8) The d- and f-Block Elements

d -Block elements: The elements lying in the middle of periodic table (between s
and p block) belonging to groups 3 to 12; period 4th to 7th are known as d – block
elements or transition metals.
Their general electronic configuration is (n-1)d1-10 ns 1-2 where (n – 1) stands for
inner d orbital which can have 1 to 10 electrons and ns 1-2 outer orbital which can
have 1 to 2 electrons.
The d-orbitals of the energy level in the atoms receive electrons giving rise to the
three rows of the transition metals- 3d, 4d and 5d while the fourth row of 6d is still
incomplete.
Electronic configuration of Cr has 3d54s1 instead of 3d44s2; the energy gap between
the two sets (3d and 4s) of orbital's is small to prevent the electron entering the 3d
orbital's. Similarly in Cu the configuration is 3d104s1 and not 3d94s2.
Transition element: A transition element is defined as the one which has
incompletely filled d orbitals in its ground state or in any one of its oxidation states.
Zinc (Zn), Cadmium (Cd) and Mercury (Hg) of group 12 have completely filled d10
configuration in their ground state as well as common oxidation state. Hence these
are not regarded as transition metals. i.e. General formula is (n-1)d10 ns2.
Various precious metals such as silver, gold and platinum and industrially important
metals like Iron, Copper and Titanium form important part of the transition metals.
Four transition series:
a. 3d – transition series: The transition elements with Scandium 'Sc' (Z= 21) to
Zinc 'Zn' (Z= 30) and having incomplete 3d orbital's is called the first transition
series. {3d & 4s orbital}
b. 4d – transition series: It consists of elements with Yttrium 'Y' (Z= 39) to
Cadmium 'Cd' (Z= 48) and having incomplete 4d orbitals. It is called second
transition series. {4d & 5s orbital}
c. 5d – transition series: It consists of elements with Lanthanum 'La' (Z= 57), to
Mercury 'Hg' (Z= 80) omitting Ce to Lu, Hafnium 'Hf' (Z= 72) having incomplete 5d
orbital's. It is called third transition series. {5d & 6s orbital}
d. 6d – transition series: It consists of elements with Actinium 'Ac' (Z= 89),
'Rf' (Z= 104) to 'Uub' (Z= 112) having incomplete 6d orbital's. It is called fourth
transition series. {6d & 7s orbital}
The Transition Elements (d-block)
General Characteristics of transition elements:
I) Physical Properties:-
a. Metallic character:-
i) All transition elements are metallic in nature, i.e. they have strong metallic bonds
due to presence of unpaired electrons. The low ionization energy and presence
of one or two electron in the outermost energy level (ns 1 or ns2) gives rise to
properties like high density, high enthalpies of atomization, high tensile strength,
malleability, ductility, hardness, lustre, high thermal and electrical conductivity
and high melting and boiling points.

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ii) The hardness of these metals is due to the presence of strong bonding due to
overlap of unpaired electrons between different metal atoms. Therefore, they
exhibit high enthalpy of atomization. Enthalpy of atomization is maximum in the
middle indicates one unpaired electron is particularly favorable for strong atomic
interaction.
iii) Cr, Mo and W have maximum number of unpaired electrons and are hard metals.
iv) Zn, Cd and Hg have no unpaired electrons and hence are soft metals.
v) Greater the number of unpaired electrons in the outermost d orbital's, greater is
the overlap between different metal atoms and greater is the strength of the
bonds.
vi) Except for Mercury (Hg), all the transition metals have typical metallic structure
(hcp, ccp, bcc)

b. Melting and boiling points:-

i) The transition metals have high m.p. & b.p (except Zn, Cd and Hg) due to
involvement of greater number of electrons from (n-1)d in addition to ns electrons
in interatomic metallic bonding.
ii) Strong metallic bonds between the atoms of these elements rise to a maximum
value and then decrease with increase in atomic number.
iii) The strength of bonding depends on the number of outer most electrons. Greater
is the number of valance electrons, stronger is the metallic bonding and m.p. is
high.
iv) Manganese (Mn) and Technetium (Tc) have low m.p. & b.p since they have half
filled d - orbitals where electrons are held tightly by nucleus so delocalisation is
less and metallic bond is weak.
v) The metallic strength increases up to the middle till d5 configuration and then
decreases with the decrease in availability of unpaired d- electrons (from Fe
onwards). Therefore, m.p. decrease after the middle because of increase an
pairing of electrons.

c. Variation in Atomic and Ionic Sizes:-

i) The atomic radii decrease from Sc to Cr because of the effective nuclear charge
increases.
ii) 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 repulsion increases.
iii) The atomic radii of elements of a particular series decrease with increase in
atomic number but this decrease in atomic radii become small after midway
because of increase in atomic no., the nuclear charge goes on increasing, the
shielding effect is small so that net electrostatic attraction between the nuclear
charge and outermost electrons increases. Consequently atomic radius
decreases.
iv) As the no. of d-electrons increase the screening effect increases. This
neutralizes the effect of increased nuclear charge due increase in atomic number
and consequently atomic radius remains almost unchanged after chromium.
v) At the end of each period, there is slight increase in atomic number because of
increased electron-electron repulsions between the added electrons in the same
orbital which exceeds the attractive forces due to increased nuclear charge.
Therefore, electron cloud expands and size increases.

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vi) The atomic radii increases while going down the group as atomic number
increases.
vii) The atomic radii of second transition series is larger than that of first transition
series because of increase in no. of outermost shell.
viii) The third transition series have nearly the same radii as metals of second
transition series because of lanthanide contraction. This is associated with the
interventions of 4f- orbital's which are filled before 5d-series. 4f- orbital have poor
screening effect which results in regular decrease in atomic radii which
compensates the expected increase in atomic size with increase in atomic no.

