116

Chapter 13

d & f BLOCK
ELEMENTS
1. d BLOCK ELEMENTS - INTRODUCTION of dblock elements placed in the middle of periodic table. These
are from group-3 to group-12. d-block elements are further
1.1 Definition
classified into four series.
“The elements in which the last differentiating electron enters
4th period (21Sc to 30Zn, 10 elements) 1st Transition series.
into the d-orbitals of the penultimate shell are called d-block
elements”. 5th period (39Y to 48Cd, 10 elements) 2nd Transition series.
The properties of these elements are intermediate between the 6th period (51La, 72Hf to 80Hg, 10 elements) 3rd Transition
properties of s-block and p-block elements. series.
These elements represent a change or transition in properties
7th period (89Ac, 104 Rf to 112Cn, 10 elements) 4th Transition
from more electropositive elements (s-block) to less
series.
electropositive elements (p-block). Therefore these elements are
called transition elements.
A transition element may also be defined as the element which
has partially filled d-orbital in their ground state or most stable
oxidation state.
Cu (Z = 29) = 1s2 2s2 2p6 3s2 3p6 3d10 4s1
Cu2+ = 1s2 2s2 2p6 3s2 3p6 3d9 (Cupric ion)
1.2 Position of d-Block Elements in Periodic Table

In modern periodic table, d-block elements are placed in

between s-block and p-block elements. There are total 10 groups
d & f BLOCK ELEMENTS
117
1.3 Electronic Configuration gets exactly half-filled with configuration 3d5 4s1 and that in
In d-block elements with increase in atomic number, the d- case of copper, it gets completely filled with configuration 3d 10
orbitals of penultimate shell i.e. (n-1) d are gradually filled by 4s1. This can be explained on the basis of exchange energy.
electrons. The general electronic configuration of d-block Thus, the electronic configuration of chromium (Z = 24) and
element is, (n-1) d1-10, ns0-2. copper (Z = 29) are 1s2 2s2 2p6 3s2 3p6 3d5 4s1 and 1s2 2s2 2p6 3s6
3p6 3d10 4s1 respectively.
Depending upon the d-orbitals of which penultimate shell (i.e. n
= 4, 5, 6, 7) are filled, four rows (called series) of ten elements 1.4 General Properties of Transition Elements
each obtained. They correspond to 3d, 4d, 5d and 6d subshells. 1.4.1 Physical Properties
Energy of ‘(n–1)d’ subshell is slightly greater than ‘ns’ subshell, All the transition elements show typical metallic properties like
hence ns orbital is filled first then (n – 1) d orbitals. high tensile strength, ductility, malleability, high thermal and
The electronic configuration of d-block elements of four series electrical conductivity and metallic lustre. With the exceptions
is shown as follows : of Zn, Cd, Hg and Mn, they have one or more typical metallic
structures at normal temperatures.
First (3d) Transition Series (Sc–Zn)
Lattice Structures of d-Block Elements
At. No. 21 22 23 24 25 26 27 28 29 30
Sc Ti V Cr Mn Fe Co Ni Cu Zn
Element Sc Ti V Cr Mn Fe Co Ni Cu Zn
hcp hcp bcc bcc X bcc ccp ccp ccp X
4s 2 2 2 1 2 2 2 2 1 2 (bcc) (bcc) (bcc, (hcp) (hcp) (hcp)
3d 1 2 3 5 5 6 7 8 10 10 ccp)

Y Zr Nb Mo Tc Ru Rh Pd Ag Cd
hcp hcp bcc bcc hcp hcp ccp ccp ccp X
(bcc) (bcc) (hcp)
Second (4d) Transition Series (Y-Cd)
La Hf Ta W Re Os Ir Pt Au Hg
At. No. 39 40 41 42 43 44 45 46 47 48
hcp hcp bcc bcc hcp hcp ccp ccp ccp X
Element Y Zr Nb Mo Tc Ru Rh Pd Au Cd (ccp, (bcc)
bcc)
5s 2 2 1 1 1 1 1 0 1 2
4d 1 2 4 5 6 7 8 10 10 10
Third (5d) Transition Series (La–Hg) The melting and boiling points of transition metals are very
At. No. 57 72 73 74 75 76 77 78 79 80 high. The high melting points of these metals are attributed to
the involvement of greater number of electrons from (n-1)d in
Element La Hf Ta W Re Os Ir Pt Au Hg addition to the ns electrons.
6s 2 2 2 2 2 2 2 1 1 2
5d 1 2 3 4 5 6 7 9 10 10
Fourth (6d) Transition Series
At. No. 89 104 105 106 107 108 109 110 111 112

Element Ac Rf Db Sg Bh Hs Mt Ds Rg Cn
7s 2 2 2 2 2 2 2 2 1 2

6d 1 2 3 4 5 6 7 8 10 10
Exceptional Configuration of Cr and Cu:
The exceptions observed in the first series are in case of
electronic configurations of chromium (Z = 24) and copper (Z =
29). It may be noted that unlike other elements, chromium and
copper have a single electron in the 4s-orbital. This is due to the
gain of additional stability by the atom by either having half-
filled configuration (i.e., containing 5 electrons in the d-
sublevel) or completely filled configuration, (i.e., containing 10
electrons in the d-sublevel). The 3d-level in case of chromium
d & f BLOCK ELEMENTS
Melting points of transition elements
In any series of transition elements the melting points rise to a
maximum at d5 except for anomalous values of Mn and Tc and
fall regularly as the atomic number increases. Mn has stable
electronic configuration (3d5 half filled, 4s2 fully filled). As a
result 3d electrons are more tightly held by the nucleus and this
reduces the delocalisation of electrons resulting in weaker
metallic bonding.
Transition elements have high enthalpies of atomisation. The
maxima at about the middle of each series indicate that one
unpaired electron per d orbital is particularly favourable for
strong interatomic interaction. In general, greater the number of
valence electrons, stronger is the resultant bonding. Metals with
very high enthalpy of atomisation tend to be noble in their
reactions.
The transition metals of the second and third series have greater
enthalpies of atomisation than the corresponding elements of the
first series.
Enthalpies of atomisation of transition elements
1.4.2 Atomic Radii
(i) The atomic radii of the transition metals lie in-between
those of s- and p-block elements.
(ii) Generally the atomic radii of d-block elements in a series
decrease with increase in atomic number but the decrease
in atomic size is small after midway.
Explanation
The atomic radius decreases with the increase in atomic
number as the nuclear charge increases whereas the
shielding effect of d-electron is small. After midway, as the
electrons enter the last but one (penultimate) shell, the
added d-electron shields (screens) the outermost electron.
Hence, with the increase in the d-electrons, screening effect
118
increases. This counterbalances the increased nuclear
charge due to increase in atomic number. As a result, the
atomic radii remain practically same after chromium. For
example in Fe, the two opposing tendencies almost
counterbalance and there is no change in the size from Mn
to Fe.
(iii) At the end of the period, there is a slight increase in
theatomic radii.
Explanation
Near the end of series, the increased electron-electron
repulsions between added electrons in the same orbitals are
greater than the attractive forces due to the increased
nuclear charge. This results in the expansion of the electron
cloud and thus the atomic radius increases.
(iv) The atomic radii increase down the group. This means
thatthe atomic radii of second series are larger than those of
first transition series. But the atomic radii of the second and
third transition series are almost the same.
The atomic radii of the elements of the second and third
transition metals are nearly same due to lanthanide
contraction (or also called lanthanoid contraction)
discussed later.)
Atomic radii of transition elements
1.4.3 Ionic Radii
(i) The trend followed by the ionic radii is the same as that
followed by atomic radii.
(ii) Ionic radii of transition metals are different in different
oxidation states.
d & f BLOCK ELEMENTS
119
(iii) The ionic radii of the transition metals are smaller than
thoseof the representative elements belonging to the same
period. 1.4.4 Ionisation Enthalpies
(i) The first ionisation enthalpies of d-block elements lie
between s-block and p-block elements. They are higher than
those of sblock elements and are lesser than those of p-
block elements.
The ionisation enthalpy gradually increases with increase in
atomic number along a given transition series though some
irregularities are observed.
d & f BLOCK ELEMENTS

