d -block Elements

• d-block elements are also called Transition elements.

• Includes elements from group 3-12
• Consists of four series of elements
• First Series - 3d series – From Sc to Zn – Filling of 3d orbital.
• Second Series - 4d series – From Y to Cd- filling of 4d orbital.
• Third series- 5d series- From La to Hg, omitting Ce to Lu—Filling of 5d orbital
• The fourth 6d series which begins with Ac is still incomplete.
➢ The two series of the inner transition metals, (4f and 5f) are known as lanthanoids
and actinoids respectively.
➢ General Electronic Configuration: (n-1)d1-10 ns1-2
1. Define a transition element.
A transition element is defined as the one which has incompletely filled (partly
filled) d orbitals in its ground state or in any one of its oxidation states.
Account for the following:
2. Which of the d-block elements may not be regarded as the transition
elements? (Or) Zinc, cadmium and mercury are not considered as true transition
elements?
Zn, Cd and Hg have completely filled d 10 configuration in their ground state as well
as in their common oxidation states. Therefore, they are not regarded as transition
elements.
3. On what ground can you say that scandium (Z = 21) is a transition
element but zinc (Zn= 30) is not?
Scandium has incompletely filled 3d orbitals in its ground state (3d 1), hence it is
regarded as a transition element. On the other hand, zinc atom has completely filled d
orbitals (3d 10) in its ground state as well as in its oxidised state. Hence it is not regarded
as a transition element.
4. Silver atom has completely filled d orbitals (4d10) in its ground state. How
can you say that it is a transition element?
Silver can exhibit +2 O.S where it has incompletely filled d- orbital; (4d 9) hence we
can say it as a transition element.
5. Though Cu, Ag and Au have completely filled d orbitals in its ground state
yet they are considered as transition element. Why?
Cu, Ag, Au metals have incompletely filled (partly filled) d orbitals in their common
oxidation state. Eg; Cu2+ - 3d9 , Ag2+ - 4d9 and Au3+ - 5d8

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 6. The transition elements have many irregularities in their electronic
configuration.
In transition elements, the (n-1)d subshell and ns subshell have very small difference
in energy. The incoming electrons may enter into ns or (n-1)d subshell. Hence, they
show many irregularities in their electronic configuration.
7. In what way is the electronic configuration of the transition elements different
from that of the non-transition elements?
In non-transition elements the valence electrons are present only in the
outermost shell while in the transition elements the valence electrons are present in the
outermost as well as d- orbitals of penultimate shell.
8.The E.C of Cu is written as [Ar] 3d 104s 1 and not as [Ar] 3d 9 4s2 . (Or) The
E.C of Cr is written as [Ar] 3d 5 4s 1 and not 3d 4 4s 2 (Or) Cr and Cu exhibit
exceptional E.C.
• Because of very little energy difference between (n-1) d and ns orbitals.
• Half and completely filled sets of orbitals are relatively more stable due to symmetry
and larger exchange energy.
PHYSICAL PROPERTIES:
I. MELTING AND BOILING POINTS:
➢ Transition metals have high melting and boiling points.
➢ Transition metals are hard and low volatility.
➢ Transition metals have high enthalpies of atomization.
➢ Exception: Zn, Cd. Hg are soft metals.

Account for the following:

1. Transition Elements have high melting and boiling points. (OR) Transition
metals are hard metals and low volatility.
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 The high melting points of transition metals is due to the involvement of greater
number of unpaired electrons from (n-1) d in addition to the ns electrons resulting in
stronger inter-atomic metallic bonding.
2. Transition Elements exhibit higher enthalpies of atomization.
The high enthalpies of atomization of transition metals are due to the involvement of
greater number of unpaired electrons from (n-1) d in addition to the ns electrons resulting
in stronger inter-atomic metallic bonding.
3. Chromium group metals (Cr, Mo and W) are hard metals and have low
volatility (OR) Cr, Mo and W have greater enthalpy of atomization.
This is due to the involvement of greater number of unpaired electrons from (n-1)d in
addition to the ns electrons and hence stronger inter-atomic metallic bonding between the
atoms resulting in higher enthalpies of atomization and hence they are very hard and have
low volatility.
4. Zn, Cd and Hg are soft metals, volatile and have low M.P (OR) Hg is a liquid.
Zn, Cd and Hg do not have any unpaired electrons and due to the absence of unpaired
electrons they have weak inter atomic interactions therefore, these are not very hard.
5. In the series Sc (Z = 21) to Zn (Z = 30), the enthalpy of atomisation of zinc is
the lowest, i.e, 126 kJ mol–1
Zn do not have any unpaired electrons(3d10). Due to the absence of unpaired electrons,
it has weak inter atomic interactions.
6. Mn, Tc (technetium) and Re metals have abnormally low melting points.
Because these metals have exactly half-filled stable electronic configuration. Hence
the electrons are held tightly by the nucleus so that the delocalization is less and the
metallic bond is much weaker than the preceding elements.
7. The metals of the second (4d) and third series (5d) have greater enthalpies of
atomisation and melting point than the corresponding elements of the first series.
This is due to the occurrence of much more frequent metal – metal bonding in
compounds of the heavy transition metals.
8. The metals of the second (4d) and third series (5d) have much more frequent
metal – metal bonding in compounds than do the 3d metals.
In the same group of d block elements, the 4d and 5d series of transition elements
have larger size than that of 3d elements (Down the group atomic size increases). Thus,
the valence electrons are less tightly held and hence can form metal - metal bond more
frequently.

