The d- and f- Block Elements

 The d-block of the periodic table contains the elements of the groups 3-12 in which the d orbitals
are progressively filled in each of the four long periods. -transition metals
 The f-block consists of elements in which 4 f and 5 f orbitals are progressively filled. -inner
transition metals
 According to IUPAC, transition metals are defined as metals which have incomplete d subshell
either in neutral atom or in their ions.
 Zinc, cadmium and mercury of group 12 have full d10 configuration in their ground state as well as
in their common oxidation states and hence, are not regarded as transition metals.
THE TRANSITION ELEMENTS (d-BLOCK)

Position in the Periodic Table: The d–block occupies the large middle section of the periodic table
flanked between s– and p– blocks in the periodic table. 3d, 4d, 5d and 6d
electronic configuration: In general the electronic configuration of outer orbitals of d–block elements
is (n-1)d1-10ns1-2.
The electronic configurations of outer orbitals of Zn, Cd, Hg are represented by
the general formula (n-1)d10ns2. The orbitals in these elements are completely filled in
the ground state as well as in their common oxidation states[+2]. Therefore, they are
not regarded as transition elements.
On what ground can you say that scandium (Z = 21) is a transition element but zinc (Z = 30) is not?
Silver atom has completely filled d orbitals (4d10) in its ground state. How can you say that it is a
transition element?
Physical Properties: All the transition elements display typical metallic properties such as high tensile
strength, ductility, malleability, high thermal and electrical conductivity and metallic lustre.
 The transition metals (with the exception of Zn, Cd and Hg) are very hard and have low
volatility.
 Their melting and boiling points are high.
The high melting points of these metals are attributed to the involvement of greater
number of electrons from (n-1)d involved in dπ-dπ metallic bonds, in addition to the ns
electrons in the interatomic metallic bonding.
  They have high enthalpies of atomisation.

 The metals of the second and third series have greater enthalpies of atomisation than the
corresponding elements of the first series;
Variation in Atomic and Ionic Sizes of Transition Metals:

 Ions of the same charge in a given series 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. It may be recalled that the shielding effect of a d electron is not that effective, hence
the net electrostatic attraction between the nuclear charge and the outermost electron
increases and the ionic radius decreases.
 The same trend is observed in the atomic radii of a given series.
 The radii of the third (5d) series are virtually the same as those of the corresponding members
of the second series.
This phenomenon is associated with the intervention of the 4f orbitals which must be filled
before the 5d series of elements begin. 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. The net result of the
lanthanoid contraction is that the second and the third d series exhibit similar radii.
 The factor responsible for the lanthanoid contraction is the imperfect shielding of one electron
by another in the same set of orbitals. However, the shielding of one 4f electron by another is
less than that of one d electron by another, and as the nuclear charge increases along the series,
there is fairly regular decrease in the size of the entire 4f n orbitals.[ Lanthanoid contraction]
 The decrease in metallic radius coupled with increase in atomic mass results in a general
increase in the density of these elements.
Why do the transition elements exhibit higher enthalpies of atomisation?
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.
Why?
Ionisation Enthalpies:
There is an increase in ionisation enthalpy along each series of the transition elements from left to right
due to an increase in nuclear charge which accompanies the filling of the inner d orbitals.
 3d electrons shield the 4s electrons from the increasing nuclear charge somewhat more
effectively than the outer shell electrons can shield one another. Therefore, the atomic radii
decrease less rapidly. Thus, ionization energies increase only slightly along the 3d series.
 The three terms responsible for the value of ionisation enthalpy are attraction of each electron
towards nucleus, repulsion between the electrons and the exchange energy.
  Exchange energy is responsible for the stabilisation of energy state. Exchange energy is
approximately proportional to the total number of possible pairs of parallel spins in the
degenerate orbitals. When several electrons occupy a set of degenerate orbitals, the lowest
energy state corresponds to the maximum possible extent of single occupation of orbital and
parallel spins (Hunds rule). The loss of exchange energy increases the stability. As the stability
increases, the ionisation becomes more difficult.
Eg: 1. Mn+ has 3d54s1 configuration and configuration of Cr+ is d5, therefore, ionisation
enthalpy
of Mn+ is lower than Cr+.
2. Fe2+ has d6 configuration and Mn2+ has 3d5 configuration. Hence, ionisation enthalpy of
Fe2+ is lower than the Mn2+.
 The lowest common oxidation state of these metals is +2.
 The second ionisation enthalpy shows unusually high values for Cr and Cu where M+ ions
have the d5 and d10 configurations respectively.
 The value for Zn is correspondingly low as the ionisation causes the removal of 4s electrons
which results in the formation of stable d10 configuration.
OXIDATION STATES:
 Transition elements show great variety of oxidation states in their compounds.
 The variability of oxidation states, a characteristic of transition elements, arises out of
incomplete filling of d orbitals
 The elements which give the greatest number of oxidation states occur in or near the middle of
the series. Example; Manganese exhibits all the oxidation states from +2 to +7.
 For Transition elements , lower oxidation state is favoured by lighter elements.
Example; in group 6, Mo(VI) and W(VI) are found to be more stable than Cr(VI).
Thus Cr(VI) in the form of dichromate in acidic medium is a strong oxidising
agent, whereas MoO3 and WO3 are not.