120
Ionisation Enthalpies of 3d Series of Transition Elements

Element Sc Ti V Cr Mn Fe Co Ni Cu Zn

Ionisation enthalpy/ Ho /kJ mol-1

i

l Ho I 631 656 650 653 717 762 758 736 745 906
lHo II 1235 1309 1414 1592 1509 1561 1644 1752 1958 1734

lHo III 2393 2657 2833 2990 3260 2962 3243 3402 3556 3837

Standard
electrode M2+/M -1.63 -1.18 -0.90 -1.18 -0.44 0.28 -0.25 +0.34 -0.76
potential Eo/V M3+/M2+ -0.37 -0.26 -0.41 +1.57 +0.77 +1.97

Explanation
The increasing ionization enthalpies are due to increased
nuclear charge with increase in atomic number which
reduces the size of the atom making the removal of outer
electron difficult.
(ii) In a given series, the difference in the ionisation enthalpies
between any two successive d-block elements is very much
less than the difference in case of successive s-block or
pblock elements.
Explanation
The addition of d electrons in penultimate shell with
increase in atomic number provides a screening effect and
thus shields the outer s electrons from inward nuclear pull.
Thus, the effects of increased nuclear charge and addition
of d electrons tend to oppose each other.
(iii) The first ionization enthalpy of Zn, Cd and Hg are,
however,very high because of the fully filled (n-1) d10 ns2
configuration.
(iv) Although second and third ionization enthalpies also,
ingeneral, increase along a period, but the magnitude of
increase for the successive elements is much higher.
(v) The high values of 3rd ionization enthalpies for Cu, Ni
andZn explain why they show a maximum oxidation state
of +2.
(vi) The first ionisation enthalpies of 5d elements are higher
ascompared to those of 3d and 4d elements. This is because
the weak shielding of nucleus by 4f electrons in 5d elements
results in greater effective nuclear charge acting on the
outer valence electrons.
1.4.5 Oxidation State
(1) With the exception of few elements, most of the d-block
elements show more than one oxidation state i.e. they show
variable oxidation states. The elements show variable
oxidation state because of following reasons:
(i) ‘(n-1) d’ and ‘ns’ orbitals in the atoms of d-block elements
have almost same energies and therefore electron can be
removed from ‘(n-1)d’ orbitals as easily as ‘ns’ orbitals
electrons.
(ii) After removing ‘s’ electrons, the remainder is called Kernel
of the metal cations. In d-block elements, the Kernel is
unstable and therefore it loses one or more electrons from
(n – 1)d electrons. This results in formation of cations with
different oxidation states.
(2) All transition elements show variable oxidation state except
last element in each series.
(3) Minimum oxidation state = Total number of 4s electrons
lost. Maximum oxidation state = (Total number of 4s
electrons lost + 3d electrons lost).
In ‘3d’ series all elements contain 2 electrons in ‘4s’ and
hence they all give a common minimum oxidation state of
+2. (Except ‘Cr’ and ‘Cu’ where minimum oxidation state
is +1.] The maximum oxidation state is given by Mn i.e.
Mn+7 in which two electrons are removed from 4s and five
unpaired electrons are removed from 3d orbitals.
(4) The highest oxidation state is shown by Ruthenium (Ru)
and Osmium (Os) i.e. +8.
(5) Across the period oxidation state increases and it is
maximum at the centre and than decreases even if atomic
number increases. The element which shows highest
d & f BLOCK ELEMENTS
121
oxidation state occur in the middle or near the middle of the The total energy, TH, for the process involving sublimation,
series and than decreases. ionisation and hydration simultaneously, i.e., for the process,
(6) Transition metals also show zero oxidation states in metal
carbonyl complex. Ms M aq e , will be the sum of the three
types of
Example : Ni in [Ni(CO)4] (Nickel tetracarbonyl) has zero
oxidation state. enthalpies, i.e.,
(7) The bonding in the compounds of lower oxidation state (+2, T HsubH i HhydH.
+3) is mostly ionic and the bonding in the compounds of
higher oxidation state is mostly covalent. Thus, TH, is the total enthalpy change when solid metal, M is
(8) The relative stabilities of some oxidation states can be (9) Cu +2 is more stable than Cu+ even when Cu+ is 3d10 while explained
on the basis of rule extra stability, according to Cu+2 is 3d due to high heat of hydration.
which d0, d5 and d10 are stable configurations. Variable oxidation states shown by 3d-series of d-block For example, the stability

order of some ions is as follows: elements.

Ti4+ (3d0, 4s0) > Ti3 (3d1, 4s0)

Mn2+ (3d5, 4s0) > Mn3+ (3d4, 4s0)
Fe3+, (3d5, 4s0) > Fe2+ (3d6, 4s0)

Oxidation States in 3d Series of Transition Elements

Element Sc Ti V Cr Mn Fe Co Ni Cu Zn
+2 +2 +2 +2 +2 +2 +2 +1 +2
+3 +3 +3 +3 +3 +3 +3 +2
+3 +4
+4 +4 +4 +4 +4
+4
+5 +5
+5
+6 +6
+6
+7

1.4.6 Standard Electrode Potentials (Eo) brought in the aqueous medium in the form of monovalent ion,
In solution, the stability of the compounds of transition metals M+ (aq).
depends upon electrode potentials. Electrode potential values
depend upon factors such as enthalpy of sublimation (or
atomisation) of the metal, the ionisation enthalpy and the
hydration enthalpy, i.e.,

subH
Ms Mg, ( subH is enthalpy of
sublimation)
Trends in the M2+/M Standard Electrode Potentials:
iH
Mg M g e, ( iH is ionisation (i) There is no regular trend in the Eo (M2+/M) values. This is
enthalpy) because their ionization enthalpies (IE1 + IE2) and
sublimation enthalpies do not show any regular trend.
M g aq hydH (ii) The general trend towards less negative Eo values along the
M aq , ( H is enthalpy of hydration) series is due to the general increase in the sum of first and
hyd
second ionization enthalpies.
d & f BLOCK ELEMENTS
122
(iii) Copper shows a unique behaviour in the series as it is (ii) The highest value for Zn is on account of very high stability
theonly metal having positive value for Eo. This explains of Zn2+ ion with d10 configuration. It is difficult to remove
why is does not liberate H2 gas from acids. It reacts only an electron from it to change it into +3 state.
with the oxidizing acids (HNO3 and H2SO4) which are (iii) The comparatively high value of Eo (Mn3+/Mn2+) shows that
reduced. The reason for positive Eo value for copper is that Mn2+ is very stable which is on account of stable d5
the sum of enthalpies of sublimation and ionization is not configuration of Mn2+.
balanced by hydration enthalpy.
(iv) The comparatively low value of Eo (Fe3+/Fe2+) is on account
Eo (M2+ Mo ) Values for Ti to Zn of extra stability of Fe3+ (d5), i.e., low third ionization
M Eo/V enthalpy of Fe.
Hyd H Mo
a Ho 11 Ho 12 Ho
Chemical Reactivity and Eo Values:
2

Ti 469 656 1309 –1866 –1.63 The transition metals vary widely in their chemical reactivity.
Some of them are highly electropositive and dissolve in mineral
V 515 650 1414 –1895 –1.18 acids whereas a few of them are ‘noble’, i.e., they do not react
Cr 398 653 1592 –1925 –0.90 with simple acids. Some results of chemical reactivity of
Mn 279 717 1509 –1862 –1.18 transition metals as related to their Eo values are given below :

Fe 418 762 1561 –1998 –0.44 (i) The metals of the first transition series (except copper) are
relatively more reactive than the other series. Thus, they are
Co 427 758 1644 –2079 –0.28
oxidized by H+ ions though the actual rate is slow, e.g., Ti
Cu 339 745 1958 –2121 0.34 and V are passive to dilute non-oxidizing acids at room
Zn 130 906 1734 –2059 –0.76 temperature.
o
(iv) The values of E for Mn, Ni and Zn are more negative than (ii) As already explained, less negative Eo values for M2+/M
expected from the general trend. This is due to greater along the series indicate a decreasing tendency to form
stability of half-filled d-subshell (d5) in Mn2+, and divalent cations.
completely filled dsubshell (d10) in Zn2+. The exceptional (iii) More negative Eo values than expected for Mn, Ni and Zn
behaviour of Ni towards Eo value from the regular trend is show greater stability for Mn2+, Ni2+ and Zn2+.
due to its high negative enthalpy of hydration.
(iv) Eo values for the redox couple M3+/M2+ indicate that Mn3+
and Co3+ ions ar the strongest oxidizing agents in aqueous
solution whereas Ti2+, V2+ and Cr2+ are strongest reducing
agents and can liberate hydrogen from a dilute acid, e.g.,
2 Cr2+ (aq) + 2 H+ (aq) 2 Cr3+ (aq) + H2 (g)