Ionic Radii: The ionic radii is smaller

than that of elements belonging to the
same period. Since metals exhibit
different oxidation states, radii of ions
also differ.
The ionic radii decrease with increase
in nuclear charge. i.e. Ionic size of M3+
cation are smaller than M2+ cation.

d. Density:-
i) All metals have high density. Within a period, the densities vary inversely with
atomic radii, ie. densities increase along a period and descends down the group
as atomic size decreases and atomic mass increases.
ii) The atomic volumes of transition elements are low because electrons are added
in (n- 1)d sub shell and not in ns subshell . Therefore, increased nuclear charge
is partly screened by the d-electrons and outer electrons are strongly attracted by
the nucleus. Hence, electrons are added in inner orbital as a result densities of
transition metals are high.

e. Ionisation enthalpy:-
i) The ionization enthalpies of d-block elements are higher than those of p-block
elements and increase along a series due to the effect of increasing nuclear
charge which would tend to attract outer electron with greater force.
ii) With the increase in electrons in d-sub shell the outer electrons are shielded
more. Thus, effect of increased nuclear charge is opposed by additional
screening effect of the nucleus and ionization enthalpy increases slowly.
iii) The irregular trend in first I.E. of first transition series elements is due to the fact
that removal of one electron alters the relatives energies of 4s and 3d orbital's.
iv) Unipositive ions have dn configuration with no 4s electron. Therefore, there is
reorganization energy which gains in exchange energy due to increase in no. of
electrons in dn configuration.

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Some exceptions observed in ionization enthalpies are:-
a) Cr and Cu have high I.E due to their half filled (d5) and completely (d10) electronic
configuration.
b) The value of second I.E. for zinc is low because ionization involves removal of an
electron resulting in stable 3d10 configuration.
c) The trend in third I.E. shows high value for Mn+2 and Zn+2 because of stable 3d5
and 3d10 electronic configuration. Similarly, I.E for Fe <I.E for Mn because of
stable 3d5 in Fe.
d) In general, third I.E. values are very high because of filled 4f-orbitals which
have poor shielding effect.

f. Oxidation state:-
i) Transition metals exhibit a larger number of oxidation states in their compound.
This is because of participation of inner (n -1)d electrons in addition to outer
ns- electrons because the energies of ns and (n -1)d electrons are almost
equal.
ii) The elements which gave the greatest number of oxidations states occur in or
near the middle of the series. Eg. Mn; oxidation states from + 2 to + 7.
iii) The lesser number of oxidation states at the extreme ends is either due to
electrons which loose or share (Sc, Ti) or too many d electrons, hence fewer
orbital are available for sharing of electrons with others, thus higher valence
cannot be attained. eg. Cu can have oxidation state of +1& +2; Zn can have
oxidation state of +2 only.
iv) Since there are partly filled d orbital's these elements exhibit certain
characteristic properties such as display of various oxidation states, formation
of coloured ions and entering into complex formation with a variety of ligands.
Cr(VI) in form of dichromate in acidic medium is a strong oxidizing agent
whereas MoO3 and WO3 are not.
v) Low oxidation state are found when a complex compound has ligands capable of
π-acceptor character in addition to σ-bonding. E.g Ni(CO)4 and Fe(CO)5, the
oxidation state of Ni and Fe is zero.

g. Trend in M2+ / M+ Standard Electrode Potential:-

The general trend in the electrode potential is found to be towards less negative
EƟ value across the series of the transition metals. This is due to the general
increase in the first and the second ionization enthalpies.
The electrode potential values for copper are found to be positive. This is due to
low hydration enthalpies as compared to high energy required to transform Cu (s)
to Cu2+ (aq). The EƟ value for Mn, Ni and Zn are more negative than the expected
from the trend.

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h. Trend in M3+ / M2+ Standard Electrode Potential:-
Except Copper and Zinc, all other elements of first transition series show +3
oxidation states to form M+3 in aqueous solution.
a) Low value of Sc reflects stability of Sc+3 which has a noble gas configuration.
b) High value for Mn shows that Mn+2 (d5) is particularly stable.
c) High value for Zn is due to removal of an electron from the stable d10
configuration of Zn2+.
d) Low value for Fe, shows extra stability for Fe +3 (d5) configuration.
e) Comparatively low value for V is related to the stability of V2+ (half-filled t2g level).

i. Trend in Stability of Higher Oxidation States:-

The highest oxidation state is generally shown among halides and oxidation.
a) Transition metals react with halogens at high temp as they have high activation
energies. High temp is required to start the reaction but heat of reaction is
sufficient to continue. The reaction. Order of reactivity: F 2> Cl2> Br2> I2
b) In general elements of 1st transition series enact in low oxidation state.
c) Since flowing is the most electronegative element, the transition elements show
high oxidations states with fluorine.
d) The highest oxidation states are found in TiX4 (tetrahalide), VF5 and CrF6.
e) The +7 oxidation states are not shown by simple halides.
f) V(V)is shown by VF5 only . Other halides undergo hydrolysis to give oxo halides
VOX3.
g) Fluorides are unstable in their low oxidation state.
E.g. V forms VX2 (X = Cl, Br or I) Cu can form CuX (X=Cl, I). Cu (II) halides are
known except the iodide.
h) The ability of oxygen to stabilize the highest oxidation state is exhibited in their
oxides. The highest oxidation states in member of group number. Eg-Sc in Sc2O3
is +3 and is a member of group 3.
i) Oxocations stabilize V(V) as VO2+, V(IV) as VO2+ and Ti (IV) as TiO2+.
j) Mn in group7 has +7 oxidation state in Mn2O7.Mangnese forms highest oxidation
state fluorides as MnF4 whereas the highest oxide is Mn2O7. This is due to
tendency of oxygen to form multiple bonds. In the covalent oxide Mn2O7, each Mn
is tetrahedrally surrounded by oxygen atoms and has Mn-O-Mn bridge.
Tetrahedral [MnO4]-2 ions are also known for V(V),Cr(VI), Mn(VI) and Mn(VII).
j. Formation of coloured ions:-
i) Most of the compounds of transition metals are coloured in solid or solution form
due to the presence of incomplete (n-1)d sub shell. Under the influence of central
metal ion, the d-ordinals of central metal split into different energy levels. This
phenomenon is called crystal field splitting.
ii) When an electron from a lower energy d orbital is excited to a higher energy
d orbital, the energy of the excitation corresponds to the frequency of light
absorbed. This frequency generally lies in the visible region.
iii) The colour observed corresponds to the complementary colour of the light
absorbed. The frequency of the light absorbed is determined by the nature of the
ligand.
iv) In aqueous solution where water molecules are the ligands, the colours of the
ions observed are purple, green, violet, blue, pink, yellow, colourless.