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 II. ATOMIC AND IONIC SIZE:
➢ Period: The ions of the same charge in a given series show progressive decrease in
radius with increasing atomic number.
➢ With the increase in atomic number, the atomic radius does not change very much
in transition series.
As the atomic number increases nuclear charge increases but the addition of electron
in the d subshell increases the screening effect which counter balance the effect of
increased nuclear charge
➢ Group: The atomic size increase from the first (3d) to the second (4d) series of the
elements but the radii of the third (5d) series are virtually the same as those of the
corresponding members of the second series.
➢ The decrease in metallic radius coupled with increase in atomic mass results in a
general increase in the density of these elements. Thus, from titanium (Z = 22) to copper
(Z = 29) the significant increase in the density may be noted.
Account for the following:
1. The ions of the same charge in a given series (Period) show progressive
decrease in radius with increasing atomic number.
This is because the new electron enters a d orbital each time the nuclear charge
increases by unity. Since the shielding effect of a d electron is not that effective, the net
electrostatic attraction between the nuclear charge and the outermost electron increases
and the ionic radius decreases.
2. The atomic radius shows an increase from the first (3d) to the second (4d)
series of the elements but the radii of the third (5d) series are virtually the same as
those of the corresponding members of the second series.
The filling of 4f before 5d orbital results in a regular decrease in atomic radii called
Lanthanoid contraction which essentially compensates for the expected increase in
atomic size with increasing atomic number.
3. What is meant by lanthanoid contraction? What is the cause of Lanthanoid
contraction?
The steady decrease in atomic and ionic sizes of Lanthanide elements (from La to Lu)
with increasing atomic number is called Lanthanoid contraction. It is due to the poor
shielding of 4f electrons.
4. What are the Consequences of lanthanoid contraction?
• Resemblance of second and third transition series:

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 The pairs of elements Zr-Hf, Nb-Ta, Mo-W, etc., possess almost the same size&
similar properties. Zr and Hf have same atomic radi. Why?
• Difficulty in separation of lanthanoids: A consequence of the lanthanoid contraction,
account for their occurrence together in nature and for the difficulty faced in their
separation in pure state.
Q. Zr and Hf occur together in nature OR Separation of Zr and Hf is difficult
from a mixture. Give reason.
• Due to lanthanoid contraction, they have similar size and similar properties.
Basicity differences: As a result of decrease in size, the covalent character of the
hydroxides increases and hence the basic strength decreases.
Q. La(OH)3 is most basic while Lu(OH) 3 is the least basic. Give reason.
Due to lanthanoid contraction, the size of ions decreases from La3+to Lu3+.Therefore
the covalent character of hydroxides increases and hence basic strength decreases.
III. IONISATION ENTHALPY:
➢ There is an increase in ionisation enthalpy along each series (Period) of the
transition elements from left to right due to an increase in nuclear charge which
accompanies the filling of the inner d orbitals. However, many small variations occur.
➢ The first ionisation enthalpy, in general, increases, the magnitude of the increase in
the second and third ionisation enthalpies for the successive elements, in general, is much
higher
Special cases: 1. Chromium & Copper 2. Zn. Cd. Hg 3. Mn & Fe
Account for the following:
1. Chromium (Cr) and Copper (Cu) has low first ionization enthalpy I.E)
Cr- Due to the loss of one electron gives stable configuration (3d 5) and Cu – due to
the loss of one electron gives stable configuration. (3d 10).
2. Zn, Cd and Hg have very high first ionization enthalpy. Give reason.
Because in Zn, Cd and Hg electron has to be removed from 4s orbital of the stable
fully filled configuration (3 d 10 4s2) . Hence large amount of energy is required to remove
the electron.
3. The third ionisation enthalpy of Mn is very high in comparison to Fe.Why?
The third ionisation enthalpy of Mn is very high because the 3rd electron has to be
removed from the stable half- filled 3d- orbital.
Mn : [Ar]3d5 4s2 Mn2+ [Ar]3d5
Fe : [Ar]3d6 4s2 Fe2+ [Ar]3d6
4. The third ionisation enthalpy for change from Fe2+ to Fe3+ is very small.
Because loss of 3rd electron gives stable configuration of 3d5 in Fe3+ ( Fe3+ =[Ar]3d5 )
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 5. The first I.E of third transition series (5d) are higher than those of first (3d)
and second transition series (4d). (OR) The IE of Hf (6th period) is higher than that
of Zr (5th period)
In the atoms of third transition series (5d), there are filled 4f- orbitals. The 4f-orbitals
have very poor shielding effect. As a result, the effective nuclear charge on the outer
valence electrons increases as a result size decreases. Hence their I.Es are higher.
6. How would you account for the irregular variation of ionisation enthalpies
(first and second) in the first series of the transition elements?
The irregular variation of ionisation enthalpies is mainly attributed due to the varying
degree of stability of different 3d configurations. For eg. d 0 , d 5, d 10are exceptionally
stable.
IV. ELECTRODE POTENTIAL & CHEMICAL REACTIVITY:
➢ The low value for Sc reflects the stability of Sc3+(d0) which has a noble gas
configuration.
➢ The highest value for Zn is due to the removal of an electron from the stable d 10
configuration of Zn2+.
➢ The comparatively high value for Mn shows that Mn2+(d5) is particularly stable,
whereas comparatively low value for Fe shows the extra stability of Fe3+ (d5 ).
➢ The comparatively low value for V is related to the stability of V2+ (half-filled t2g
level)
NOTE : Reducing agent- means undergoes Oxidation- Loses electron
Oxidising agent – means undergoes Reduction- gains electron.
Account for the following:
1. Cr2+ is reducing and Mn3+ is oxidising when both have d 4 configuration.
Cr2+ is reducing as its configuration changes from d 4 to d 3, the d3 having a half-filled
t2g 3 level. On the other hand, the change from Mn3+ to Mn2+ results in the half-filled (d 5)
configuration which has extra stability.
Cr- : [Ar]3d5 4s1 Mn : [Ar]3d5 4s2 Fe : [Ar]3d6 4s2
Cr2+ : [Ar]3d4 Mn3+ : [Ar]3d4 Fe2+ : [Ar]3d6
Cr3+ : [Ar]3d3 ( t2g 3 ) Mn2+ : [Ar]3d5 Fe3+ : [Ar]3d5
2. Which is a stronger reducing agent Cr2+ or Fe2+ and why?
Cr2+ is stronger reducing agent than Fe2+ This can be explained in terms of E°
(M3+/M2+) value. E° (Cr3+/Cr2+) has high negative value (-0.41V) indicating that
Cr2+would change into Cr3+ readily ( t2g3) whereas when Fe 2+ d 6 changes to Fe3+ d 5.
Fe2+ changes from d6 to d5 – stable half- filled d5 configuration

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 Cr2+ Changes from d 4 to d 3 - stable half- filled t2g 3configuration
Half- filled t2g 3 configuration is more stable than d5 configuration.
3. Why is the E° value for the (Mn3+/Mn2+) couple much more positive than that
for (Cr3+/Cr2+) or (Fe3+/Fe2+) Explain.
Much larger third ionisation energy of Mn (where the required change is d 5 to d 4 is
mainly responsible for this. This also explains why the +3 state of Mn is of little
importance.
Cr : [Ar]3d5 4s1 Mn : [Ar]3d5 4s2 Fe : [Ar]3d6 4s2
Cr2+ : [Ar]3d4 Mn3+ : [Ar]3d4 Fe2+ : [Ar]3d6
Cr3+ : [Ar]3d3 ( t2g 3 ) Mn2+ : [Ar]3d5 Fe3+ : [Ar]3d5
4. The E° (M2+/M) value for copper is positive (+0. 34V). What is possibly the
reason for this?
The positive value of E° (M2+/M) for Cu is due to its high enthalpy of atomization and
high value of enthalpies of ionisation (ΔiH°1+ ΔiH°2), that the sum of enthalpies of
sublimation and IE is not balanced by its low hydration enthalpy. Therefore, high energy
is required to transform Cu(s) to Cu2+ (aq).
5. Cu+ ion is not stable in aqueous solutions. (Or)Copper(I) has d10 configuration,
while copper (II) has d9 configuration, still copper (II) is more stable in aqueous
solution than copper(I).
Copper (I) compounds are unstable in aqueous solution and undergo
disproportionation.