1.4.7 Catalytic Properties

Most transition elements and their compounds have good
catalytic properties because
(a) They possess variable oxidation state.
(b) They provide a large surface area for the reactant to
beabsorbed.
Some Common Catalysts
Catalysts Uses
Eo (M2 Mo ) values for Ti to Zn
TiCl4 + Al (C2H5)3 Ziegler-Natta catalyst, used in
Trends in the M3+/M2+ Standard Electrode Potentials: polymerisation of ethylene

(i) A very low value for Eo (Sc3+/Sc2+) reflects the stability of V2O5 Contact process SO2 SO3
Sc3+ ion which has a noble gas configuration. Fe Haber Bosch process
d & f BLOCK ELEMENTS
123
PdCl2 Wacker’s process for Mn2+ 3d5 5 5.92 5.96
CH3CHO manufacturing
Fe 2+
3d6 4 4.90 5.3 – 5.5
Pd Hydrogenation of alkene, Co 2+
3d7 3 3.87 4.4 – 5.2
alkyne Ni2+ 3d8 2 2.84 2.9 – 3, 4
Pt/PtO
Adam’s catalyst for selective Cu2+ 3d9 1 1.73 1.8 – 2.2
reduction 2+
Zn 3d10 0 0
Pt Catalytic convertor, for
cleaning car exhaust fumes 1.4.9 Complex Formation
Transition metal ions form a large number of complex
Pt/Rh Ostwald’s process :
compounds. Complex compounds are those which have a metal
NH3 NO ion linked to a number of negative ions (anions) or neutral
Cu Oxidation of alcohols molecules having lone pairs of electrons. These ions or
molecules are called ligands. They donate lone pairs of electrons
to the central transition metal ion forming coordinate bonds.
1.4.8 Magnetic Behaviour
A few examples are given below :
When a magnetic field is applied to substances, mainly two
types of magnetic behaviour are observed: diamagnetism and [Fe(CN)6]3–, [Fe(CN)6]4–, [Cu(NH3)4]2+, [Zn(NH3)4]2+,
paramagnetism. [Ni(CN)4]2– and [PtCl4]2–
Diamagnetic substances are repelled by the applied field while Such complex compounds are not formed by s - and p - block
the paramagnetic substances are attracted. Most of the transition elements.
metal ions are paramagnetic due to the presence of unpaired
Explanation. The transition elements form complexes because
electrons. Each such electron having a magnetic moment
of the following reasons :
associated with its spin angular momentum and orbital angular
momentum. (i) Comparatively smaller size of their metal ions.
In first transition elements series the orbital angular magnetic (ii) Their high ionic charges and high charge/size ratio.
moment is insignificant the orbital contribution is quenched by (iii) Availability of vacant d-orbitals so that these orbitals
the electric fields of the surrounding atoms so magnetic moment canaccept lone pairs of electrons donated by the ligands.
is equal to the spin magnetic moment only.
1.4.10 Formation of Coloured Compounds
It can be calculated by using the formula:
Transition elements form coloured ions due to presence of
incompletely filled d-orbitals and unpaired electrons. They can
eff n(n 2)BM
undergo d-d transition by absorbing colour from visible region
n no. of unpaired electron. and radiating complementary colour, e.g. Cu2+ (blue),
V2+(violet), Cr3+(green). Cu+(3d10), Zn2+(3d10), Cd2+(4d10),
The magnetic moment increases with the increasing number of
Sc3+(3d0 ) are white due to presence of no unpaired electrons and
unpaired electrons. Thus, the observed magnetic moment is
cannot undergo dd transition.
directly related to the number of unpaired electrons present in
the atom, molecule or ion. Colour of Ions of 3d Series
Magnetic Moments of 3d Series Ions Configuration Example Colour
Ion Unpaired Magnetic moment 3d0 Sc3+ colourless
electron(s)
Calculated Observed 3d0 Ti4+ colourless
Sc3+ 3d0 0 0 0 3d1 Ti3+ purple
Ti3+ 3d1 1 1.73 1.75 3d1 V4+ blue
Tl2+ 3d2 2 2.84 2.76 3d2 V3+ green
3
V2+ 3d 3 3.87 3.86 3d3 V2+ violet
Cr2+ 3d4 4 4.90 4.80 3d3 Cr3+ violet
d & f BLOCK ELEMENTS
124
3d4 Mn3+ violet
3d4 Cr2+ blue
3d5 Mn2+ pink
3d5 Fe3+ yellow
3d6 Fe2+ green
3d63d7 Co3+Co2+ bluepink
3d8 Ni2+ green
3d9 Cu2+ blue
Alloy Formation
3d10 Zn2+ colourless
1.4.11 Interstitial Compounds
The transition metals form a large number of interstitial 2. IMPORTANT COMPOUNDS OF
compounds in which small atoms such as hydrogen, carbon, TRANSITION ELEMENTS
boron and nitrogen occupy the empty spaces (interstitial sites)
in their lattices (Fig.). 2.1 Oxides and Oxocations

They are represented by formulae like TiC, TiH2, Mn4N, Fe3H, (i) The metals of the first transition series form oxides with
Fe3C etc. However, actually they are non-stoichiometric oxygen at high temperature.
materials, (ii) The oxides are formed in the oxidation, states +1 to +7.
e.g., TiH1.7, VH0.56 etc. and the bonds present in them are neither (iii) The highest oxidation state in the oxides of any
typically ionic nor covalent. Some of their important transitionmetal is equal to its group number, e.g., 7 in
characteristics are as follows:
Mn2O7. Beyond group 7, no higher oxides of iron above
(i) They are very hard and rigid, e.g., steel which is an Fe2O are known. Some metals in higher oxidation state
interstitial compound of Fe and C is quite hard. Similarly,
stabilize by forming oxocations, e.g., VV as VO 2 , VIV as
some borides are as hard as diamond.
VO2+ and TiIV as TiO2+.
(ii) They have high melting points which are higher than those
of the pure metals. (iv) All the metals except scandium form the oxides with
(iii) They show conductivity like that of the pure metal. theformula MO which are ionic in nature. As the oxidation
(iv) They acquire chemical inertness. number of the metal increases, ionic character decreases,
e.g., Mn2O7 is a covalent green oil. Even CrO3 and V2O5
1.4.12 Alloy Formation have low melting points.
Alloys are homogeneous solid solutions of two or more metals 2 8/3 3 4 7
obtained by melting the components and then cooling the melt.
MnO Mn O34 Mn O23 MnO2 Mn O27
These are formed by metals whose atomic radii differ by not
more than 15% so that the atoms of one metal can easily take up (v) In general, the oxides in the lower oxidation states of
the positions in the crystal lattice of the other. themetals are basic and in their higher oxidation states, they
As transition metals have similar atomic radii and other are acidic whereas in the intermediate oxidation state, the
characteristics, hence they form alloys very readily. oxides are amphoteric.
Alloys are generally harder, have higher melting points and For example, the behaviour of the oxides of manganese may
more resistant to corrosion than the individual metals. be represented as follows :
2 8/3 3 4 7
The most commonly used are the ferrous alloys the metals
chromium, vanadium, molybdenum, tungsten and manganese MnO Mn O34 Mn O23 MnO2 Mn O27
Basic Amphoteric Amphoteric Amphoteric Acidic
are used in the formation of alloy steels and stainless steels.
Some alloys of transition metals with non-transition metals are
also very common. e.g., brass (Cu + Zn) and bronze (Cu + Sn) Thus, Mn2O7 dissolves in water to give the acid HMnO4.
d & f BLOCK ELEMENTS
125
2.2 Potassium Dichromate, K2Cr2O7
2.2.1 Preparation Process
It is prepared from the ore called chromite or ferrochrome or
chrome iron, FeO.Cr2O3. The various steps involved are as
follows :
(i) Preparation of Sodium Chromate:
The ore is finely powdered, mixed with sodium carbonate Structure of chromate and dichromate ions
and quick lime and then roasted, i.e., heated to redness in a 2.2.3 Properties of Potassium Dichromate
reverberatory furnace with free exposure to air when (a) Colour and Melting Point: It forms orange crystals which
sodium chromate (yellow in colour) is formed and carbon melt at 669 K.
dioxide is evolved. Quick lime keeps the mass porous and
(b) Solubility: It is moderately soluble in cold water but freely
thus facilitates oxidation.
soluble in hot water.
4FeCr2O4 + 8Na2CO3+ 7O2 8Na2CrO4 + 2Fe2O3 + 8CO2 (c) Action of Heat: When heated to a white heat, it decomposes
with the evolution of oxygen.
Chromite ore Sod. chromate Ferric oxide
After the reaction, the roasted mass is extracted with water 4K Cr O22 7 4K CrO24 2Cr O2 3 3O2
when sodium chromate is completely dissolved while ferric (d) Action of Alkalies: When an alkali is added to an orange
oxide is left behind. Ferric oxide is separated out by filtration. red solution of dichromate, a yellow solution results due to
the formation of chromate.
(ii) Conversion of Sodium Chromate into Sodium Dichromate:
The filtrate containing sodium chromate solution is treated K Cr O2 2 7 KOH 2K CrO2 4 H O2
with concentrated sulphuric acid when sodium chromate is Pot. dichromate Pot.chromate or Cr O2 72
converted into sodium dichromate.
2OH 2CrO42 H O2
2Na CrO24 H SO24 Na Cr O2 2 7 Na SO2
4 H O2 On acidifying, the colour again changes to orange red due
Sod.chromate Conc. Sod.dichromate to the reformation of dichromate.
Sodium sulphate being less soluble crystallizes out as
2 K CrO2 4 H SO2 4 K Cr O2 2 7 K SO2 4 H
decahydrate, Na2SO4. 10H2O and is removed. The clear
solution is then evaporated in iron pans to a specific gravity O2 or 2 CrO24 2H Cr O2 72 H O2
of 1.7 when a further crop of sodium sulphate is formed. It
is removed and the solution is cooled when orange crystals This interconversion is explained by the fact that in
of sodium dichromate, Na2Cr2O7. 2H2O separate on dichromate solution, the Cr O2 72 ions are invariably in
standing. equilibrium with CrO24 ions at pH = 4, i.e.,
(iii) Conversion of Na2Cr2O7 into K2Cr2O7 :
Hot concentrated solution of sodium dichromate is treated Cr O272 H O2 pH 4