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v) When white light falls on the compounds, some part of its energy corresponding
to certain colour is absorbed and the electron gets raised from lower energy to
higher energy & the excess colour is transmitted. The observed colour is
complementary of colour absorbed. Eg-Ti+3 (d1) is purple.
vi) Transition metal ions containing completely filled d orbital's such as Zn2+, Cd2+,
Hg2+, Cu+ are generally white.
Similarly transition metal ions containing completely empty d - orbital's are white.
E.g. Sc3+, Ti4+.

k. Complex Formation:-
a) Complex compound are those in which the metal ions bind a number of anions or
neutral molecules giving complex species with characteristic properties.
b) Transition metals form a large no. of complexes due to
(i) presence of vacant d – orbital's of suitable energy
(ii) smaller size of metal ions
(iii) higher charge on cations. E.g. [PtCl4]2-, [Cu(NH3)4]2+, [Fe(CN)6]4– etc.
l. Chemical Reactivity and EƟ values:-
i) Many transition metals are electropositive and dissolve in mineral acids.
ii) Metals of first series with exception of Cu are relatively more reactive and are
oxidized by 1M H+ though actual rate is low.
iii) The EƟ values for Mn2+ / M indicates a decrease to form divalent cation across
the series. EƟ values for Mn, Ni and Zn are more negative than general trend.
iv) The stabilities of half-filled d subshell (d5) in Mn2+ and completely filled
d subshell (d10) in Zn are related to their EƟ values; for Ni EƟ value is related to
highest negative enthalpy of hydration.
v) Mn3+ and Co3+ ion are strongest oxidizing agents in aqueous solution.
Ti2+, V2+ and Cr2+ are strong reducing agents and liberate hydrogen from dilute
acid. 2Cr2+ (aq) + 2H+(aq) 2Cr3+(aq) + H2(g)

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m. Magnetic properties:-
i) When magnetic field is applied to a substance; two types of magnetic behaviour
are observed: diamagnetism and paramagnetism.
ii) Most of transition metals are paramagnetic in nature due to presence of
unpaired electrons. It increases from Sc to Cr and then decreases because of
number of unpaired electrons in d-orbital's. Larger the number of unpaired
electrons in a substance, larger is the magnetic moment and larger is the
paramagnetic behavior.
iii) Diamagnetic substances are repelled by the applied magnetic field while the
paramagnetic substances are attracted whereas the ferromagnetic substances
are attracted the most. Each unpaired electron has a magnetic moment
associated with its spin angular momentum and orbital angular momentum.

For the compounds of the 1 st transition series, the contribution of orbital angular
momentum is effectively less and hence is of no significance. For these, the
magnetic moment is determined by the number of unpaired electrons and can be
calculated by ‘spin only’ formula:
µ = √n(n+2) where n= no. of unpaired e-; µ = Magnetic moment in Bohr
magnetron (MB) units.
µ increases with the increasing number of unpaired electrons. Thus the observed
magnetic moment gives a useful indication about the number of unpaired electrons
present in the atom, molecule or ion.

E.g. Calculate the magnetic moment of Mn2+ if the at no. Z= 25

So, d5 has 5 unpaired electrons, n=5

µ = 5(5+2)

= 5.92 MB
n. Catalytic properties:-
a) Transition metals show catalytic property because of their ability to adopt multiple
oxidation states and to form complexes.
Catalysts at a solid surface involve the formation of bond between reactant
molecules and atoms of the surface of the catalyst. (first row utilize 3d and 4s
electron for bonding). This has the effect of increasing the concentration of the
reactants at the catalyst surface and also weakening of the bonds in the reacting
molecules & the activation energy is lowered, moreover transition metals can
change their oxidation states.

E.g.- Fe3+ catalyses the reaction between I2 & persulphate ions.

2 I- + S2O82- I2 + 2SO42-

b) Most of transition metals are used as catalyst because of

(i) presence of incomplete or empty d – orbital's,
(ii) large surface area,
(iii) variable oxidation state,
(iv) ability to form complexes, e.g., Fe, Ni, V2O3, Pt, Mo, Co and used as catalyst.

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 o. Formation of Interstitial compounds:-
i) Transition metals have voids or interstitials in which C, H, N, B etc. can fit into
resulting in formation of interstitial compounds.
ii) They are non – stoichiometric, i.e., their composition is not fixed, e.g., steel and
are neither typically ionic nor covalent. E.g. TiC, Mn4N, Fe3H; VH0.56 and TiH1.7
iii) They are harder and less malleable and ductile, chemically inert.
iv) Physical & Chemical characteristics of these compounds

(a) High m.pt, higher than pure metals. (b) Very hard, some borides approach
diamond in hardness (c) Retain metallic conductivity (d) Chemically inert.

p. Alloys formation:-
i) An alloy is a blend of metals prepared by mixing the components.
ii) Alloys are homogenous solid solutions in which the atoms of one metal are
distributed randomly among the atoms of the other but the metals should have
similar metallic radii within 15% of each other.
iii) The alloys formed have high m.pt & are hard. Eg. Alloys of Cr, V, W, Mo, Mn etc,
stainless steel is an alloys of Fe, Ni, Cr.
iv) Alloys of transition metals with non-transition metals, such as Brass (Cu-Zn),
Bronze (Cu- Sn). Metals form alloys due to similar ionic size.

