148 d AND f BLOCK ELEMENTS

Alkaline KMnO4 used for this test is known as Baeyer’s (vii) It oxidises potassium iodide to iodine
reagent. It is used for oxidation of a number of organic
2KMnO 4  3H 2 SO 4  10KI 
o K 2SO 4  2MnSO 4 
compounds.
(c) In acidic medium. Potassium permanganate in the 8H 2 O  5I 2
presence of dil. sulphuric acid, i.e., in acidic medium, acts
as a strong oxidising agent because of the reaction (viii) It oxidises HX (where X = Cl, Br, l) to X2

2KMnO4  3H 2SO 4 
o K 2SO 4  2MnSO 4  3H 2 O  5O 2KMnO 4  3H 2SO4  10 HX 
o K 2SO4  2MnSO 4 

or MnO 4  8H   5 e  8H 2 O  5X 2
o Mn 2   4H 2 O.
(ix) It oxidises ethyl alcohol to acetaldehyde
Since in the above reaction, MnO 4 ion gains 5 electrons
2KMnO4  3H 2SO 4  5CH3 CH 2 OH 
o K 2SO 4  2MnSO4 
of five atoms of oxygen are available from two molecules
of KMnO4. Hence. 5CH 3 CHO  8H 2 O.
Mol. wt. 158 Uses.
Eq. wt. of KMnO 4 31.6
5 5
(i) It is often used in volumetric analysis for the estimation
Some oxidizing properties of KMnO4 in the acidic medium. of ferrous salts, oxalates, iodides and hydrogen peroxide.
These are given below : However, it is not a primary standard because it is difficult
to obtain it in the pure state and free from traces of MnO2.
(i) It oxidises H2S to S.
It is, therefore, always first standardised with a standard
2KMnO 4  3H2SO 4  5H 2 S 
o K 2SO4  2MnSO 4  2H 2 O  5O solution of oxalic acid.

(ii) It oxidises sulphur dioxide to sulphuric acid. Remember that volumetric titrations inolving KMnO4 are
carried out only in presence of dilute H2SO4 but not in the
2KMnO4  5 SO2  2H 2 O 
o K 2 SO4  2MnSO 4  2H 2SO 4 presene of HCl or HNO3. This is because oxygen produced
from KMnO4 + dill. H2SO4 is used only for oxidizing the
 
(iii) It oxidises nitrites NO 2 to nitrates NO3 , arsenites reducing agent. Moreover, H2SO4 does not give any
oxygen of its own to oxidiize the reducign agent. In case
AsO 33  to arsentates AsO 34 and sulphites and
HCl is used, the oxygen produced from KMnO4 + HCl is
thiosulphates to sulphates. partly used up to oxidize Hcl to chlorine and in case HNO3
is used, it itself acts as oxidizing agent and partly oxidizes
2KMnO 4  3H 2SO4  5KNO2 
o K 2SO4  2MnSO4 
the reducing agent.
3H 2 O  5KNO3 (ii) It is used as a strong oxidising agent in the laboratory as
well as in industry. It is a favourite and effective oxidising
(iv) It oxidises oxalates or oxalic acid to CO2
agent used in organic synthesis Alkaline potassium
2KMnO 4  3H 2SO4  5C2 H 2 O 4 
o K 2 SO4  2MnSO 4  permanganate is used for testing unsaturation in organic
chemistry and is known as Baeyer’s reagent.
8H 2 O  10 CO 2 (iii) Potassium permanganate is also widely used as a
(v) It oxidises ferrous sulphate to ferric sulphate (i.e., ferrous disinfectant and germicide. A very dilute solution of
salt to ferric salt). permanganate is used for washing wounds and gargling
for mouth sore. It is also used for purifying water of
2KMnO 4  8H 2SO4  10FeSO4 
o K 2SO4  2MnSO 4  stinking wells.
(iv) Because of its strong oxidizing power, it is also used for
5Fe2 SO4 3
 8H 2 O
bleaching of wool, cottong, silk and other textile fibres
(vi) It oxidises H2O2 to H2O and O2. This is because acidified and also for decolourisation of oils.
KMnO4 is a stronger oxidising agent than H2O2.

2KMnO 4  3H 2SO4  5H 2 O2 
o K 2SO4  2MnSO4 

8H 2 O  5O 2
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d AND f BLOCK ELEMENTS 149

THE LANTHANIDE SERIES

1. INTRODUCTION

These elements are classified by the filling up of the

antipenultimate 4f energy levels.