with calculated amount of potassium chloride when 2CrO42 2H

Orange red Yellow
potassium dichromate, being much less soluble than sodium
dichromate chromate
salt, crystallizes out on cooling as orange crystals.
(e) Action of Concentrated Sulphuric Acid :
Na Cr O2 27 2KCl K Cr O2 2
(i) In cold, red crystals of chromic anhydride (chromium
7 2NaCl
Sodium dichromate Potassium dichromate trioxide) are formed.

2.2.2 Structures of Chromate and Dichromate Ions K Cr O22 7 2H SO24 2CrO3 2KHSO4 H O2
2–
The chromate ion, CrO4 is tetrahedral and the dichromate ion, (ii) On heating the mixture, oxygen is evolved.
2–
Cr2O7 is made up of two tetrahedra sharing one corner with
Cr– O–Cr bond angle of 126°.
d & f BLOCK ELEMENTS
126
2K Cr O2 2 7 8H SO2 4 2K SO2 K Cr O2 2 7 H SO2 4 3SO2 K SO24 Cr SO2
4 2Cr2 SO4 3 + 8H2O + 3O2 4 3 3H O2
(viii) It oxidises stannous salts to stannic salts
(f) Oxidising Properties: It is a powerful oxidising agent. In the
presence of dilute sulphuric acid, one molecule of Cr O2 7
2 14 H 3Sn2 2 Cr3 3 Sn4 7 H O2
potassium dichromate furnishes 3 atoms of available
oxygen as indicated by the equation : (ix) It oxidises ethyl alcohol to acetaldehyde and acetic acid.

4H K Cr O2 27 4H SO2 4 K SO2 4 Cr SO2

K Cr O2 2 7 4H SO2 4 K SO2 4 Cr2 SO4 3 + 2O
4 3 4H O 3O2

+ 3O or Cr O2 72 14H 6e 2Cr3 7H O2 CH CH OH O22 CH CHO3 H O2

Ethyl alcohol

Mol. wt. 294

Eq. wt. of K Cr O2 2 7 49 CH CHO O3 CH COOH3
Acetaldehyde Acetic acid
6 6
(i) It liberates I2 from KI Test for a drunken driver : The above reaction helps to test
whether a driver has consumed alcohol or not. He is asked to
K Cr O2 2 7 7H SO2 4 6KI 4K SO2 breathe into the acidified K2Cr2O7 solution taken in a test tube.
If the orange colour of the solution changes into green colour
4 Cr2 SO4 3
(due to Cr2(SO4)3 formed in the reaction), the driver is drunk,
3I2 7H O2 otherwise not.
(ii) It oxidises ferrous salts to ferric salts (g) Chromyl Chloride test : (Reaction with a chloride and conc.
sulphuric acid). When heated with concentrated hydrochloric
K Cr O2 2 7 7H SO2 4 6FeSO4 K SO2 acid or with a chloride and strong sulphuric acid, reddish brown
4 Cr SO2 4 3 vapours of chromyl chloride are obtained.
K Cr O2 2 7 4KCl 6H SO2 4 2CrO Cl2 2
3Fe2 SO4 3 2H O2 6KHSO4 3H O2
Chromyl chloride
(iii) It oxidises H2S to sulphur Red vapour

K Cr O2 4H SO2 3H S2 K SO2 (h) Reaction with Hydrogen Peroxide : Acidified K2Cr2O7

2 7 4
solution reacts with H2O2 to give a deep blue solution due
4 Cr2 SO4 3
to the formation of peroxo compound, CrO (O2)2.
+ 7H2O + 3S
(iv) It oxidises sulphites to sulphates and thiosulphates to
sulphates and sulphur Cr O2 72 2H 4 H O2 2 2 CrO5 5 H O2

The blue colour fades away gradually due to the decomposition

K Cr O2 2 7 4H SO2 4 3Na SO23 K SO24
of CrO5 into Cr3+ ions and oxygen.
Cr SO2 4 3

+ 4H2O + 3Na2SO4
(v) It oxidises nitrites to nitrates The structure of CrO5 is in which Cr is in +6
oxidation
K Cr O2 2 7 4 H SO24 3NaNO2 K SO2 state.
4 Cr SO2 4 3
2.2.4 Uses of Potassium Dichromate
+ 3 NaNO3 + 4 H2O
(i) In volumetric analysis, it is used as a primary standard for
(vi) It oxidises halogen acids to halogen the estimation of Fe2+ (ferrous ions) and I– (iodides) in redox
titrations.
K Cr O2 27 14 HCl 2KCl 2CrCl3 7H O2
3Cl2 (ii) In industry, it is used
(vii) It oxidises SO2 to sulphuric acid (a) In chrome tanning in leather industry.
d & f BLOCK ELEMENTS
(b) In the preparation of chrome alum K2SO4.Cr2(SO4)3. 24H2O
and other industrially important compounds such as Cr2O3,
CrO3, CrO2Cl2, K2CrO4, CrCl3 etc.
(c) In calico printing and dyeing.
(d) In photography and in hardening gelatine film.
(iii) In organic chemistry, it is used as an oxidising agent.
NOTE
127
2K MnO24 H O2 O32KMnO4 2KOH O2
The carbon dioxide process is uneconomical as one third of the
original manganate is reconverted to manganese dioxide.
However, this process has the advantage that the potassium
carbonate formed as a by-product can be used for the oxidative
fusion of manganese dioxide. In the chlorine process, potassium
chloride obtained as a by-product is lost.
2.3.2 Structure of Manganate and Permanganate ions

Both manganate MnO24 and permanganate MnO 4

Unlike K2Cr2O7, Na2Cr2O7 is not used in volumetric analysis
because it is deliquescent. ions are tetrahedral. Here the -bonding takes place by overlap
2.3 Potassium Permanganate (KMnO4) of p orbitals of oxygen with d orbitals of manganese. The green
manganate ion is paramagnetic because of one unpaired electron
2.3.1 Preparation Methods but the permanganate ion is diamagnetic due to the absence of
On a large scale, it is prepared from the mineral, pyrolusite, any unpaired electron.
MnO2. The preparation involves the following two steps: Its intense colour and diamagnetism along with
(i) Conversion of MnO2 into Potassium Manganate: temperaturedependent weak paramagnetism can be explained
by molecular orbital theory.
The finely powdered pyrolusite mineral is fused with
potassium hydroxide or potassium carbonate in the
presence of air or oxidising agent such as potassium nitrate
or potassium chlorate when green coloured potassium
manganate is formed.