Some important compounds of transition elements:

Oxides and Oxoanions of Metals:-
i.These oxides are generally formed by the reaction of metals with oxygen at high
temperatures.
ii.All the metals except scandium form MO oxides which are ionic.
iii.The highest oxidation number in the oxides, coincides with the group number and
is attained in Sc2O3 to Mn2O7. Beyond group 7, no higher oxides of iron above
Fe2O3 are known.
iv.Besides the oxides, the oxocations stabilise VV as VO2+, VIV as VO2+ and TiIV as
TiO2+.
v.As the oxidation number of a metal increases, ionic character decreases. In the
case of Mn, Mn 2O7 is a covalent green oil. Even CrO3 and V2O5 have low melting
points. In these higher oxides, the acidic character is predominant. Thus, Mn 2O7
gives HMnO4 and CrO3 gives H2CrO4 and H2Cr2O7.
vi.V2O5 is, however, amphoteric though mainly acidic and it gives VO43– as well as
VO2+ salts. In vanadium there is gradual change from the basic V 2O3 to less basic
V2O4 and to amphoteric V2O5. V2O4 dissolves in acids to give VO2+ salts. Similarly,
V2O5 reacts with alkalies as well as acids to give VO43 − and VO4+ respectively. The
well characterised CrO is basic but Cr2O3 is amphoteric.

Potassium dichromate K2Cr2O7

Preparation: Dichromates are generally prepared from chromate, which in turn are
obtained by the fusion of chromite ore (FeCr 2O4) with sodium or potassium
carbonate in free access of air.
4 FeCr2O4 + 8 Na2CO3 + 7 O2 → 8 Na2CrO4 + 2 Fe2O3 + 8 CO2
chromite ore Sodium Chromate

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The yellow solution of sodium chromate is filtered and acidified with sulphuric acid to
give a solution from which orange sodium dichromate, Na 2Cr2O7. 2H2O can be
crystallised.
2Na2CrO4 + 2 H+ → Na2Cr2O7 + 2 Na+ + H2O
Sodium Chromate Sodium dichromate

Sodium dichromate is more soluble than potassium dichromate, hence it is prepared

by treating the solution of sodium dichromate with potassium chloride.
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. The oxidation state of chromium in chromate and dichromate is the same.
2 CrO42– + 2H+ → Cr2O72– + H2O
Cr2O72– + 2 OH- → 2 CrO42– + H2O
The structures of chromate ion, CrO42– and the dichromate ion, Cr2O72– are shown
below.

The chromate ion is tetrahedral whereas the dichromate ion consists of two
tetrahedra sharing one corner with Cr–O–Cr bond angle of 126°.

Uses: 1) Potassium dichromate is a very important chemical used in leather industry

and as an oxidant for preparation of many azo compounds.
2) Sodium and potassium dichromates are strong oxidising agents; the sodium salt
has a greater solubility in water and is extensively used as an oxidising agent in
organic chemistry.
3) Potassium dichromate is used as a primary standard in volumetric analysis.
In acidic solution, its oxidizes as:
Cr2O72– + 14H+ + 6e– → 2Cr3+ + 7H2O (EƟ = 1.33V)
Thus, acidified potassium dichromate will oxidise iodides to iodine, sulphides to
sulphur, tin(II) to tin(IV) and iron(II) salts to iron(III).
The half-reactions are noted below:
6 I– → 3I2 + 6 e–; 3 Sn2+ → 3Sn4+ + 6 e–
–
3 H2S → 6H + 3S + 6e ;
+
6 Fe2+ → 6Fe3+ + 6 e–
The full ionic equation may be obtained by adding the half-reaction for potassium
dichromate to the half-reaction for the reducing agent, for e.g.,
Cr2O72– + 14 H+ + 6 Fe2+ → 2 Cr3+ + 6 Fe3+ + 7 H2O
Potassium permanganate KMnO4
Preparation: Potassium permanganate is prepared by fusion of MnO 2 with an alkali
metal hydroxide and an oxidising agent like KNO 3. 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

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Commercially it is prepared by the alkaline oxidative fusion of MnO 2 followed by the
electrolytic oxidation of manganate (Vl).
Fused with KOH, Electrolytic oxidation in
oxidised with air or KNO3 alkaline solution

MnO2 MnO42- ; MnO42- MnO4-

manganate ion manganate permanganate ion
In the laboratory, a manganese (II) ion salt is oxidised by peroxodisulphate to
permanganate.
2Mn2+ + 5S2O82– + 8H2O → 2MnO4– + 10SO42– + 16H+
Potassium permanganate forms dark purple (almost black) crystals which are
isostructural with those of KClO4. The salt is not very soluble in water (6.4 g/100 g of
water at 293 K), but when heated it decomposes at 513 K.
2KMnO4 → K2MnO4 + MnO2 + O2
It has two physical properties of considerable interest: its intense colour and its weak
temperature dependent paramagnetism. These can be explained by the use of
molecular orbital theory which is beyond the present scope.
The manganate and
permanganate ions are
tetrahedral; the green manganate
is paramagnetic with one unpaired
electron but the permanganate is
diamagnetic. The π-bonding takes
place by overlap of p orbitals of
oxygen with d orbitals of
manganese.
Acidified permanganate solution
oxidises oxalates to carbon
dioxide, iron(II) to iron(III), nitrites to nitrates and iodides to free iodine.
The half-reactions of reductants are:
COO–
5I → 10CO2 + 10e–
–
COO
5 Fe2+ → 5 Fe3+ + 5e–
5 NO2– + 5H2O → 5 NO3– + 10H+ + l0e–
10 I– → 5 I2 + 10e–
The full reaction can be written by adding the half-reaction for KMnO4 to the half-
reaction of the reducing agent, balancing wherever necessary.
If we represent the reduction of permanganate to manganate, manganese dioxide
and manganese(II) salt by half-reactions,
MnO4– + e– → MnO42– (EƟ = + 0.56 V)
MnO4– + 4H+ + 3e– → MnO2 + 2H2O (EƟ = + 1.69 V)
– –
MnO4 + 8H + 5e → Mn + 4H2O
+ 2+
(EƟ = + 1.52 V)
We can very well see that the hydrogen ion concentration of the solution plays an
important part in influencing the reaction. Although many reactions can be
understood by consideration of redox potential, kinetics of the reaction is also an
important factor. Permanganate at [H+] = 1 should oxidise water but in practice the
reaction is extremely slow unless either manganese(ll) ions are present or the
temperature is raised.