Name a transition element which does not exhibit variable oxidation states.
Which of the 3d series of the transition metals exhibits the largest number of oxidation states and why?
Why is Cr2+ reducing and Mn3+ oxidising when both have d4 configuration?
Magnetic Properties: Compounds of transition metal show varieties of magnetic properties.
 Many of the transition metal ions are paramagnetic.
 Paramagnetism arises from the presence of unpaired electrons.
 Each electron having a magnetic moment associated with its spin angular momentum and orbital
angular momentum.
The magnetic moment is determined by the number of unpaired electrons and is calculated by using the
‘spin-only’ formula, i.e.,
µ nn 2
where n is the number of unpaired electrons and μ is the magnetic moment in units of Bohr magneton
(BM).
A single unpaired electron has a magnetic moment of 1.73 Bohr magnetons (BM).

Ni+2 3d8
Calculate the ‘spin only’ magnetic moment of M2+(aq) ion (Z = 27), (Z = 25), (Z = 29),
1. (Z = 27) Electronic Confi. M+2  1s2, 2s2, 2p6, 3s2, 3p6, 3d7 3 unpaired e- 3.8BM
2. (Z = 25) Electronic Confi. M+2  1s2, 2s2, 2p6, 3s2, 3p6, 3d5 5 unpaired e- 5.8BM
3. (Z = 29) Electronic Confi. M+2  1s2, 2s2, 2p6, 3s2, 3p6, 3d9 1 unpaired e- 1.73BM
Alloy Formation: Alloys may be homogeneous solid solutions in which the atoms of one metal are
distributed randomly among the atoms of the other. Such alloys are formed by atoms with metallic radii
that are within about 15 percent of each other. Because of similar radii and other characteristics
of transition metals, alloys are readily formed by these metals.
Some Important Compounds of Transition Elements
1. Potassium dichromate K2Cr2O7 :
Step I 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. The reaction with
sodium carbonate occurs as follows:
4 FeCr2O4 + 8 Na2CO3 + 7 O2 8 Na2CrO4 + 2 Fe2O3 + 8 CO2
Step II The yellow solution of sodium chromate is filtered and acidified with sulphuric acid to give a
solution from which orange sodium dichromate, Na2Cr2O7. 2H2O can be crystallised.
2Na2CrO4 + 2 H+ Na2Cr2O7 + 2 Na+ + H2O
Step III Sodium dichromate is more soluble than potassium dichromate. The latter is therefore,
prepared by treating the solution of sodium dichromate with potassium chloride.
Na2Cr2O7 + 2 KCl K2Cr2O7 + 2 NaCl
Orange crystals of potassium dichromate crystallise out.
Properties:
 The chromates and dichromates are interconvertible in aqueous solution depending upon pH of
the solution. The oxidation state of chromium in chromate and dichromate is the same.
CrO42– + 2H+ Cr2O72– + H2O
Cr2O72– + 2 OH- 2 CrO42– + H2O
 The chromate ion is tetrahedral whereas 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.
Cr2O72– + 14H+ + 6e– 2Cr3+ + 7H2O (EV= 1.33V)
6 I– 3I2 + 6 e– (iodide ions  Iodine)
3 Sn2+ 3Sn4+ + 6 e–
3 H2S 6H+ + 3S + 6e–
6 Fe2+ 6Fe3+ + 6 e–