2MnO2 + 4KOH + O2 2K2MnO4 + 2H2 O

2MnO2 + 2K2CO3 + O2
MnO2 + 2KOH + KNO3
3MnO2 + 6KOH + KClO3
Potassium manganate
Structure of manganate and permanganate ions
2K2MnO4 + 2 CO2
2.3.3 Properties of Potassium Permanganate
K2MnO4 + KNO2 + H2O (a) Colour : Potassium permanganate exists as deep purple
black prisms with a greenish lustre which become dull in air
3K2MnO4 + KCl + 2H2O due to superficial reduction.

(ii) Oxidation of Potassium Manganate to Potassium (b) Solubility : It is moderately soluble in water at room
Permanganate: temperature and it is more soluble in hot water.
Potassium manganate thus formed undergoes (c) Action of Heat : When heated to 513 K, it readily
disproportionation in the neutral or acidic solution as decomposes giving oxygen.
follows, if allowed to stand for some time : 2KMnO4 K MnO2 4 MnO2 O2
VI VII IV
Pot. manganate
2
3 MnO 4 4H 2 MnO 4 MnO2 2 H O2
Manganateion Permanganate ion
At red heat, potassium manganate formed decomposes into
potassium manganite (K2MnO3) and oxygen.
The fused mass is extracted with water and the solution after
filtration is converted into potassium permanganate by 2K MnO24 2K MnO2 3 O2
bubbling carbon dioxide, chlorine or ozonised oxygen (d) Action of heat in current of hydrogen : When heated in a
through the green solution. current of H2, solid KMnO4 gives KOH, MnO and water
3K MnO24 2CO2 2KMnO4 MnO2 2K CO23 vapours.

2KMnO4 5H2 2KOH 2MnO 4H O2

2K MnO2 4 Cl2 2KMnO4 2KCl
d & f BLOCK ELEMENTS
128
(e) Oxidising Property. Potassium permanganate is powerful 5Fe2 SO4 3 8H O2
oxidising agent. The actual course of reaction depends on
(vi) It oxidises H2O2 to H2O and O2. This is because acidified
the use of the permanganate in (a) acidic medium (b) neutral
KMnO4 is a stronger oxidising agent than H2O2.
medium or (c) alkaline medium.
(i) In acidic medium : Potassium permanganate in the presence 2KMnO4 3H SO24 5H O2 2 K SO24 2MnSO4
of dil. sulphuric acid, i.e., in acidic medium, acts as a strong
8H O2 5O2
oxidising agent because of the reaction
(vii) It oxidises potassium iodide to iodine
2KMnO 3H SO4 24 K SO24 2MnSO 3H O 5O4 2 2KMnO4 3H SO24 10KI K SO24 2MnSO4
2
or MnO 4 8H 5e Mn 4H O.2 8H O2 5I2

Since in the above reaction, MnO 4 ion gains 5 electrons of (viii) It oxidises HX (where X = Cl, Br, I) to X2
five atoms of oxygen are available from two molecules of
2KMnO4 3H SO24 10 HX K SO24 2MnSO4
KMnO4. Hence.
8H O2 5X2
Mol. wt. 158
Eq. wt. of KMnO4 31.6 (ix) It oxidises ethyl alcohol to acetaldehyde
5 5 2KMnO 3H SO 5CH CH OH4 2 4 3 2
Some oxidizing properties of KMnO4 in the acidic medium: K SO 2MnSO2 4 4

These are given below :

5CH CHO3 8H O.2
(i) It oxidises H2S to S.
(ii) In neutral solution :
2KMnO 3H SO 5H S4 24 2 K SO 2MnSO 2H O 5O2 Potassium permanganate acts as a moderate oxidising agent
4 4 2 in neutral aqueous solution because of the reaction :
(ii) It oxidises sulphur dioxide to sulphuric acid. 2KMnO4 H O2 2KOH 2MnO2 3O
or
2KMnO 5SO 2H O4 2 2 K SO 2MnSO 2H SO2 4

4 2 4 MnO 4 2H O2 3 e MnO2 4OH

Thus, MnO 4 ion gains 3 electrons. Also, according to the

(iii) It oxidises nitrites NO 2 to nitrates NO3 , above equation, in neutral medium, from two moles of
arsenites permanganate, three oxygen atoms are available. In fact,
during the course of reaction, the alkali generated renders
AsO33 to arsentates AsO34 and sulphites and the medium alkaline even when we start with neutral
thiosulphates to sulphates. solutions.
Hence, Eq. wt. of KMnO4 in neutral or weakly alkaline
2KMnO 3H SO 5KNO4 2 4 2 K SO
medium
2MnSO2 4 4
Mol. wt. 158
3H O2 5KNO3
52.67
(iv) It oxidises oxalates or oxalic acid to CO2 3 3
Some oxidizing properties of KMnO4 in the neutral
2KMnO 3H SO 5C H O4 2 4 2 24 K
medium. These are given below :
SO2 4 2MnSO4
(i) It oxidises hot manganous sulphate to manganese dioxide.
8H O2 10 CO2
2KMnO 3MnSO 2H O4 4 2 K SO 2H SO 5MnO2 4 2
(v) It oxidises ferrous sulphate to ferric sulphate (i.e., 4 2
ferroussalt to ferric salt).
Presence of ZnSO4 or ZnO catalyses the oxidation.
2KMnO 8H SO 10FeSO4 2 4 4 K SO2 (ii) It oxidises sodium thiosulphate to sodium sulphate.
4 2MnSO4
d & f BLOCK ELEMENTS
129
8KMnO 3Na S O H O4 2 2 3 2 3K
SO 8MnO2 4 2

3Na SO24 2KOH

Alkaline KMnO4 used for this test is known as Baeyer’s
(iii) It oxidises hydrogen sulphide to sulphur. reagent. It is used for oxidation of a number of organic
2KMnO4 4H S2 2MnS SK SO24 4H O2 compounds.
2.3.4 Uses of Potassium Permanganate
(iii) In alkaline solution : In strongly alkaline solution, MnO 24
(i) It is often used in volumetric analysis for the estimation of
(manganate) ion is produced.
ferrous salts, oxalates, iodides and hydrogen peroxide.
2KMnO4 2KOH 2K MnO24 H O2 O or However, it is not a primary standard because it is difficult
to obtain it in the pure state and free from traces of MnO 2.
MnO 4 e MnO24
It is, therefore, always first standardised with a standard
Mol. wt. 158 solution of oxalic acid.
Eq. wt. of KMnO4 158 (ii) Volumetric titrations inolving KMnO4 are carried out only
1 1 in presence of dilute H2SO4 but not in the presence of HCl
Potassium manganate is also further reduced to MnO2 when or HNO3. This is because oxygen produced from KMnO4 +
dil. H2SO4 is used only for oxidizing the reducing agent.
a reducing agent is present.
Moreover, H2SO4 does not give any oxygen of its own to
K MnO24 H O2 MnO2 2KOH O oxidize the reducing agent. In case HCl is used, the oxygen
produced from KMnO4 + HCl is partly used up to oxidize
or MnO24 2H O2 2e MnO2 4OH HCl to chlorine and in case HNO3 is used, it itself acts as
oxidizing agent and partly oxidizes the reducing agent.
So the complete reaction is :
(iii) It is used as a strong oxidising agent in the laboratory as
2KMnO4 H O2 2MnO2 2KOH 3O wellas in industry. Alkaline potassium permanganate is
or used for testing unsaturation in organic chemistry and is
MnO 4 2H O2 3 e MnO2 4OH known as Baeyer’s reagent.