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A few important oxidising reactions of KMnO 4 are given below:
1. In acid solutions:
(a) Iodine is liberated from potassium iodide :
10 I– + 2MnO4– + 16H+ ——> 2Mn2+ + 8H2O + 5 I2
(b) Fe ion (green) is converted to Fe3+ (yellow):
2+

5Fe2+ + MnO4– + 8H+ ——> Mn2+ + 4H2O + 5Fe3+

(c) Oxalate ion or oxalic acid is oxidised at 333 K:
5C2O42– + 2MnO4– + 16H+ ——> 2Mn2+ + 8H2O + 10CO2
(d) Hydrogen sulphide is oxidised, sulphur being precipitated:
H2S —> 2H+ + S2– ; 5S2– + 2MnO–4 + 16H+ ——> 2Mn2+ + 8H2O + 5S
(e) Sulphurous acid or sulphite is oxidised to a sulphate or sulphuric acid:
5SO32– + 2MnO4– + 6H+ ——> 2Mn2+ + 3H2O + 5SO42–
(f) Nitrite is oxidised to nitrate:
5NO2– + 2MnO4– + 6H+ ——> 2Mn2+ + 5NO3– + 3H2O

2. In neutral or faintly alkaline solutions:

(a) A notable reaction is the oxidation of iodide to iodate:
2MnO4– + H2O + I– ——> 2MnO2 + 2OH– + IO3–
(b) Thiosulphate is oxidised almost quantitatively to sulphate:
8MnO4– + 3S2O32– + H2O ——> 8MnO2 + 6SO42– + 2OH–
(c) Manganous salt is oxidised to MnO 2; 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.

Uses: Besides its use in analytical chemistry, potassium permanganate is used as a

favourite oxidant in preparative organic chemistry. Its uses for the bleaching of wool,
cotton, silk and other textile fibres and for the decolourisation of oils are also
dependent on its strong oxidising power.

The Inner Transition elements (f- Block)

General electronic configuration is (n-2) f1-14 (n-1)d0-1 ns2 where (n – 2) stands for
inner energy level.
Consists of two series:-

1) Lanthanoides (Ln) - General Configuration is [Xe] 4f 1-14 5d 0-1 6s2. The last
electron enters a 4f- orbital called 4f- block or inner transition series. These are
also called Lanthanides or Lanthanons as they come immediately after
Lanthanum. These 14 elements were called rare earths.

2) Actinoides (Ac) - General Configuration is [Rn] 5f 1-14 6d 0-1 7s2. The last electron
enters a 5f- orbital called 5f- block or second inner transition series. These are
also called Actinides or Actinons as they come immediately after Actinium.

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 Lanthanoides

Lanthanoid Contraction - The shielding of one 4f electron by another less than that
by one d electron & the increase in nuclear charge along the series.

Lanthanoid contraction is caused by the steady decrease in the atomic and ionic
radii of the members of the third transition series which is very similar to the
corresponding second series.
The almost identical radii of Zirconium -Zr (160 pm) and Hafnium -Hf (159), a
consequence of the lanthanoid contraction, account their occurrence together in
nature and for the difficulty faced in their separation.

Oxidation states.:- Ln3+ & La3+ compounds are predominant species. +2 & +4 ions
in solution or in solid compounds are also obtained occasionally.
Ce (IV) formation is favoured due to extra stability of noble gas configuration, but it
is a strong oxidant reverting to the common +3 state.
Pr, Nd, Tb and Dy also exhibit +4 state but only in oxides, MO 2.Eu2+ is formed by
losing the two s- electrons & its configuration +7 is formed.
General Characteristics:-

Properties and use :- Ln are silvery white soft metals and tarnish rapidly in air.
Hardness increases with increasing atomic number. M.pt. ranges from 1000K –
1200 K but Samarium (Sm) is steel hard. (m.pt 1623K)
They have typical metallic structure and are good conductors of heat and electricity.

Colour Ln3+ are coloured both in solid and in aqueous solution due to the presence
of f electrons. La3+ and Lu3+ do not show any colour. However absorption bands are
narrow probably because of the excitation within f level.

Paramagnetism: Due to presence of unpaired electrons in the incomplete 4f

subshell Ln are paramagnetic. Ln3+ are paramagnetic except La3+ & Ce4+ (f0 type)
and Yb2+ & Lu3+ (f14 type). Paramagnetism rises to maximum in Neodymium .

Freda
Ionization enthalpies I.E. depends on the degree of stability of empty, half filled and
completely filled orbital's of f-level. This is indicated from the abnormally low values
of the third ionization enthalpy of Lanthanum, Gadolinium, Lutetium.

Chemical behaviour

In general earlier members of the series are quite reactive similar to Ca, with
increasing atomic number they behave more like aluminum.
Ln3+ (aq) +3e- ——> Ln(s)
The metals combine with hydrogen when gently heated in the gas. The carbides, Ln 3C,
Ln2C3 and LnC2 are formed when the metals are heated with carbon. They liberate hydrogen
from dilute acids and burn in halogens to form halides. They form oxides M 2O3 and
hydroxides M(OH)3. The hydroxides are definite compounds, not just hydrated oxides. They
are basic like alkaline earth metal oxides and hydroxides.

Their general reactions are depicted in Fig.

Use :- i) Used in the production of alloy steels for plates & pipes eg. Mischmetal is
an alloy which consists of a lanthanoid metal ( ̴ 95%) and iron (̴ 5%) and trace of S,
C, Ca and Al. A good amount of this allay is used in Mg-based alloy to produce
bullets, shell & lighter flint.
ii) Mixed oxides of Ln are used as catalyst in petroleum cracking.
iii) Ln oxides are used as phosphors in television screens & similar fluorescing
surfaces.
Actinoids:-

Although the naturally occurring elements & the earlier member have relatively long
half lives, the latter members have values ranging from a day to 3 minutes for Lr
(Z=103) These facts and high radioactivity renders their study more difficult.

Electronic Configuration: All the actinoids have the electronic configuration of 7s 2

and variable occupancy of the 5f and 6d subshells. The fourteen electrons are
formally added to 5f, though not in thorium (Z = 90) but from Pa onwards the 5f
orbitals are complete at element 103.

Freda
The irregularities in the electronic configurations of the actinoids like those of in the
lanthanoids are related to the stability of f o , f7 and f14 occupancies of the 5f orbital's.
Eg. Am : [Rn] 5f77s2 Cm : [Rn] 5f76d17s2

Ionic Sizes: Decrease in size due to increase in the effective nuclear charge on the
outermost shell and poor shielding by 5f electrons. This is referred to as actinoid
contractions.