6. The d1 configuration is very unstable in ions. Give reason.

The ions in d1 configuration have greater tendency to acquire more stable d0
configuration by losing the one d-electron and act as reducing agent.
GENERAL CHARACTERISTICS OF TRANSITION ELEMENTS:
➢ Transition metals show variable oxidation states.
➢ Transition metal ions are paramagnetic in nature.
➢ Transition metals generally form coloured ions.
➢ Transition metals form complexes.
➢ Transition metals and its compounds act as catalyst.
➢ Transition metals form alloys.
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 ➢ Transition metals form interstitial compounds.
I. OXIDATION STATES:
1. Transition elements show a great variety of oxidation states in its compounds.
Due to the participation of inner (n-1) d- electrons in addition to outer ns- electrons in
bond formation since the energies of (n-1) d- and ns- subshells are almost equal.
2. Name the element of the first -row transition series (3d) which exhibits the
largest no of Oxidation states? Why?
Manganese, it exhibits all the oxidation states from +2 to +7 due to the maximum
number of unpaired electrons.
3. What is the highest oxidation state shown by transition metal in the 3d series?
Manganese (+7)
4. What is the highest oxidation state shown by any transition metal?
+8 (Osmium (Os) and (Ru) ruthenium)
5. Name the element of the first-row transition series (3d) which exhibits +1
oxidation state most frequently and why?
Copper, Because Cu +1 has stable [Ar] 3d10 configuration.
6. Name a transition element which does not exhibit variable Oxidation state.
Scandium (+3)
7. A transition metal exhibits higher oxidation state in oxides and fluorides.
Because fluorine and oxygen are small in size, the most electronegative elements and
best oxidizing element, hence they can oxidise the metal to its highest oxidation states.
8. The highest oxidation state is exhibited in oxoanions of a metal.
The ability of oxygen to stabilise these high oxidation states exceeds that of fluorine
due to the ability of oxygen to form multiple bonds to metals. Eg : The highest Mn
fluoride is MnF4 whereas the highest oxide is Mn2O7.
9. The lowest oxide of transition metal is basic, the highest is amphoteric/acidic.
In the lower oxidation state of the metal, some of the valence electrons of the metal
atom are not involved in bonding. Hence, it can donate electrons and behave as a base. In
the higher oxidation state, valence electrons are involved in bonding and are not available
for donation. Instead, effective nuclear charge is also high. Hence, it can accept electrons
and behave as an acid.
NOTE: Low oxidation states for transition metals are found when a complex
compound has ligands capable of π-acceptor character in addition to the σ-bonding.
For example in metal carbonyls like Ni(CO)4 and Fe(CO)5, the oxidation state of
nickel and iron is zero.

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 11. Why Mn2+ compounds are more stable than Fe2+ towards oxidation to their
+3-oxidation state.
Mn2+ Due to the stable half- filled d5 sub-shell it is not easily oxidised to Mn3+. Fe 2+
(3d6) only after the loss of one electron it will get stable half- filled sub-shell. Hence, Fe2+
is easily oxidised to +3 oxidation state.
12. Classify the following oxides in the increasing order of acidic strength.
Mn2O7, MnO2, Mn3O4, Mn2O3 , MnO
The increasing order of acidic strength of the oxides is
MnO (+2)< Mn3O4 ( +8/3) <Mn2O3 ( +3) < MnO2 ( +4) < Mn2O7 ( +7).
NOTE :
➢ Higher the oxidation state of the metal, higher the acidic strength of the oxides.
➢ As the oxidation number of the metal increases, ionic character decreases.
13. 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.
• Dichromate ion Cr2O7 2-, Oxidation state of Cr is + 6. and its group number 6.
• Permanganate ion, MnO4-Oxidation state of Mn is + 7 and its group number is 7.
14. How is the variability in oxidation states of transition metals different from
that of the non-transition metals? Illustrate with examples.
• In transition elements, the oxidation states differ by one unit (Fe2+and Fe3+; Cu+ and
Cu2+). In non-transition elements, the oxidation states differ by 2 unit, for example, +2
and +4 (Group 16) or +3 and +5 ( Group 15), etc.
• In the p–block ( non-transition element) the lower oxidation states are favoured by
the heavier members (due to inert pair effect). Eg: TlCl is more stable than TlCl 3 . The
opposite is true in the groups of d-block. For example, in group 6, Mo(VI) and W(VI) are
found to be more stable than Cr(VI).
15. How would you account for the increasing oxidising power in the series?
VO2+ < Cr2O7 2- < MnO4 - ?
This is due to the increasing stability of the lower species to which they are reduced.
16. Cobalt (II) is stable in aqueous solution but in the presence of complexing
reagents it is easily oxidised.Why?
Co (III) has greater tendency to form coordination complexes than Co (II). Hence in
the presence of ligands, Co (II) changes to Co (III). i.e. the CFSE more than compensates
the 3rd ionisation enthalpy.
17. What is meant by ‘disproportionation’ of an oxidation state? Give two
examples.