which is the same as that for neutral medium. Hence, (iv) Potassium permanganate is also widely used as a
equivalent weight of KMnO4 in weakly alkaline medium is disinfectantand germicide. A very dilute solution of
same as that in the neutral medium, viz., 52.67 permanganate is used for washing wounds and gargling for
mouth sore. It is also used for purifying water of stinking
Some oxidizing properties of KMnO4 in the alkaline medium: wells.
These are given below :
(v) Because of its strong oxidizing power, it is also used
(i) It oxidises potassium iodide to potassium iodate. forbleaching of wool, cotton, silk and other textile fibres
2KMnO4 H O KI2 2MnO2 2KOH KIO 3
and also for decolourisation of oils.
Pot. iodate
1. f BLOCK ELEMENTS - INTRODUCTION
or
The innter transition elements are also known as f-block
I 6OH IO3 3H O2 6 e elements. There are two f-block series, lanthanoids (the fourteen
In this case, iodine is not liberated unlike the case of acidic elements following lanthanum) and actinoids (the fourteen
medium. elements following actinium). The lanthanoids resemble each
other closely. They have only one stable oxidation state and their
Similar reaction takes place with KBr.
chemistry resembles largely with each other. On the other hand,
(ii) It oxidises olefinic compounds to glycols, i.e., when an the chemistry of the actinoids is much more complicated due to
olefinic compound is shaken with alkaline KMnO 4, pink the occurrence of a wide range of oxidation states and
colour of KMnO4 is discharged. radioactive nature.
d & f BLOCK ELEMENTS
130
2. THE LANTHANIDE SERIES The 4f electrons in the antipenultimate shell are very
The 14 elements after La-57 are collectively called lanthanoides effectively shielded from their chemical environment outside
or lanthanide series or 4f series. Some times, lanthanoides are the atom by the 5s and 5p electrons. Consequently the 4f
electrons do not take part in bonding. Whether the f orbitals are
collectively represented by symbol Ln.
filled or empty has little effect on the normal chemical
2.1 Electronic Confignration properties. However, it does affect their spectra and their
These elements have electronic configration [Xe]4f1-14 5d0-1 6s2. magnetic properties.
They have 6s2 common but with variable occupancy of 4f and
5d level. The electronic configurations of all tripositive ions are
of the form 4f1-14.
2.2 Oxidation State
The sum of the first three ionization energies for each element
are low. Thus the oxidation state (+III) is ionic and Ln 3+
dominates the chemistry of these elements. The Ln2+ and Ln4+
ions that do occur are always less stable than Ln3+.
Oxidation numbers (+II) and (+IV) do occur, particularly when
they lead to :
1. a noble gas configuration e.g. Ce4+ (f 0)

2. a half filled f shell, e.g. Eu2+ and Tb4+ (f7)

3. a completely filled f level, e.g. Yb2+ (f14).

NOTE

Electronic Configuration and Oxidation States of Lanthanoides

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
7 2 6
Europium Eu [Xe] 4f 6s [Xe] 4f (+ 2) +3
Gadolinium Gd [Xe] 4f 7 5d1 6s2 [Xe] 4f 7 +3
9 2 8
Terbium Tb [Xe] 4f 6s [Xe] 4f +3 (+ 4)
Dysprosium Dy [Xe] 4f 10 6s2 [Xe] 4f 9 +3 (+ 4)
11 2 10
Holmium Ho [Xe] 4f 6s [Xe] 4f +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
d & f BLOCK ELEMENTS
131
2.3 Atomic and Ionic Radii (Lanthanide Contraction) members of the third transition series to be very similar to those
In lanthanide series, with increasing atomic number, there is a of the corresponding members of the second series. The almost
progressive decrease in the atomic as well as ionic radii of identical radii of Zr (160 pm) and Hf (159 pm), a consequence
of the lanthanoid contraction, account for their occurrence
Atomic and Ionic Radii of Lanthanoides
Atomic Electronic configurations Radii/pm
Number
Name Symbol Ln Ln2+ Ln3+ Ln4+ Ln Ln3+
57 Lanthanum La 5d16s2 5d1 4f0 187 106
58 Cerium Ce 4f15d16s2 4f2 4f1 4f0 183 103
59 Praseodymium Pr 4f36s2 4f3 4f2 4f1 182 101
60 Neodymium Nd 4f46s2 4f4 4f3 4f2 181 99
61 Promethium Pm 4f56s2 4f5 4f4 181 98
62 Samarium Sm 4f66s2 4f6 4f5 180 96
7 6
63 Europium Eu 4f76s2 4f 4f 199 95
64 Gadolinium Gd 4f75d16s2 4f75d1 4f7 180 94
65 Terbium Tb 4f96s2 4f9 4f8 4f7 178 92
66 Dysprosium Dy 4f106s2 4f10 4f9 4f8 177 91
67 Holmium Ho 4f116s2 4f11 4f10 176 89
68 Erbium Er 4f126s2 4f12 4f11 175 88
69 Thulium Tm 4f136s2 4f13 4f12 174 87
70 Ytterbium Yb 4f146s2 4f14 4f13 173 86
71 Lutetium Lu 4f145d16s2 4f145d1 4f14
– –
trivalent ions from La3+ to Lu3+. This regular decrease in the together in nature and for the difficulty faced in their separation.
atomic and ionic radii with increasing atomic number is known
as lanthanide contraction.
As we move along the lanthanide series, the nuclear charge
increases by one unit at each successive element. The new
electron is added into the same subshell (4f subshell). As a
result, the attraction on the electrons by the nucleus increases
and this tends to decrease the size. Further, as the new electron
is added into the f-subshell, there is imperfect shielding of one
electron by another in this subshell due to the shapes of these f-
orbitals. This imperfect shielding is unable to counterbalance
the effect of the increased nuclear charge. Hence, the net result
is a contraction in the size though the decrease is very small.
It is interesting to note that in lanthanides, the decrease in the
atomic radius for 14 elements [Ce (58) to Lu (71)] is only 11pm
(from 183 to 172 pm). Similarly, decrease in ionic radii from
Ce3+ to Lu3+ is only 17 pm (103 to 86 pm).
The cumulative effect of the contraction of the lanthanoid series,
known as lanthanoid contraction, causes the radii of the
d & f BLOCK ELEMENTS
132
Trends in ionic radii of lanthanoids
d & f BLOCK ELEMENTS
2.4 Magnetic Behaviour
Paramagnetism is shown by the positive ions of lanthanides
except La3+ (lanthanum ion, f0) and Lu3+ (lutetium ion, f14). This
property of the lanthanides is due to presence of unpaired
electrons in the incomplete 4f subshell.
Lanthanides differ from transition elements in the fact that their
magnetic moments do not obey ‘spin only’ formula, viz.,
eff n (n 2) B.M. where n is the number of unpaired
electrons. This because in case of transition elements, the orbital
contribution is quenched by the electric field of the environment
but in case of lanthanides, 4f orbitals lie to deep to be quenched.
Hence, their magnetic moment is calculated by considering spin
as well as orbital contribution, i.e,
eff 4 S (S 1) L (L 1) B.M.
where S is spin quantum number and L is orbital quantum
number.
NOTE
Separation of the Lanthanide Elements
Since the change in ionic radius is very small, the chemical
properties are similar. This makes the separation of the element
in pure state difficult. Separation is done by Ion Exchange
methods which is based on the ionic size.
2.5 Colour
The lanthanides are silvery white metals. However, most of the
trivalent metal ions are coloured, both in the solid state and in
aqueous solution. This is due to the partly filled-f-orbitals which
permit f-f transition.
NOTE
Lanthanides ions with x f electrons have a similar colour to
those with (14–x) f electrons e.g., La3+ and Lu3+ are colourless,
Sm3+ and Dy3+ are yellow and Eu3+ and Tb3+ are pink.
2.6 Chemical Reactivity
Chemically the earlier members of the lanthanide series are
quite similar to calcium but, with increasing atomic number,
they behave more like aluminium.
These metals combine with hydrogen when gently heated in
hydrogen gas to from hydrides (LnH3).
When these metals are heated with carbon, they give carbides,
Ln3C, Ln2C3 and LnC2.
They liberate hydrogen from dilute acids and burn in halogens
to form halides (LnX3).
133
They form oxides M2O3 and hydroxides M(OH)3. The oxides
and hydroxides are basic like alkaline earth metal oxides and
hydroxides.
Chemical reactions of the lanthanoids
The hydroxides Ln(OH)3 are precipitated as gelationous
precipitates by the addition of NH4OH to aqueous solutions.
These hydroxides are ionic and basic. They are less basic than
Ca(OH)2 but more basic than Al(OH)3 which is amphoteric. The
metals, oxides and hydroxides all dissolve in dilute acids,
forming salts. Ln(OH)3 are sufficiently basic to absorb CO2 from
the air and form carbonates. The basicity decreases as the ionic
radius decreases from Ce to Lu. Thus Ce(OH)3 is the most basic,
and Lu(OH3), which is the least basic, is intermediate between
Scandium and Yttrium in basic strength. The decrease in basic
properties is illustrated by the hydroxides of the later elements
dissolving in hot concentrated NaOH, forming complexes.
Yb(OH)3 + 3NaOH 3Na+ + [Yb(OH)6]3–
Lu(OH)3 + 3NaOH 3Na+ + [Lu(OH)6]3–
2.7 Uses of Lanthanides
The lanthanoids are mainly used for :
(i) Production of alloy steels for plates and pipes
(ii) Production of Mischmetall, it is an alloy containing (95%)
lanthanoid metals + (5%) iron + traces of S, C, Ca and Al.
(iii) Mischmetall is used as Mg based alloy to produce
bulletsshell and lighter flints.
(iv) Mixed oxides of lanthanoids are used as catalyst in
petroleumcracking.
(v) Some lanthanide oxides are used as phosphors in
televisionscreens and similar fluorescing surfaces.
3. THE ACTINIDES SERIES
The actinoids include the fourteen elements from Th to Lr.
d & f BLOCK ELEMENTS
134
The actinoids are radioactive elements and the earlier members oxidation states. The maximum oxidation state first increases
have relatively long half-lives, the latter ones have half-life upto the middle of the series and then decreases, e.g., it increases
values ranging from a day to 3 minutes for lawrencium (Z from + 4 from Th to +5, +6, and +7 for Pa, U and Np but
=103). The latter members could be prepared only in nanogram decreases in the succeeding elements.
quantities. The actinides resemble lanthanides in having more compounds
3.1. Electronic Configuration in +3 state than in the +4 state. However, the compounds in the
All the actinoids have the electronic configuration of 7s 2 and +3 and +4 state tend to undergo hydrolysis.
variable occupancy of the 5f and 6d subshells. The fourteen 3.3 Atomic and Ionic Radii
electrons are formally added to 5f, though not in thorium (Z = The actinides show actinide contraction (very much like
Atomic and Ionic Radii of Actinoids
Atomic Electronic configurations* Radii/pm
Number Name Symbol M M3+ M4+ M3+ M4+
89 Actinium Ac 6d17s2 5f0 111
90 Thorium Th 6d27s2 5f1 5f0 99
91 Protactinium Pa 5f26d17s2 5f2 5f1 96
92 Uranium U 5f36d17s2 5f3 5f2 103 93
93 Neptunium Np 5f46d17s2 5f4 5f3 101 92
5 4
94 Plutonium Pu 5f67s2 5f 5f 100 90
6 5
95 Americium Am 5f77s2 5f 5f 99 89
7 1 2 6
96 Curium Cm 5f 6d 7s 5f7 5f 99 88
9 2 8 7
97 Berkelium Bk 5f 7s 5f 5f 98 87
9 8
98 Callifornium Cf 5f107s2 5f 5f 98 86
99 Einstenium Es 5f117s2 5f10
5f 9
– –
100 Fermium Fm 5f127s2 5f11
5f10
– –
101 Mendelevium Md 5f137s2 5f12
5f11
– –
102 Nobelium No 5f147s2 5f13
5f12
– –
103 Lawrencium Lr 5f146d17s2 5f14 5f13
– –

