRANSITION Q- Why d block/transtion are well known for their complex following gaseous ions:
WHY Zinc, cadmium and mercury are formatioon (i) Mn3+, (ii) Cr3+, (iii) V3+
not regarded as transition metals.? The tendency to form complex ions is due to and (iv) Ti3+.
(i) the high charge on the transition metal ions, Which one of these is the
A transition element is defined as an (ii) the availability of d-orbitals for accommodating electrons most stable in aqueous
Element which has incompletely filled d- donated by the ligand atoms
orbitals in its ground state or any one of its solution?
oxidation states
Q why zn cd and hg have low
Zinc, cadmium and mercury of group 12 melting and boiling points What is meant by ‘disproportionation’? Give two examples
have full d 10 configuration in their ground zinc, mercury and cadmium have
of disproportionation reaction in aqueous
state as well as in their common oxidation fully filled d-orbitals, therefore,
states and hence, are not regarded as there is no covalent bonding solution.
transition metals. amongst the atoms of these Ans. Disproportionation reactions are those reactions in
elements. This accounts for their which the same substance undergoes oxidation as well as
low melting and boiling points.
reduction. In disproportionation reaction, oxidation number
Explain giving reasons: of an element increases as well as decreases to form two
(i) Transition metals and many of their compounds show paramagnetic different products. For example,
behaviour.
(ii) The enthalpies of atomisation of the transition metals are high.
(iii) The transition metals generally form coloured compounds.
(iv) Transition metals and their many compounds act as good catalyst.

(I) Substances containing unpaired electrons are said to be paramagnetic. A

diamagnetic substance is one in which all the electrons are paired. Except the
ions of d 0 (Sc3+, Ti4+) and d10 (Cu+, Zn2+) configurations, all other simple
ions of transition elements contain unpaired electrons in their (n – 1) d
subshell and are, therefore, paramagnetic. The magnetic moments (μ) of the
elements of first transition series can be calculated with the unpaired
electrons (n) by the spin only formula.
(ii) The transition elements exhibit high enthalpy of atomisation because they
have large number of unpaired electrons in their atoms. Due to this they have
stronger interatomic interaction.
(III) Most of the transition metal ions in solution as well as in solid states are
coloured. This is due to the partial absorption of visible light. The absorbed
light promotes the electron from one orbital to another orbital of the same d-
subshell. Since the electronic transition occurs within the d-orbitals of
the transition metal ions, they are called d–d transitions. It is because of these
d–d transitions occurring in a transition metal ion by absorption of visible light
that they appear coloured.
(iv) Most of the transition metals and their compounds possess catalytic
properties. The catalytic activity of transition metal ions is attributed to the
following two reasons:
(i) Variable oxidation states due to which they can form a variety of unstable
intermediate products.
(ii) Large surface area so that the reactants are adsorbed on the surface and
come close to each other facilitating the reaction process.
What are the consequences of lanthanoid
contraction?
(i) The properties of second and third transition series are similar.
(ii) Basic strength decreases from La(OH)3 to Lu(OH)3.
(iii) Lanthanide contraction makes separation of lanthanoids possible.
What are alloys? Name an important alloy which contains
some of the lanthanoid metals. Mention
its uses.
Ans. An alloy is a homogeneous mixture of two or more
metals, or metals and non-metals. An important alloy
containing lanthanoid metals is misch metal which contains
95% lanthanoid metals and 5% iron alongwith traces of S, C,
Ca and Al. It is used in Mg-based alloy to produce bullets,
shells and lighter flints.
What are interstitial compounds? Why are such
compounds well known for transition metals?
Ans. Interstitial compounds are those in which small
atoms occupy the interstitial sites 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 lattices of transition metals.
What is lanthanoid contraction?
Lanthanide contraction is the gradual decrease in the atomic and ionic
size of lanthanoids with an increase in atomic number.
Causes of lanthanide contraction:
With an increase in the atomic number, the positive charge on nucleus
increases by one unit and one more electron enters same 4f subshell.
The electrons in 4f subshell imperfectly shield each other. Shielding in a
4f subshell is POOR than in d subshell.
With the increase in nuclear charge, the valence shell is pulled slightly
towards the nucleus. This causes lanthanide contraction.
Due to improper shielding effect of 4f orbitals lanthanoid
contraction occurs

Unfiled Notes Page 1

 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] 3d5 4s1
29Cu – [Ar] 3d10 4s1
This is due to the extra stability of half-filled
and completely-filled electronic
configurations. (d5 or d10)
Atomic and ionic radii
In a given transition series, the atomic and ionic radii first decreases, then become
constant and increases towards the end of the series. This is because in transition
elements the new electron enters in a 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).

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

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 I.Es 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.