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 When an element in a particular oxidation undergoes oxidation and reduction
simultaneously, it is known as disproportionation. For example, manganese (VI) becomes
unstable relative to manganese (VII) and manganese (IV) in acidic solution.

II. MAGNETIC PROPERTIES:

1. Many of the transition metals and their compounds show paramagnetic
behaviour.Give reason.
Para magnetism arises due to the presence of unpaired electrons in the (n-1) d orbitals
NOTE:
• Greater the number of unpaired electrons, greater is the paramagnetic character and
larger is the magnetic moment.
• Magnetic moment can be calculated by the spin only formula
µ=√𝑛(𝑛 + 2)
2. Calculate the magnetic moment of a divalent ion in aqueous solution if its atomic
number is 25.
M=[Ar]3d5 4s2
M2+=[Ar]3d5
µ= ⬚√𝑛(𝑛 + 2)= √5(5 + 2)=5.92BM
3. Calculate the ‘spin only’ magnetic moment of M2+ (aq) ion (Z = 27).
M 2+ = [Ar] 3d7 -3unpaired electrons. =3.87BM
NOTE:
➢ Diamagnetic substances are repelled by the applied field and all the electrons are
paired.
➢ Paramagnetic substances are weakly attracted by the magnetic field and have
unpaired electrons.
➢ Ferromagnetic substances are strongly attracted by applied field. It is an extreme
form of Para magnetism.
III. FORMATION OF COLOURED IONS:
1. Most of the compounds of transition metals are coloured in the solid form or
solution form. Why?
This is due to the presence of unpaired electron in the (n-1) d subshell. Hence, they
can undergo d-d transition by absorbing light of suitable frequency from the visible
region and emitting complementary colour.
2. Why Zn2+ salts are white while Ni2+ salts are blue?
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 Zn 2+ has completely filled 3d10 orbital while Ni2+ has incompletely filled 3d8 orbitals.
which can undergo d-d transition.
3. Scandium forms no coloured ions, yet it is regarded as a transition element.
Explain why?
Scandium in the ground state has one electron in the 3d subshell. Hence, it is regarded
as a transition element. However, in its common oxidation state of +3, it has no electrons
in 3d subshell (3d0). Hence no d-d transition and does not form coloured ions.
IV. FORMATION OF COMPLEX COMPOUNDS:
Transition metals form a large number of complex compounds. Give reason.
• This is due to the comparatively smaller sizes of the metal ions.
• Due to their high ionic charges.
• Due to the availability of vacant d orbitals for bond formation with ligands.
V. CATALYTIC PROPERTIES:
Transition metals and their compounds are known for their catalytic activity.
(Or) Why does Vanadium pentoxide act as a catalyst?
• Ability of transition metal to adopt multiple oxidation states
• Presence of incompletely filled d- orbitals.
• Large surface of the metals.
Eg : Vanadium(V) oxide (in Contact Process), finely divided iron (in Haber’s
Process), and nickel (in Catalytic Hydrogenation).
VI. FORMATION OF INTERSTITIAL COMPOUNDS:
1. Transition elements form interstitial compounds. Give reason.
Due to the presences of voids of suitable size in which small atoms like H, C or N are
trapped inside the crystal lattices of metals.
2. What are Interstitial Compounds?
Interstitial compounds are those which are formed when small atoms like H, C or N
are trapped inside the crystal.
3. List the characteristics of interstitial compounds.
• Interstitial Compounds have high melting points, higher than those of pure metals.
• They are very hard, some borides approach diamond in hardness.
• They retain metallic conductivity.
• They are chemically inert
VII. ALLOY FORMATION:
1. Transition elements form alloys with other transition metals easily.
The transition metals are quite similar in radii and one metal can substitute the atoms
of other metal in its crystal lattice.
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 2. What are alloys? Give examples.
An alloy is a blend of metals prepared by mixing the components. Alloys may be
homogeneous solid solutions in which the atoms of one metal are distributed randomly
among the atoms of the other.
• • Eg: Brass (copper-zinc) and Bronze (copper-tin).
• • Ferrous alloys: chromium, vanadium, tungsten, molybdenum and manganese
are used for the production of a variety of steels and stainless steel.
THE INNER TRANSITION ELEMENTS ( f BLOCK ELEMENTS)
1. What are inner transition elements? How are they classified? Write their
general electronic configuration.
• Inner transition elements are the elements in which the last electron enters the f-
orbital and are called f-block elements.
• The f-block consists of the two series, lanthanoids (the fourteen elements following
lanthanum) where filling of 4f orbital takes place.
• Actinoids (the fourteen elements following actinium) where filling of 5f orbital takes
place.
2. Electronic configuration is (n-2) f1-14 (n-1) d0-1 ns2
Oxidation state
➢ Common oxidation state +3.
➢ Occasionally +2 and +4 in solution and solid compounds.
➢ The irregularity arises mainly from the extra stability of empty, half-filled or filled
f subshell.
➢ Why Ce(IV) is a good analytical reagent?
It is a strong oxidant reverting to the common +3 state.
➢ Eu2+ is formed by losing the two s electrons and its f 7 configuration accounts for
the formation of this ion. However, Eu2+ is a strong reducing agent changing to the
common +3 state.
➢ Yb2+ which has f 14 configuration is a reductant.
➢ Tb(IV) has half-filled f-orbitals and is an oxidant.
5. General Characteristics:
➢ Many trivalent lanthanoid ions are coloured both in the solid state and in aqueous
solutions. Colour of these ions may be attributed to the presence of unpaired f electrons
( f-f transition).
➢ Neither La3+ nor Lu3+ ion shows any colour (f 0 and f14) but the rest do so.
However, absorption bands are narrow, probably because of the excitation within f level.
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 ➢ The lanthanoid ions other than the f 0 type (La3+ and Ce4+) and the f 14 type (Yb2+
and Lu3+) are all paramagnetic. The Para magnetism rises to maximum in neodymium.
CHEMICAL REACTIONS OF LANTHANOIDS