Oxidation State: 5f orbital can & do participate in bonding. Common oxidation state
is +3 The maximum oxidation state increases from +4 in Th, +5 in Pa, +6 in U and +7
in Np but decreases in succeeding elements.

General Characteristics:- These metals are all silvery in appearance but display a
variety of structures due to irregularities in metallic radii which are greater in
lanthanoids.

Physical and Chemical Reactivity The actinoids are highly reactive when they are
finely divided.
The action of boiling water on them, for example, gives a mixture of oxide and
hydride and combination with most non metals takes place at moderate
temperatures. Hydrochloric acid attacks all metals but most are slightly affected by
nitric acid owing to the formation of protective oxide layers; alkalies have no action.

Magnetic Properties:- The magnetic properties of the actinoids are more complex
than those of the lanthanoids. The variation in the magnetic susceptibility of the
actinoids with the number of unpaired 5 f electrons is similar to the corresponding
lanthanoids, the latter have higher values.

Ionization Enthalpy : The I.E. of early actinoids is lesser than that of early Ln as
when 5f orbitals are beginning to be occupied, they will penetrate less into the inner
core of electrons. The 5f electrons, will therefore be more effectively shielded from
the nuclear charge than are the 4f electrons of the corresponding Ln because of the
outer electrons are less firmly held, they are available for bonding in the actinoids.

Comparison With Lanthanoids:-

1. Structural variability in actinoids is obtained due to irregularities in metallic radii
which are greater then lanthanoids.
2. Magnetic properties in actinoids are more complex than lanthanoids.
3. Ionization enthalpies of early actinoids, though not accurately known are lower
than early lanthanoids. This is because 5f electrons penetrate less into the inner
core and hence the outer electron are less firmly held, they are available for
bonding in actinoids.

Freda
Applications of d-and f Block Elements
1 Iron and steel are important construction materials. Their production is based on
reduction of iron oxides, removal of impurities, and addition of carbon and
alloying metals such as Cr, Mn, and Ni.
2 TiO is used in pigment industry.
3 MnO2 is used in battery cells. Also Zn and Ni/Cd.
4 Elements of group 11 are coinage metals (worthy).
5 V2O5 catalyses oxidation of SO2 in contact process,
6 Iron catalyst is used in Haber’s process.
7 TiCl4 and Al(CH3)3 forms Ziegler-Natta Catalyst.
8 Ni complexes are used in polymerization of alkynes.

Difference between Lanthanoids & Actinoids:-

Lanthanoids Actinoids
1. Exhibit +3 oxidation state while +2, +4 1. Exhibit +3 oxidation state while +4,
is seen only in few elements. +5, +6, +7 is seen.
2. Show small tendency to form
2. Form complexes.
complexes.
3. Except Promethium they are non-
3. All are radioactive.
radioactive.
4. Ln are less basic. 4. Ac are more basic.

Recently discovered elements (February 2016):-

 Nihonium and symbol Nh, for the element 113,
 Moscovium and symbol Mc, for the element 115,
 Tennessine and symbol Ts, for the element 117, and
 Oganesson and symbol Og, for the element 118.

Extra Questions

1. Define transition elements.

2. What is the position of the d block elements in the periodic table?
Ans. The d block elements are in the middle of s and p blocks, comprising the
groups 3 to 12. They are the four rows of elements in the periods 4th (3d
series), 5th (4d series), 6th (5d series) and 7th (6d series).
3. Why Zn, Cd and Hg of group 12 are not regarded as transition metals?
4. Why d- block elements are named as ‘transition elements'?
5. Write the general electronic configuration of d block elements.
7. Write the general electronic configuration of f- block elements.
8. Name a member of the lanthanoid series which is well known to exhibit +4
oxidation state.
Ans. Cerium
9. The outer electronic configuration of Cr is 3d 5 4s1 instead of 3d44s2, why?
Ans. Half filled (3d5) orbitals are relatively more stable, hence one electron of 4s
orbital jumps to 3d orbital.
10. The outer electronic configuration of Cu is 3d 10 4s1instead of 3d94s2, why?
Ans. Completely filled (3d10) orbitals are relatively more stable, hence one electron
of 4s orbital jumps to 3d orbital.

Freda
13. Why do transition metals have higher enthalpies of atomization?
Ans. Involvement of a large number of unpaired electrons of d orbitals favour
stronger inter atomic interactions resulting in stronger bonds between the
atoms of a metal and higher enthalpies of atomization.
14. Name one 3d series elements, that do not show variable oxidation states.
Ans. Sc (+3)
15. Transition metals exhibit variable oxidation states in its compounds, why?
Ans. Transition metals exhibit variable oxidation states in its compounds due to the
availability of both ns & (n – 1) d electrons for bond formation.
16. Name 3d series metal which shows highest oxidation state.
Ans. The highest oxidation state shown by 3d series transition metals is +7 by Mn
17. Name a metal in the 3d series of transition metals which exhibit +1 oxidation
state most frequently.
Ans. Copper
20. Why transition metals and their compounds shows paramagnetic behaviour?
Ans. The transition metal ions are generally containing one or more unpaired
electrons in them & hence their compounds are generally paramagnetic.
21. Name an of alloys of transition metals with non transition metals.
Ans. Brass (Cu & Zn) or Bronze (Cu & Sn)
22. What is the action of neutral or faintly alkaline permanganate solution on
iodide?
Ans. Alkaline permanganate solution oxidize iodide to iodate.
23. What happens when potassium permanganate is heated to 513 K ?
Ans. Potassium permanganate decomposes at 513K to potassium manganate,
manganese dioxide and oxygen.
25. Write the spin-only formula used to calculate the magnetic moment of metal
ions.
Ans. The magnetic moment is determined by using the spin only formula, where n
is the number of unpaired electrons and μ is the magnetic moment in units of
Bohr magneton (BM).
26. Why is Sc3+ (or Zn2+) diamagnetic?
Ans. Sc3+ (Z=21) 3d0 no unpaired electron, n=0, μ=0.
(or Zn2+(Z=30) 3d10 no unpaired electron, n=0, μ=0)
27. What is the most common oxidation state of lanthanoids and actionoids?
Ans. The most common oxidation state of lanthanoids and actionoids is +3.
28. What is Actinoid contraction?
29. Actinoid contraction is more than lanthanoid contraction. Give reason.
Ans. The actinoid contraction is, more than lanthanoid contraction due to poor
shielding by 5f electrons from nuclear charge.
30. Actionoids show larger number of oxidation states than lanthanoids. Why?
Ans. In actinoids 5f, 6d and 7s levels are of comparable energies, hence electrons
from these orbitals are available to lose or share.
32. Why transition metals forms alloys readily?
Ans. Transition metals readily form alloys with other transition metals because of
their similar radii
33. Give one use of transition metal alloy.
34. Name two characteristic properties exhibited by d – block elements due to their
partly filled d orbitals.