How would you account for the irregular variation of ionisation enthalpies (first and second) in first
series of the transition elements?
Ans. Irregular variation of ionisation enthalpies is mainly attributed to varying degree of stability of different 3d
configuration (e.g., d 0 , d 5 , d 10 are exceptionally stable).
2+ 2+
Which is a stronger reducing agent— Cr or Fe and why?
Ans. Cr2+ is a stronger reducing agent than Fe2+ because after the loss of one electron Cr2+ becomes Cr3+
which has more stable t 3 2g (half-filled) configuration in a medium like water.

Explain why Cu+ ion is not stable in aqueous solutions?

In aqueous solution Cu+ undergoes disproportionation to form a more stable Cu2+ ion.
2Cu+ (aq)--> Cu2+(aq) + Cu(s)
The higher stability of Cu2+ in aqueous solution may be attributed to its greater negative ∆hyd.Ho than that of Cu+. It
compensates the second ionisation enthalpy of Cu involved in the formation of Cu2+ ions.

Why are Mn2+ compounds more stable than Fe2+ compounds towards oxidation to their +3 state?
Ans. Electronic configuration of Mn2+ is 3d5 which is half-filled and hence stable. So, 3rd ionisation enthalpy is
very high, i.e., 3rd electron cannot be easily lost. In case of Fe2+, electronic configuration is 3d6. Thus, it can lose
one electron easily to give the stable configuration 3d5.

Unfiled Notes Page 1


Name the oxo-metal anions of the first series of
the transition metals in which the metal
exhibits the oxidation state equal to its group
number.
Cr2O7 2– and CrO4 2– (group no. = oxid. state of Cr = 6)
MnO4 – (group no. = oxidation state of Mn = 7)
Vanadate: VO3 – (group no. = oxidation state of V = 5)
(i) The lowest oxide of transition metal is basic, the
highest is amphoteric/acidic.
Ans. (i) The lowest oxide of transition metal is basic
because the metal atom has low oxidation state. This
means that it can donate valence electrons which are
not involved in bonding to act like a base.
Whereas the highest oxide is acidic due to the highest
oxidation state as the valence electrons are
involved in bonding and are unavailable. For example,
MnO is basic whereas Mn2O7 is acidic.
(ii) A transition metal exhibits higher oxidation states
in oxides and fluorides.
(ii) A transition metal exhibits higher oxidation states in
oxides and fluorides because oxygen and fluorine
are highly electronegative elements, small in size (and
strongest oxidising agents). For example, osmium
shows an oxidation states of +6 in OsF6 and vanadium
shows an oxidation state of +5 in V2O5.
(iii) The highest oxidation state is exhibited in oxo-
anions of a metal.
(iii) Oxometal anions have the highest oxidation state,
e.g., Cr in has an oxidation state of +6
whereas Mn in MnO4– has an oxidation state of +7. This
is again due to the combination of the metal
with oxygen, which is highly electronegative and
oxidising element.
Unfiled Notes Page 1
In what way is the electronic configuration of
transition elements different from that of the
nontransition elements?
Ans. Transition elements contain incompletely filled
d-subshell, i.e., their electronic configuration is
(n – 1) d 1 – 10 ns1 – 2 whereas non-transition
elements have no d-subshell or their subshell is
completely filled and have ns1 – 2 or ns2 np1 – 6 in
their outermost shell.
How is the variability in oxidation states of
transition metals different from that of the non
transition metals? Illustrate with examples.
Ans. The oxidation states of transition elements differ
from each other by unity e.g., Fe2+ and Fe3+, Cu+ and
Cu2+ (due to incomplete filling of d-orbitals) whereas
oxidation states of non-transition elements normally
differ by two units e.g., Pb2+ and Pb4+, Sn2+ and
Sn4+, etc.
(i) Of the d4 species, Cr2+ is strongly reducing
while manganese (III) is strongly oxidising.
(i) E° value for Cr3+/Cr2+ is negative (–0.41 V)
whereas E° value for Mn3+/Mn2+ is positive (+1.57
V). Thus, Cr2+ ions can easily undergo oxidation to
give Cr3+ ions and, therefore, act as strong
reducing agent. On the other hand, Mn3+ can
easily undergo reduction to give Mn2+ and hence
act as oxidising agent.
Cobalt (II) is stable in aqueous solution but in
the presence of complexing reagents it is
easily oxidised.
This is because in presence of complexing reagents
the CFSE value compensates more than the third
ionisation energy of cobalt.
The d1 configuration is very unstable in ions.
The ions with d 1 configuration have the tendency
to lose the only electron present in d-subshell to
acquire stable d 0 configuration. Therefore, they
are unstable and undergo oxidation or
disproportionation.
Sunday, August 21, 2022
11:33 AM
(i) the stability of Fe3+ in acid solution as
compared to that of Cr3+ and Mn3+.
(i) Higher the reduction potential of a species, greater
is the ease with which it undergo reduction. Among
these pairs, Mn3+/Mn2+ has largest positive
reduction potential. Hence Mn3+ can be easily
reduced to Mn2+ i.e., Mn3+ is least stable. Cr3+/Cr2+
has a negative Eo value, therefore, Cr3+ is most
stable. Fe3+/Fe2+ has a positive value but small.
Hence, Fe3+ is more stable than Mn3+ but less stable
than Cr3+.
Unfiled Notes Page 1
(ii) the ease with which iron can be oxidised as
compared to the similar process for either Cr or
Mn metals.
Lower the reduction potential or higher the oxidation
potential of a species, greater is the ease with which it
undergo oxidation. Among these pairs, Mn2+/Mn has
the most negative reduction potential or most
positive oxidation potential. Therefore, it will be most
easily oxidised. Thus, the decreasing order of their
ease of oxidation is Mn > Cr > Fe.
5