90) but from Pa onwards the 5f orbitals are complete at element lanthanide contraction) due to poor shielding effect of the 5f-
103. The irregularities in the electronic configurations of the electrons. As a result, the radii of the atoms or ions of these
actinoids, like those in the lanthanoids are related to the metals decrease regularly across the series. The contraction is
stabilities of the f0, f7 and f14 occupancies of the 5f orbitals. Thus, greater from element to element in this series due to poorer
the configurations of Am and Cm are [Rn] 5f7 7s2 and [Rn] shielding by 5f electrons compared to 4f electrons in
5f76d17s2. Although the 5f orbitals resemble the 4f orbitals in lanthanoides. This is because 5f orbitals extend in space beyond
their angular part of the wavefunction, they are not as buried as 6s and 6p orbitals whereas 4f orbitals are buried deep inside the
4f orbitals and hence 5f electrons can participate in bonding to atom.
a far greater extent than 4f orbitals in case of lanthanoides.
3.2 Oxidation State
Unlike lanthanides, actinides show a large number of oxidation
states. This is because of very small energy gap between 5f, 6d
and 7s subshells. Hence, all their electrons can take part in bond
formation. The dominant oxidation state of these element is +3
(similar to Lanthanides). Besides +3 state, Actinides also exhibit
an oxidation state of +4. Some Actinides show still higher
d & f BLOCK ELEMENTS
135
3.4 Magnetic Behaviour Differences :
Like lanthanides, the actinides are strongly paramagnetic. The The show differences in some of their characteristics as follows
variation in magnetic susceptibility of actinides with the :
increasing number of unpaired electrons is similar to that of
Difference between Lanthanides and Actinides
lanthanides but the values are higher for the actinides than the
lanthanides. Lanthanides Actinides

3.5 Colour (i) Besides + 3 oxidation (i) Besides +3 oxidation

state they show + 2 and +4
These metals are silvery white. However, actinide cations are oxidation states only in few
generally coloured. The colour of the cation depends upon the cases.
number of 5f-electrons. The cations containing no 5f-electron or
having seven 5f-electrons (i.e., exactly half-filled f-subshell) are (ii) Most of their ions are
colourless. The cations containing 2 to 6 electrons in the colourless.
5fsubshell are coloured both in the crystalline state as well as in (iii)They have less tendency
aqueous solution. The colour arises due to f–f transition e.g. towards complex formation.
Ac3+ (5f 0) = colourless, U3+ (5f 3) = Red, Np3+ (5f 4) = Blue,
Pu3+
(iv) Lanthanides compounds
(5f 5) = Violet, Am3+ (5f 6) = Pink, Cm3+ (5f 7) = Colourless, are less basic.
Th3+ (5f 0) = Colourless as so on. (v) They do not form
oxocation.
3.6 Chemical Reactivity
Actinides show almost similar chemical behaviour to (vi) Except promethium,
lanthanides. they are non-radioactive.
(vii) Their magnetic
properties can be explained
easily.
state, they show higher
oxidation states of +4, +5,
+6, + 7.
(ii) Most of their ions are
coloured.
(iii) They have greater
tendency towards complex
formation.
(iv) Actinides compounds
are more basic.
(v) They from oxocations.
e.g. UO22 ,PuO22 and UO .
(vi) They are radioactive.
(vii) Their magnetic
properties cannot be
explained easily.

Chemical reactions of the actinides

4. COMPARISON OF LANTHANIDES AND
ACTINIDES
Similarities :
As both lanthanides and actinides involve filling of f-orbitals,
they show similarities in many respects as follows :
(i) Both show mainly oxidation state of +3.
(ii) Both are electropositive and very reactive.
(iii) Both exhibit magnetic and spectral properties.
(iv) Actinides exhibit actinide contraction like
lanthanidecontraction shown by lanthanides.
d & f BLOCK ELEMENTS
136

SUMMARY
d-Block Elements
• d-block elements are those in which the last electron goes to
(n-1) d-orbitals.
• General electronic configurations of d-block elements is :
ns1-2, (n-1)d1-10
• Transition metals have high values of melting and boiling
points which are due to the presence of strong metallic
bonding in these metals.
• Due to lanthanide contraction, atomic radii for the elements
of 3rd transition series are almost equal to those for the
elements of 2nd transition series.
• The values of ionisation energies increase as we move from
left to right in each series.
• Except for Cu, E°red values for other metals of Ist transition
series are negative.
• Excepting a few metals, most of the metals show several
oxidation states. This is due to the fact that (n-1)d and ns
orbitals have almost the same energy.
• Transition metal ions which contain partially filled dorbitals
are usually coloured. The colour arises because of d-d
transition. Transition metal ions with d0 or d10 configuration
are colourless because d-d transition is not possible in such
ions.
• Transition metals form interstitial compounds.
• Many transition metals and their alloys and compounds act
as catalysts in many chemical reactions.
• General electronic configuration of f-block elements is ns2,
(n-1)d0-1, (n-2)f1-14
• + 3 oxidation state (O.S.) is the most stable O.S. of
lanthanides.
• There is a steady decrease in atomic and ionic (M³+ ions)
radii of lanthanides. This steady decrease in atomic and
ionic radii is called lanthanide contraction.
• Magnetic moment value of lanthanides and actinides is
calculated by considering both orbital spin contribution. µeff
value is given by µeff = 4S (S+1)+L(L+1) B.M, here S spin
quantum number and L= orbital quantum number
• Mischmetal is an important alloy of lanthanides. It contains
90% lanthanides (La= 40%, Ce and other lanthanides= 50%
) , Fe = 5% and traces of other elements like C, S, Al, Ca.
• The actinide elements lying beyond U (Np-93 to Lw-103)
are called trans-uranic or trans-uranium elements.
• Unlike lanthanides, actinides show a large number of
oxidation states.
• Actinides have lower values of ionisation energies.
• Most of actinide halides form complex compounds with
alkali metal halides. The degree of complex formation for
the ions decreases as : M4+ > MO22+ > M3+ > MO2+.
• Thorium is used in atomic reactors and in the treatment of
cancer. Uranium is used as a nuclear fuel. Plutonium is used
as a fuel for atomic reactors as well as for making atomic
bombs.