Freda
35. Name two typical metallic properties displayed by transition elements.
Ans. High tensile strength, ductility malleability, high thermal and electrical
conductivity and metallic luster etc.
36. What are interstitial compounds? Give example.
Ans. Interstitial compounds are those which are formed when small atoms like H, C
or N are trapped inside the crystal lattices of transition metals. Example; TiC,
Mn4N, Fe3H, VH0.56 and TiH1.7, etc.
38. Calculate the ‘spin only’ magnetic moment of M2+ (aq) ion (Z = 27).
Ans. M (z= 27 , 3d7 4s2) M+2 (3d7 4s0) hence it has 3 unpaired electrons n= 3
= 3(3+2) = 3.87 BM
39. The second ionisation enthalpy is high for Cr and Cu , why?
40. Why first ionisation enthalpy of Cr is lower than that of Zn ?
42. What is the action of heat on potassium permanganate ? Give equation.
Ans. It decomposes at 513K to potassium manganate, manganese dioxide and
oxygen. 2KMnO4 -------> K2MnO4 + MnO2 + O2
43. What is the action of neutral or faintly alkaline permanganate solution on
iodide? Give equation.
Ans. Alkaline permanganate solution oxidize iodide to iodate.
I- + 2MnO4- + H2O -------> IO3- + 2MnO2 + 2OH-
44. Explain the oxidising action of acidified potassium dichromate on (iron(II)
salts) Fe +2 ions and write the ionic equations for the reaction.
Ans. Acidified potassium dichromate oxidises iron(II) salts to iron(III).
Cr2O72− + 14H+ + 6Fe2+ → 2Cr3+ + 6Fe3+ + 7H2O
46. Give reason “transition metals and their many compounds acts as good
catalysts”.
47. Explain giving reason “transition metals form a large number of complex
compounds”.
48. What is the effect of increasing pH on a solution of potassium dichromate?
Ans. On increasing the pH of the solution Potassium dichromate (orange)
becomes potassium chromate (yellow) Cr 2O72- + 2OH- → 2CrO42- + H2O
49. What happens when H2S is passed into potassium dichromate in acidic
medium? Give the equation.
50. What is ‘disproportionation’ of an oxidation state ? Give one example of
disproportionation reaction in aqueous solution.
54. The chemistry of actionoids is more complicated than lanthanoids. Why?
Ans. The actinoids are radioactive elements having half lifes varying. Some
members can be prepared only in nanogram quantities. These facts render
their study more difficult.
56. What happens when (a) A lanthonoid reacts with dilute acids? (b) A
lanthonoid reacts with water?
Ans. (a) When lanthonoid reacts with dilute acids, it liberates hydrogen gas.
(b)When lanthonoid reacts with water, it forms lanthanoid hydroxide and
liberate hydrogen gas.
57. What is the gas liberated when i) crystals of potassium permanganate is
heated to 513K ? ii) acidified potassium permanganate is treated with oxalate
ion at 333K?
Ans. i) When crystals of potassium permanganate is heated to 513K Oxygen (O2)
gas is liberated. ii) Acidified potassium permanganate when treated with
oxalate ion at 333K liberates Carbon dioxide (CO 2) gas.
58. What is the composition of mischmetall? Give its one use.

Freda
60. How does the neutral or faintly alkalline potassium permanganate solution
react with (a) Iodide (b) thiosulphite? Write the ionic equations for the reactions
in neutral or faintly alkaline solutions

Goa Board Questions:-

March 2008
Q1. Write a chemical equation to show the action of acidified permanganate solution on
iodide. (1 marks)
Q2. What are transition elements? Mention the d-block elements which are not
considered as transition elements giving a reason. (3 marks)
Q3. Name the last element in the series of lanthanoids and write its electronic
configuration. (1 marks)

March 2009
Q1. Write a balanced chemical equation involving the action of acidified KMnO 4 on
ferric ions. (1 marks)
Q2. Explain the following properties of transition elements: (3 marks)
i) Paramagnetic character ii) Oxidation states iii) Alloy formation
Q3. Write the electronic configuration of Pm. (Z = 61) (1 marks)

March 2010
Q1. With the help of the electronic configuration of the two transition elements Mn and V,
explain giving reasons which one of them is more paramagnetic. (2 marks)
Q2. With respect to transition elements explain the following properties: (3 marks)
i. Formation of complex compounds.
ii. Formation of alloys.
iii. Formation of interstitial compounds.

March 2011
Q1. What is lanthanoid contraction? Write the electronic configuration of Lu +2 ion.
(Atomic mass of Lu = 71) (2 marks)
Q2. Answer the following: (3 marks)
i) State why the transition metals exhibit high melting points?
ii) How is sodium chromate converted to potassium dichromate? Write its
chemical equation.
iii) Why chromium and iron can be readily mixed to produce stainless steel?

March 2012
Q1. With respect to transition / inner transition elements, answer the following: (2)
i. Reasons for the catalytic properties of transition elements.
ii. What is lanthanoid contraction?