Q. Write the balanced chemical reaction for the following:

a) Ferrous sulphate is treated with acidified Potassium dichromate K2Cr2O7
Ans: Red. half reaction - Cr2O7 + 14H + 6e– 2Cr + 7H2O
2– + 3+

Ox. half reaction - 6 Fe2+ 6Fe3+ + 6 e–

Cr2O72– + 14 H+ + 6 Fe2+ 2 Cr3+ + 6 Fe3+ + 7 H2O
b)NaI is treated with acidified Potassium dichromate K2Cr2O7
c) Stannous Chloride is treated with acidified Potassium dichromate K2Cr2O7
d) H2S is passed through acidified Potassium dichromate K2Cr2O7
2. Potassium permanganate KMnO4
a) Potassium permanganate is prepared by fusion of Pyrolusite(MnO2) with an alkali metal
hydroxide and an oxidising agent like KNO3. This produces the dark green K2MnO4 which
disproportionates in a neutral or acidic solution to give permanganate.
2MnO2 + 4KOH + O2 2K2MnO4 + 2H2O
3MnO42– + 4H+ 2MnO4– + MnO2 + 2H2O
b) In the laboratory, a manganese (II) ion salt is oxidised by peroxodisulphate to permanganate.
2Mn2+ + 5S2O82– + 8H2O 2MnO4– + 10SO42– + 16H+
c) Commercially it is prepared by the alkaline oxidative fusion of MnO2 followed by the electrolytic
oxidation of manganate (Vl).
Fused with KOH, oxidised
with air or KNO3 2
2-
MnO2 MnO4
manganate ion
 Electrolytic oxidation in
alkaline solution
2- -
MnO4 MnO4
manganate permanganate ion

Properties:
1. Potassium permanganate forms dark purple (almost black) crystals.
2. The salt is not very soluble in water (6.4 g/100 g of water at 293 K),
3. when heated it decomposes at 513 K.
2KMnO4 K2MnO4 + MnO2 + O2
4.Its diamagnetism along with temperature-dependent weak paramagnetism.
5. The manganate and permanganate ions are tetrahedral; the - 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.
6. Acidified permanganate solution oxidises -
a)oxalates to carbon dioxide,
b)iron(II) to iron(III), nitrites to nitrates and iodides to free iodine.
Red. half reaction -
Acidic medium- MnO4– + 8H+ + 5e– Mn2+ + 4H2O
Basic medium- MnO4– +2H2O + 3e– MnO2 + 4OH-
Ox. half reaction -
1. 5 COO–
COO–  10CO2 + 10e–
2. 5 Fe2+ 5 Fe3+ + 5e–
3. 5NO2– + 5H2O 5NO3– + 10H+ + 10 e–
4. 10I– 5I2 + 10e–
Q. Write the balanced chemical reaction for the following:
a) Ferrous sulphate is treated with acidified Potassium permanganate
Ans: Red. half reaction -
Ox. half reaction - Fe2+ Fe3+ + e–

b)NaI is treated with acidified Potassium permanganate

c) NaNO2 is treated with acidified Potassium permanganate
d) Oxalic acid is treated with acidified Potassium permanganate
e) Hydrogen sulphide is passed through acidified Potassium permanganate
f) Sodium sulphite is treated with acidified Potassium permanganate
Q. Write the balanced chemical reaction for the following:
a) KI solution is treated with alkaline Potassium permanganate
b) Sodium Thiosulphate is treated with alkaline Potassium permanganate