Uses of Lanthanoids:
Q. What is misch metal. Mention its uses.
Mischmetal which consists of a lanthanoid metal (~ 95%) and iron (~ 5%) and
traces of S, C, Ca and Al is used in Mg-based alloy to produce bullets, shell and
lighter flint.
➢ Mixed oxides of lanthanoids are employed as catalysts in petroleum cracking.
➢ Some individual Ln oxides are used as phosphors in television screens and similar
fluorescing surfaces.
➢ The best single use of the lanthanoids is for the production of alloy steels for plates
and pipes.
ANSWER THE FOLLOWING:
1. Ce (III) can easily be oxidised to Ce (IV). Explain why? (Or) Ce forms a tetra -
positive ion, Ce4+ in solutions.
Ce(III) has 4f1 . It can be easily oxidized because it can readily lose an electron to
acquire the stable 4fs configuration and form Ce(IV).
2. Use Hund’s rule to derive the electronic configuration of Ce3+ ion, and
calculate its magnetic moment on the basis of ‘spin-only’ formula.
Ce= [Xe] 4f1 5d1 6s2 ( n=1 ), μ = √1(1+2) =√3 =1.72BM
3. Actinoid contraction is greater from element to element than lanthanoid
contraction.
In actinoids, 5f orbitals are filled. The actinoid contraction is greater from element to
element due to poor shielding of 5f electrons than by 4f electrons.
4. Actinoids shows a wide range of oxidation states than lanthanoids.
Due to the comparable energies of 5f, 6d and 7s subshells, all can take part in bond
formation.
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 5. The chemistry of the actinoid elements is not so smooth as that of the
Lanthanoids.
Actinoids shows a large number of oxidation states and actinoids are radioactive.
6. Name a member of the lanthanoid series which is well known to exhibit +4
oxidation state.
Cerium (Z = 58)
Potassium dichromate K2Cr2O7
Describe the preparation of potassium dichromate from iron chromite ore.
Dichromates are generally prepared from chromate, which in turn are obtained by the
fusion of chromite ore (FeCr2O4) with sodium or potassium carbonate in free access of
air.
4 FeCr2O4 + 8 Na2CO3 + 7 O2 8 Na2CrO4 + 2 Fe2O3 + 8 CO2
The yellow solution of sodium chromate is filtered and acidified with H2SO4 to give a
solution from which orange sodium dichromate, Na2Cr2O7. 2H2O can be crystallised.
2Na2CrO4 + 2 H+ Na2Cr2O7 + 2 Na+ + H2O
Sodium dichromate is more soluble than potassium dichromate. The latter is therefore,
prepared by treating the solution of sodium dichromate with KCl.
Na2Cr2O7 + 2 KCl K2Cr2O7 + 2 NaCl
Orange crystals of potassium dichromate crystallise out.
The chromates and dichromates are interconvertible in aqueous solution depending
upon pH of the solution.
Q. What is the effect of increasing pH on a solution of potassium dichromate?
On increasing the pH, i.e., on making the solution alkaline, dichromate ions (orange
coloured) are converted into chromate ions and thus, the solution turns yellow.