Unfiled Notes Page 1

6

Unfiled Notes Page 1

7

Unfiled Notes Page 1

8

Unfiled Notes Page 1

9

Potassium Dichromate, K2Cr2O7: It is Potassium permanganate, KMnO4:

prepared from the chromite ore. Different It is prepared by fusion of pyrolusite, MnO2,
reactions involved in the preparation of with KOH in the presence of an oxidising agent
potassium dichromate from chromite ore are:

Unfiled Notes Page 1

10

THE INNER TRANSITION ELEMENTS ( f-BLOCK) Chemical properties

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 lanthanidesThe 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
Uses of Lanthanides
contraction.
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%)
Reason: In lanthanides, as the atomic number increases, the nuclear
and iron (~ 5%) and traces of S, C, Ca and Al.
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
A great deal of mischmetall is used in Magnesium based alloy to produce
shielding effect. So the nucleus can attract the outer most electrons
bullets, shell and lighter flint.
strongly and as a result the radii decreases.
Mixed oxides of lanthanoids are employed as catalysts in petroleum cracking.
Some Ln oxides are used as
Consequences:
phosphors in television screens and similar fluorescing surfaces.
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

The Actinoids or Actinones
in nature. So their isolation is difficult.
The 14 elements after actinium in the 7th period of modern periodic table are
called actinides or
3) The basic character of their hydroxides decreases from lanthanum to
actinoids or actinones. They include elements from 90Th to 103Lr. Most of
lutetium. i.e, La(OH)3 is more basic than Lu(OH)3.
them are artificially prepared and are short lived. They are radioactive. The
elements after Uranium are artificially prepared and so they are called trans-
Oxidation number
uranium elements or trans-uranic elements.
In lanthanoids, the most common oxidation state is +3. However, +2 and
+4 ions in solution or in solid compounds are also obtained. This
Atomic and ionic radii
irregularity arises mainly from the extra stability of empty, half-filled or
In actinoid series the atomic and ionic radii decreases regularly from left to
filled f subshells. Cerium shows the oxidation state +4 due to its noble gas
right. This is known as Actinoid contraction.
configuration. Pr, Nd, Tb and Dy also exhibit +4 state but only in oxides,
MO2. Eu and Yb shows +2 oxidation state because of the stable f7 or f14
Oxidation state
configuration. Sm shows +2 oxidation state also.
Common oxidation state of actinoids is +3. The elements in the first half of the
series show higher
General properties of Lanthanoides
oxidation states. The maximum oxidation state increases from +4 in Th to +5,
All the lanthanoids are silvery white soft metals and tarnish rapidly in air.
+6 and +7 respectively in Pa, U and Np but decreases in succeeding elements.
Their hardness increases with increasing atomic number. They have
typical metallic structure and are
The actinoids resemble the lanthanoids in having more compounds in +3 state
good conductors of heat and electricity. Most of the lanthanoid ions are
than in the +4 state.
coloured both in the solid state and in aqueous solutions. Colour of these
Comparison between lanthanoids and acinoids
ions is due to the presence of f electrons. But La3+ or Lu3+ ion are
1. Most of the actinoids are artificially prepared and are radioactive.
colourless. The lanthanoid ions other than the f 0 type (La3+ and Ce4+)
and the f 14 type (Yb2+ and Lu3+)
2. The first ionisation enthalpy of early actinoids is lower than those of
are all paramagnetic. The paramagnetism rises to maximum in
lanthanoids.
neodymium.
3. Actinoid contraction is greater from elements to elements than lanthanoid
contraction. This is due to greater shielding effect of 5f electrons.

Unfiled Notes Page 1

11

Unfiled Notes Page 1