OXIDATION STATES:
 Transition elements show great variety of oxidation states in their compounds.
 The variability of oxidation states, a characteristic of transition elements, arises out of
incomplete filling of d orbitals
 The elements which give the greatest number of oxidation states occur in or near the middle of
the series. Example; Manganese exhibits all the oxidation states from +2 to +7.
 For Transition elements , lower oxidation state is favoured by lighter elements.
Example; in group 6, Mo(VI) and W(VI) are found to be more stable than Cr(VI).
Thus Cr(VI) in the form of dichromate in acidic medium is a strong oxidising
agent, whereas MoO3 and WO3 are not.

Name a transition element which does not exhibit variable oxidation states.
Which of the 3d series of the transition metals exhibits the largest number of oxidation states and why?
Why is Cr2+ reducing and Mn3+ oxidising when both have d4 configuration?
What is meant by ‘disproportionation’ of an oxidation state? Give an example.
When a particular oxidation state becomes less stable relative to other oxidation states, then it changes
to one lower and one higher state, it is said to undergo disproportionation. For example, manganese (VI)
becomes unstable relative to manganese(VII) andmanganese (IV) in acidic solution.
3 MnVIO4 2– + 4 H+ 2 MnVIIO–4 + MnIVO2 + 2H2O
Trends in the M2+/M Standard Electrode Potentials:
 The thermochemical parameters related to the transformation of the solid metal atoms to M2+
ions in solution are, aH0(M), iH10 , 1H20 hydH0(M )
2+
+2
M(s)  M (aq)
 The general trend towards less negative E0 values across the series is related to the general
increase in the sum of the first and second ionisation enthalpies.
 note that the E0values for Mn, Ni and Zn are more negative than expected from the general
trend. Where as the stabilities of half-filled d subshell (d5) in Mn2+ and completely filled d subshell
(d10) in zinc(Zn+2)are related to their E0 values; for nickel(Ni+2), E0 value is related to the highest
negative enthalpy of hydration.
 The highest oxidation number in the oxides coincides with the group number. But group-8
onward this does not hold good.
 The ability of oxygen to stabilise the highest oxidation state is demonstrated in the oxides. This is
due to high electronegativity of Oxygen.
 The ability of oxygen to stabilise these high oxidation states exceeds that of fluorine. Thus the
highest Mn fluoride is MnF4 whereas the highest oxide is Mn2O7.
 The ability of oxygen to form multiple bonds to metals explains its superiority.

The E0(M2+/M) value for copper is positive (+0.34V). What is possible reason for this?
(Hint: consider its high aH0and low hydH0)
The unique behaviour of Cu,
 having a positive E0, accounts for its inability to liberate H2 from acids.
Only oxidising acids (nitric and hot concentrated sulphuric) react with Cu, the acids being
reduced.
 The high energy to transform Cu(s) to Cu2+(aq) is not balanced by its hydration enthalpy.
 Many copper (I) compounds are unstable in aqueous solution and undergo disproportionation.
2Cu+ Cu2+ + Cu
The stability of Cu2+ (aq) rather than Cu+(aq) is due to the much more negative hydH0of Cu2+ (aq)
than Cu+, which more than compensates for the second ionisation enthalpy of Cu.
 Cu2+ oxidises I– to I2
2Cu+2 + 4I-  Cu2I2(s) + I2
Trends in the M3+/M2+ Standard Electrode Potentials
low value will favour [M+2 M+3 ]
high value will favour [M+3  M+2 ]
The low value of E0(M3+/M2+) for Sc reflects the stability of Sc3+ which has a noble gas configuration d0.
The highest value of E0(M3+/M2+) for Zn is due to the removal of an electron from the stable d10
configuration of Zn2+.
The comparatively high value of E0(M3+/M2+) for Mn shows that Mn2+(d5) is particularly stable.
Comparatively low value of E0(M3+/M2+) for Fe shows the extra stability of Fe3+ (d5).
The comparatively low value of E0(M3+/M2+) for V is related to the stability of V2+ due to half-filled t2g level.
An examination of the E0values for the redox couple M3+/M2+ shows that,
Mn3+ and Co3+ ions are the strongest oxidising agents in aqueous solutions.
The ions Ti2+, V2+ and Cr2+ are strong reducing agents and will liberate hydrogen from a dilute
acid, e.g.,
2 Cr2+(aq) + 2 H+(aq) 2 Cr3+(aq) + H2(g)
Q. Write the balanced chemical reaction for the following:
a) Ferrous sulphate is treated with acidified Potassium permanganate
 Ans: Red. half reaction - MnO4 + 8H + 5e– Mn + 4H2O
– + 2+