Structure of Chromate and dichromate ions

The chromate ion is tetrahedral whereas the dichromate ion consists of two tetrahedra
sharing one corner with Cr–O–Cr bond angle of 126°.
Chemical properties
Sodium and potassium dichromates are strong oxidising agents; Potassium dichromate
is used as a primary standard in volumetric analysis. In acidic solution, its oxidising
action can be represented as follows:
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 ------------(1)
Acidified potassium dichromate will oxidise iodides to iodine,
2 I– I2 + 2 e– ---------(2) x3
6 I– 3I2 + 6 e– ---------(3)
Equation(1) +equation(3)
Cr2O72-+14H++ 6 I– 2Cr3++7H20+3I2
sulphides to sulphur.
---------(1)
+ –
H2S 2H +S + e --------(2)x3
3 H2S 6H+ + 3S + 6e– --------(3)
Equation(1) +equation(3)
Cr2O72-+8H++3 H2S 2Cr3++7H20+3S
tin(II) to tin(IV)
Cr2O72-+14H++ 6 e- 2Cr3++7H20-------(1)
Sn2+ Sn4+ + 2 e–---------(2)x3
3 Sn2+ 3Sn4+ + 6 e–---------(3)
Equation(1) +equation(3)
Cr2O72-+14H++ 3 Sn2+ 3Sn4++ 2Cr3++7H20
4. Iron(II) salts to iron(III)
Cr2O72-+14H++ 6 e- 2Cr3++7H20-------(1)
Fe2+ Fe3+ + e–-----(2)x6
6 Fe2+ 6Fe3+ + 6 e–-----(3)
Equation(1) +equation(3)
Cr2O72-+14H++ 6 Fe2+ 6Fe3++ 2Cr3++7H20
Potassium permanganate KMnO4
KMnO4 is prepared by fusion of MnO2 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.
2MnO2 + 4KOH + O2 2K2MnO4 + 2H2O
2–
3MnO4 + 4H +
2MnO4– + MnO2 + 2H2O
Commercially it is prepared by the alkaline oxidative fusion of MnO2 followed by the
electrolytic oxidation of manganate (Vl).

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 Properties
KMnO4 forms dark purple (almost black) crystals which are isostructural with those of
KClO4.
Action of heat
Q. What happens when KMnO4 is heated at 513K?
when heated it decomposes at 513 K

Properties
The manganate and permanganate ions are tetrahedral; the p- 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 permanganate is diamagnetic due
to the absence of unpaired electron.
Q. Draw the structure of MnO4- and Mn2O72-

Chemical reactions
Oxidising action
(i) It oxidises KI to I2
MnO4– + 8H+ + 5e– Mn2+ + 4H2O -------(1)x2
2MnO4– + 16H+ + 10e– 2Mn2+ + 8H2O
2 I– I2 + 2 e– ---------(2) x5
10I– 5I2 + 10e– ---------(3)
Eqn(1) +Eqn(3)
2MnO4– + 16H++10I– 2Mn2+ + 8H2O + 5I2
(ii) Fe2+ ion(green)is converted to Fe3+ (yellow)
Fe2+ Fe3++ e–-----(2)x5
5 Fe2+ 5 Fe3++5 e– ------(3)
MnO4– + 8H+ + 5e– Mn2+ + 4H2O -------(1)
Eqn(1) +Eqn(3)
5 Fe2++MnO4– + 8H+ 5 Fe3++ Mn2+ + 4H2O
(iii) Oxalate ion or oxalic acid is oxidized at 333K .
MnO4– + 8H+ + 5e– Mn2+ + 4H2O -------(1)x2
2MnO4– + 16H+ + 8e– 2Mn2+ + 8H2O -------(2)
C2O42- 5CO2+ 2e- ---- (3)x5
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 5C2O42- 5CO2+ 5e-+10e-
Eqn(2) +Eqn(3)
5C2O42-+ 2MnO4– + 16H+ 2Mn2+ +5CO2+ 8H2O
(iv) H2S is oxidised, S being precipitated.