Q2. Write the balanced chemical equations for the following reactions: (2 marks)
i. Sodium chromate is acidified with sulphuric acid.
ii. Oxidation of thiosulphate ions with KMnO 4 in an alkaline medium.
March 2013
Q1. Write the complete chemical equation for the following: (2 marks)
i) Oxidation of Fe2+ by Cr2O72- in an acidic medium.
ii) Oxidation of S2O32- by MnO4- in a neutral aqueous medium.
Q2. Explain giving reasons: (2 marks)
i) Transition metals and their compounds are generally found to be good
catalysts.
ii) The actinoids exhibit a larger number of oxidation states than the
corresponding lanthanoids.

Freda
March 2014
Q1. Give reasons: (2 marks)
i) In the transition series enthalpy of atomization increases to maximum in the
middle of each series.
ii) Regular decrease in ionic sizes of lanthanides from La 3+ to Lu3+.
Or
Q1. Give reasons: (2 marks)
i) d-block elements form a large number of complex compounds.
ii) Actinoid contraction is greater from element to element than lanthanoid
contraction.
Q2. Draw the structure of the MnO4- ion, represent its oxidizing property with the
help of its reaction with oxalic acid in an acidic medium. (2 marks)

March 2015
Q1. Define Lanthanoid contraction.
Write the electronic configuration of Gd (Z = 64) and Lu (Z = 71). (1 marks)
Q2. Give reasons for each of the following : (2 marks)
i) Transition metals form a large number of complex compounds.
ii) Manganese exhibits largest number of oxidation states.

March 2016
Q1. The electronic configurations for Samarium atom and Samarium (III) ion are
______ and _____ respectively. (1 marks)
# [Xe] 4f 6 6s2 and [Xe] 4f 3 6s2 # [Xe] 4f 6 6s2 and [Xe] 4f 5
# [Xe] 4f 7 6s1 and [Xe] 4f 5 # [Xe] 4f 5 and [Xe] 4f 6 6s2
Q2. Write balanced ionic equation for oxidation of sulphide ion due to the action of
acidified K2Cr2O7. (2 marks)
Q3. Answer the following: (2 marks)
(i) Transition elements form interstitial compounds. Explain.
(ii) Write the variable oxidation states exhibited by the transition element
chromium, Cr in its compounds.

March 2017
Q1. The electronic configuration for Terbium atom and Terbium (IV) ion are______
(1 marks)
# [Xe] 4f 9 5d2 6s2 and [Xe] 4f 7 # [Xe] 4f 9 6s2 and [Xe] 4f 7 6s2
1 9 2
# [Xe] 4f and [Xe] 4f 6s # [Xe] 4f 9 6s2 and [Xe] 4f 7
Q2. Account for the following: (3 marks)
(i) Write the ionic equation to show the disproportionation of K 2MnO4 in
acidic solution.
(ii) Transition metals form coloured complexes.
(iii) Transition metals exhibit catalytic properties.

March 2018
Q1. The metal which has the lowest melting point is ______ (1 marks)
# Cesium # Mercury # Manganese # Copper
Q2. Draw the structure of the manganate ion. Give reasons for the following:
i. Transition metals form a large number of complexes. (3 marks)
ii. Zirconium and Hafnium are difficult to separate.
March 2019
Q1. Draw the structure of dichromate ion.
Given below are the transition metal ions of 3d series: (3 marks)
2+ 2+ 3+ 2+
Zn , Cu , Cr , Sc
a) Select the ion which is colourless, giving the reason.
b) Select the ion which is most paramagnetic, giving the reason.

Freda
 OR
Q1. Draw the structure of chromate ion.
Given below are the transition metal ions of 4d and 5d series: (3 marks)
Zr, Mo, Hf, Cd
a) Select the soft metals, giving the reason.
b) Select the pair of metals which occur together as minerals, giving the reason.

March 2020
Q1. The electronic configuration of some lanthanoids are: (1 marks)
1 1 2 7 2
Ce : [Xe] 4f 5d 6s Eu : [Xe] 4f 6s
Yb : [Xe] 4f 146s2 Sm : [Xe] 4f66s2
Among the given lanthanoid ions, the ion that is diamagnetic is _______.
# Ce+2 # Eu+2 # Yb+2 # Sm+2
Q2. With respect to transition elements, answer the following: (3 marks)
c) Write the correct stoichiometry and formula of the products (A) and (B) in the
chemical reactions given below:
4FeCr2O4 + 8Na2CO3 + 7O2 → 8Na2CrO4 + (A) + 8CO2
2MnO4- + 5NO2- + 6H+ → 2Mn2+ + (B) + 3H2O
d) Give reasons for the following:
i. Fe is a transition element but Zn is not.
ii. Transition metals form interstitial compounds.
March 2022
Q1. Write the electronic configuration of Gd+3 ion: (1 mark)
(Atomic number of Gd = 64)
Q2. Select the pair of elements from the following which have almost similar atomic radii:
Titanium, Niobium, Iron, Tantalum (1 mark)
Q3. Give scientific reasons for the following with respect to the transition elements:
(3 marks)
i. Fe can form large number of interstitial compound.
ii. The third ionization enthalpy of Manganese is very high.
iii. Ti+3 ion exhibits colour in aqueous solution whereas Sc +3 ion is colourless, though
both have same oxidation state.
March 2023
Q1.Give reasons: (5 marks)
a. Actinoids exhibit multiple oxidation states.
b. Transition metals are used as catalyst.
OR
c. Zr and Hf show similar atomic radii though they belong to different transition series.
d. Mn exhibits largest number of oxidation states in the first-row transition metals i.e. 3d
series.
Q2. Do as directed:-
a. Among the following alloys which are alloys of copper?
Solder, steel, Bronze, Cast iron, Brass, Nitinol
b. Why are interstitial compounds important?
c. Acidified potassium permagnate reacts with oxalate ion. What is the change in the
oxidation number of Mn in this reaction.
March 2024
Q1. What is lanthanoid contraction? Write the general formula of the oxide formed
when lanthanoid burns in oxygen. (2)
OR
Write the electronic configuration of Gd (Z = 64). Write the general formula of the
sulfide formed when lanthanoid is heated with sulphur.
Q2. Write a balanced equation for the preparation of potassium dichromate from sodium
dichromate. Write any 2 reasons for catalytic properties of transition metals. Why Zn 2+
salts are colourless while Cu2+ are coloured? (3)

Freda