Ox. half reaction - Fe2+ Fe3+ + e–

b)NaI is treated with acidified Potassium permanganate

c) NaNO2 is treated with acidified Potassium permanganate
d) Oxalic acid is treated with acidified Potassium permanganate
e) Hydrogen sulphide is passed through acidified Potassium permanganate
f) Sodium sulphite is treated with acidified Potassium permanganate
Q. Write the balanced chemical reaction for the following:
a) KI solution is treated with alkaline Potassium permanganate
b) Sodium Thiosulphate is treated with alkaline Potassium permanganate
c)Manganous salt is oxidised to MnO2; the presence of zinc sulphate
or zinc oxide catalyses the oxidation:
2MnO4– + 3Mn2+ + 2H2O ——> 5MnO2 + 4H+
Note:
 Permanganate titrations in presence of hydrochloric acid are unsatisfactory since hydrochloric
acid is oxidised to chlorine.
 Permanganate titrations in presence of Nitric acid are unsatisfactory since Nitric acid also acts as
an oxidising agent.

Red. Half Reaction MnO4– + 8H+ + 5e– Mn2+ + 4H2O ]x2

Ox. Half Reaction 10 Cl– 5Cl2 + 10e–
Overall reaction

THE INNER TRANSITION ELEMENTS ( f-BLOCK)

The f-block consists of the two series, lanthanoids (the fourteen elements following lanthanum) and
actinoids (the fourteen elements following actinium).

S.No. Property Lanthanoids Actinoids

1-14 1 2 -14 2
1 Electronic Confi. 4f 5d0- 6s 5f0 6d0-27s
2 Atomic and The overall decrease in atomic and ionic radii There is a gradual decrease
ionic radii from lanthanum to lutetium (the lanthanoid in the size of atoms or M3+
contraction), is attributed to the imperfect ions across the
shielding of one electron Series, referred to as the
by another in the same sub-shell. actinoid contraction. The
contraction is, however,
greater from element to
element in this series
resulting from poor shielding
by 5f electrons.
3 OxidationStates 1.Common Ox. State - +3 There is a greater range of
2.However, occasionally +2 and +4. This oxidation states, which is in
 irregularity (as in ionisation part attributed to the fact
enthalpies) arises mainly from the extra that the 5f, 6d and 7s levels
stability of empty, half-filled are of comparable energies.
or filled f subshell. The maximum oxidation
Ex. 1. CeIV is favoured by its state increases from +4 in Th
noble gas configuration(f0). to +5, +6 and +7respectively
2. Eu2+ is formed with f 7 Confi. in Pa, U and Np.
3. Yb2+ which has f 14 Confi.
4. TbIV has half-filled f-orbitals.
Give reason:
1. CeIV is a strong oxidant.
2. Eu2+ is a strong reducing agent.
3. Yb2+ is a reductant.
4. TbIV is an oxidant.
4. Chemical 1.The actinoids are highly
Properties reactive metals, especially
when finely divided.
2.The action of boiling water
on them, gives a mixture of
oxide and hydride.
3.Combination with most
non metals takes place at
moderate temperatures.
4.Hydrochloric acid attacks
all metals but most are
slightly affected by nitric
acid owing to the formation
of protective oxide layers.
5. Alkalies have no action.