2. PHYSICAL PROPERTIES

Electronic Configuration and oxidation states

Element Electronic Electronic Oxidation States
Configuration Configuration of M3+

Lanthanum La [Xe] 5d1 6s2 [Xe] +3

Cerium Ce [Xe] 4f1 5d1 6s2 [Xe] 4f 1 +3 (+ 4)

Praseodymium Pr [Xe] 4f 3 6s2 [Xe] 4f 2 +3 (+ 4)

Neodymium Nd [Xe] 4f 4 6s2 [Xe] 4f 3 (+2) +3

Promethium Pm [Xe] 4f 5 6s2 [Xe] 4f 4 (+2) +3

Samarium Sm [Xe] 4f 6 6s2 [Xe] 4f 5 (+2) +3

Europium Eu [Xe] 4f 7 6s2 [Xe] 4f 6 (+ 2) +3

Gadolinium Gd [Xe] 4f 7 5d1 6s2 [Xe] 4f 7 +3

Terbium Tb [Xe] 4f 9 6s2 [Xe] 4f 8 +3 (+ 4)

Dysprosium Dy [Xe] 4f 10 6s2 [Xe] 4f 9 +3 (+ 4)

Holmium Ho [Xe] 4f 11 6s2 [Xe] 4f 10 +3

Erbium Er [Xe] 4f 12 6s2 [Xe] 4f 11 +3

Thulium Tm [Xe] 4f 13 6s2 [Xe] 4f 12 (+ 2) +3

Ytterbium Yb [Xe] 4f 14 6s2 [Xe] 4f 13 (+ 2) +3

Lutetium Lu [Xe] 4f14 5d1 6s2 [Xe] 4f 14 +3

2.1 Oxidation state Oxidation numbers (+II) and (+IV) do occur, particularly
when they lead to :
The sum of the first three ionization energies for each element
are low. Thus the oxidation state (+III) is ionic and Ln3+
1. a noble gas configuration e.g. Ce4+ (f 0)

dominates the chemistry of these elements. The Ln2+ and 2. a half filled f shell, e.g. Eu2+ and Tb4+ (f7)
Ln4+ ions that do occur are always less stable than Ln3+. 3. a completely filled f level, e.g. Yb2+ (f14).

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 150 d AND f BLOCK ELEMENTS

As we move along the lanthanide series, the nuclear charge

NOTE increases by one unit at each successive element. The new
electron is added into the same subshell (viz., 4f). As a result,
The 4f electrons in the antipenultimate shell are very the attraction on the electrons by the nucleus increases and
effectively shielded from their chemical environment this tends to decrease the size. Further, as the new electron
outside the atom by the 5s and 5p electrons. Consequently is added into the f-subshell, there is imperfect shielding of
the 4f electrons do not take part in bonding. They are one electron by another in this subshell due to the shapes
neither removed to produce ions nor do they take any of these f-orbitals. This imperfect shielding is unable to
significant part in crystal field stabilization or complexes. counterbalance the effect of the increased nuclear charge.
Crystal field stabilization is very important with the d- Hence, the net result is a contraction in the size though the
block elements. The octahedral splitting of f orbitals 'o is decrease is very small. It is interesting to note that in
only about 1kJ mol–1. Whether the f orbitals are filled or lanthanides, the decrease in the atomic radius for 14 elements
empty has little effect on the normal chemical properties. [Ce (58) to Lu (71)] is only 11pm (from 183 to 172 pm).
However, it does affect their spectra and their magnetic Similarly, decrease in ionic radii from Ce3+ to Lu3+ is only
properties. 17 pm (103 to 86 pm)
The contraction is similar to that observed in any transition
series. The cause is also similar, just as in the transition
2.2 Atomic radius
series where the contraction is due to imperfect shielding of
In lanthanide series, with increasing atomic number, there is one d electron by another. But the shielding of one 4f electron
a progressive decrease in the atomic as well as ionic radii of by another is less than one d electron by another with
increase in nuclear charge along the series.
trivalent ions from La3+ to Lu3+. This regular decrease in the
atomic and ionic radii with increasing atomic number is
known as lanthanide contraction.

Atomic and Ionic radii (pm) of lanthanum and lanthanoids.

Element La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu

Atomic Radii (Ln) 187 183 182 181 181 180 199 180 178 177 176 175 174 173 172

Ionic Radii (Ln3+) 106 103 101 99 98 96 95 94 92 91 90 89 88 87 86

2.3 Magnetic behaviour calculated by considering spin as well as orbital contribution,

i.e,
Paramagnetism is shown by the positive ions of lanthanides
except La3+ (lanthanum ion, f0) and Lu3+ (lutetium ion, f14). P eff 4 S (S  1)  L (L  1) B.M.
This property of the lanthanides is due to presence of where S is spin quantum number and L is orbital quantum
unpaired electrons in the incomplete 4f subshell. number.
lanthanides differ from transition elements in the fact that
their magnetic moments do not obey ‘spin only’ formula, NOTE

viz., P eff n ( n  2) B.M. where n is the number of Separation of the Lanthanide Elements
unpaired electrons. This because in case of transition Since the change in ionic radius is very small, the chemical
elements, the orbital contribution is quenched by the electric properties are similar. This makes the separation of the
field of the environment but in case of lanthanides, 4f orbitals element in pure state difficult. Separation is done by Ion
lie to deep to be quenched. Hence, their magnetic moment is Exchange methods which is based on the ionic size.

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