USES
• Used as an oxidising agent.
• Used for the bleaching of wool,cotton.silk and other textile fibres.
• For the decolourisation of oils.
Q Compare the chemistry of actinoids with that of lanthanoids with special
reference to
(i) electronic configuration (ii) oxidation states
(iii) atomic and ionic sizes (iv) chemical reactivity.
OR
Give three points of difference between lanthanoids and actinoids.
Property Lanthanoids Actinoids
Electronic The general electronic The general electronic
configuration configuration of lanthanoids is configuration of actinoids is
[Xe] 4f 1–14 5d 0 –1 6s2 [Rn] 5f 1–14 6d 0 –1 7s2
Lanthanoids belong to 4f-series Actinoids belong to 5f-series.

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 oxidation Lanthanoids show limited Actinoids show a large number of
states oxidation states (+2, +3, +4), out of oxidation
which, +3 is most common. This is states(+3,+4,+5,+7)because of
because of a large energy gap small energy gap between 5f, 6d
between 4f, 5d and 6s subshells. and 7s subshells.

atomic and Both shows decrease in size of In actinoids, it is called actinoid

ionic sizes their atoms or ions in +3 oxidation contraction. However, the
state. In lanthanoids, the decrease is contraction is greater from element
called lanthanoid contraction. to element in actinoids due to
poorer shielding by 5f-electrons.
chemical These are less reactive metals. These are highly reactive metals
reactivity
Q. In the following ions:
Mn3+, V3+, Cr3+, Ti4+
(Atomic no: Mn = 25, V = 23, Cr = 24, Ti = 22)
(i) Which ion is most stable in an aqueous solution?
(ii) Which ion is the strongest oxidizing agent?
(iii) Which ion is colourless?
(iv) Which ion has the highest number of unpaired electrons?
(i) Cr3+ because of half- filled t2g level.
(ii) Mn3+, as the change from Mn3+ to Mn2+ results in stable half filled (d 5)
configuration.
(iii) Ti4+, as Ti4+ has empty d-orbitals therefore d-d transition cannot occur in Ti4+.
(iv) Mn3+ (3d 44s0). It has 4 unpaired electrons.

Q. Eo values of Mn, Ni and Zn are more negative than expected. Give reason.
Negative Eo values for Mn2+ and Zn2+ are related to stabilities of half-filled and fully filled
configurations, respectively. But for Ni2+, Eo value is related to the highest negative enthalpy of
hydration.
Q. (i) The elements of 3d transition series are given as:
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 Sc,Ti, V, Cr, Mn, Fe, Co, Ni, Cu and Zn
Answer the following:
(a) Which element has the highest m.p. and why?
(b) Which element is a strong oxidising agent in +3 oxidation state and why?
(c) Which element is soft and why?
a) Cr, the highest melting point of Cr due to greater number of electrons (5) from 3d in
addition to 4s electrons in interatomic metallic bonding.
(b) Mn, because the change from Mn3+ (d 4) to Mn2+ (d 5) results in the half- filled
configuration which has extra stability.
(c) Zn, in Zn (3d 10 4s 2) all the electrons present in d-orbitals are paired and hence metallic
bonds present in it are weak. That is why, it is soft.
Q. (a) In the titration of FeSO4 with KMnO4 in the acidic medium, why is dil. H2SO4
used instead of dil. HCl?
(a) Dil. H2SO4 is an oxidising agent and oxidises FeSO4 to Fe2(SO4)3. Dil. HCl is a reducing
agent and liberates chlorine on reacting with KMnO4 solution. Hence, the part of the oxygen
produced from KMnO4 is used up by HCl.
(b) Ce4+ is used as an oxidising agent in volumetric analysis. Give reason.
Ce4+ has the tendency to attain +3 oxidation state which is more stable and so it is used as an
oxidising agent in volumetric analysis.
Q. Predict which of the following will be coloured in aqueous solution?
Ti3+,V3+,Cu+,Sc3+,Mn2+,Fe3+,Co2+ . Give reasons for each.
An ion is coloured when it has one or more unpaired electrons. Thus, Ti3+, V3+ ,Mn2+, Fe3+
and Co2+ are coloured, due to the presence of unpaired electrons and d-d transitions. Cu+ and
Sc3+ are colourless.
Q.Calculate the number of unpaired electrons in the following gaseous ions:
(i) Mn3+, (ii) Cr3+, (iii) V3+ and (iv) Ti3+.
Which one of these is the most stable in aqueous solution?
Ans. (i) Mn3+ = 3d 4 = 4 unpaired electrons (ii) Cr3+ = 3d 3 = 3 electrons
(iii) V3+ = 3d 2 = 2 electrons (iv) Ti3+ = 3d 1 = 1 electron.
Q. Which series amongst the first, second and third series of transition elements have
the highest first ionization enthalpy and why?

Third series has the highest first ionization energy due to poorest shielding effect of
the fully filled 4f subshell.
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