f-Block Elements
• The elements in which the last electron enters f-orbital of
(n-2)th shell are called f-block elements. f-block elements
are of two types lanthanides and actinides.
d & f BLOCK ELEMENTS

137
d AND f BLOCK ELEMENTS
SOLVED
EXAMPLES
Example - 1
Why Cr and Cu show exceptional configuration ?
Sol. By deviating from normal configuration, Cr and Cu
acquires half-filled and fully filled configurations which
gives them extra stability. Hence they show exceptional
configuration.
Cr [Ar] 3d5 4s1 and Cu [Ar] 3d10 4s1
Example - 2
In what way is the electronic configuration of the
transition elements different from that of the
nontransition elements ?
Sol. Transition elements have incomplete penultimate dorbitals
while penultimate orbitals of representative elements (s
- and p - block elements) are completely filled up. The
general valence shell configuration of s-block (group 1
and 2) elements is ns1–2 and for p-block elements (group
13 to 18) is ns2 np1–6. The valence shell configuration of
transition elements can be written as (n – 1) d1–9 ns1–2 .
Example - 3
What are the characteristics of the transition elements
and why are they called transition elements ? Which of
the d-block elements may not be regarded as the
transition elements?
Sol. The important characteristics of transition metals are:
(i) All transition elements are metallic in nature, e.g., all are
metals.
(ii) These metals exhibit variable oxidation states.
(iii) Transition metal atoms or ions generally form the
complexes with neutral, negative and positive ligands.
(iv) Compounds of transition metals are usually coloured.
(v) The compounds of these metals are usually paramagnetic
in nature.
(vi) Transition metals and their compounds act as good
catalysts, i.e., they show catalytic activities.
138
(vii) These metals form various alloys with other metals of
the series.
(viii) These metals form interstitial compounds with C, N,
Band H.
The presence of partially filled d-orbitals in the
electronic configuration of atomic and ionic species of
these elements is responsible for the characteristic
properties of transition elements. They are called
transition elements because of their position in the
periodic table. These elements lie in the middle of
periodic table between s and p-block (i.e., between
group 2 and group 13). A transition element may be
defined as a element whose atom or at least one of its
simple ions contain partially filled d-orbitals, e.g., iron,
copper, chromium, nickel etc. The general
characteristic electronic configuration may be written
as (n – 1) d1–10ns1–2.
The elements of group 12 i.e., Zinc, Cadmium, and
Mercury are generally not regarded as transition
elements as their atoms and all ions formed have
completely filled d-orbitals i.e., these do not have
partially filled d-orbitals in atomic state or common
oxidation state (Zn2+, Cd2+, Hg2+)
Zn (30) = [Ar] 4s23d10 Zn2+ = [Ar] 3d10 4s0
2 10
Cd (48) = [Kr] 5s 4d Cd2+ = [Kr] 4d10 5s0
2 10
Hg (80) = [Xe] 6s 5d Hg2+ = [Xe] 5d10 6s0
Example - 4
Explain giving reason
(i) Transition metals and many of their compounds show
paramagnetic behaviour.
(ii) The enthalpies of atomisation of the transition metals are
high.
(iii) The transition metals generally form coloured
compounds.
(iv) Transition metals and their many compounds act as good
catalyst.
Sol.
(i) Due to presence of unpaired electrons
(ii) The metallic bonds in transition elements are very strong
due to participation of (n 1) d electrons along with
valence s-electrons in the bond formation. Therefore, the
d AND f BLOCK ELEMENTS
cleavage of these bonds is extremely difficult and
consequently, enthalpies of atomization are high.
(iii) Due to d-d transitions
(iv) They exhibit variable oxidation states and have large
Sol. Some time transition metal species in same oxidation state
surface area, hence acts as good catalysts
Example - 5
How would you account for the following :
139
Example - 6
What is meant by disproportionation ? Give two
examples of disproportionation reaction in aqueous
solution.
undergo a chemical change in such a way that some
species get both oxidised and reduced. For example,
Cr(V) and Mn(VI) species undergo disproportionation
reaction in acidic medium as follows:

(a) Of the d4 species Cr2+ is strongly reducing while 3CrO43 8H 2CrO4 2 Cr3 4H O2
manganese(III) is strongly oxidising. Crin 5 o.s. Cr in o.s.

(b) Cobalt(II) is stable in aqueous solution but in the

presence of complexing reagents it is easily 3MnO43 4H 2MnO4 MnO2 2H O2
oxidized. Mn in 6 o.s. Mn in Mn in
7 o.s 4 o.s.

(c) The d1 configuration is very unstable in ions?

Here, we can say that Cr in +5 oxidation state undergo
Sol. disproportionation into its +6 and +3 states. Similarly,
Mn in +6 oxidation state undergo disproportionation
(a) Of d4 species, Cr2+ has 3d4 configuration and tends to into +7 and +7 oxidation states.
loose one electron to acquire d3 configuration as it is
highly stable and best metallic specie available for Example - 7
complex formation. Cr3+ can accommodate six lone pair Give reasons for the following :
of electrons from ligands due to sp3d2 hybridisation e.g.
[Cr(NH3)6]3+ Mn3+ although have d4 configuration but (a) Transition metals have high enthalpies of
tends to become Mn2+ stable specie by acquiring one atomisation.
electron to attain d5 configuration. It becomes exactly
(b) Among the lanthenoids Ce(III) is easily oxidisedto
half filled on one hand and more energy is released in
gain of electron due to higher nuclear charge. Ce(IV).

(b) Co2+ is stable in aqueous solution because it get
surrounded and weakly bonded to water molecules. In
presence of strong ligands and air it gets oxidised tc
Co(III) as strong ligands get co-ordinated more strongly
with Co(III). The electronic configuration of Co(II) and
Co(III) are :
Co(II) = [Ar]18 4s03d7 and Co(III) = [Ar]18 4s03d6
In Co(III) specie, 6 lone pairs of electrons from ligands
are accommodated by sp3d2 hybridisation which is not
possible in Co(II).
(c) Some species with d1 configuration are reducing and
tends to loose one electron to acquire d4 stable
configuration. Some other species with d1 configuration
like Cr(V) and Mn(VI) undergo disproportionation.
(c) Fe3+/Fe2+ redox couple has less positive electrode
potential than Mn3+/Mn2+ couple.
(d) Copper (I) has d10 configuration while copper(II)
has d9 configuration, still copper(II) is more stable
in aqueous solution than copper(I).
(e) The second and third transition series elements have
almost similar atomic radii.
Sol.
(a) The metallic bonds in transition elements are very
strong due to participation of (n – 1) d electrons along
with valence s-electrons in the bond formation.
Therefore, the cleavage of these bonds is extremely
difficult and consequently, enthalpies of atomization
are high.

(b) Ce3 Ce4 e

4f5d 6so o 4f 5d 6so o o
d AND f BLOCK ELEMENTS
Spontaneous oxidation due to more stability of Ce4+ ion
as compared to Ce3+ ion due to more stable
configuration of Ce4+ ion.
(c) Mn3 3e Mn2
(more spontaneous due to higher stability of Fe3+)
Fe3 e Fe2
(less spontaneous due to higher stability of Fe3+) Sol.
Due to stability of half filled d-orbitals, Mn2+ is more (i)
stable than Mn3+ and thus its reduction is more
spontaneous. Similarly Fe3+ is more stable than Fe2+ and
thus its reduction is less spontaneous.
(d) Copper (II) has lower reduction electrode potential
than copper (I), hence. Copper(I) is oxidised to copper Sc Ti V Cr Mn Fe Co Ni Cu Zn
(II) in the presence of strong ligands and air.
(e) It is due to lanthanoid contraction. It arises due to poor
shielding effect of d and f electrons.
Example - 8
Explain the following facts (ii)
(a) transition metals act as catalysts.
(b) chromium group elements have the highest
meltingpoints in their respective series.
(c) transition metals form coloured complexes.
Sol.
(a) The catalytic activity of transition metals is attributed to
the following reasons :
(i) Because of their variable oxidation states transition
metals form unstable intermediate compounds and
provide a new path with lower activation energy for the
reaction.
(ii) In some cases, the transition metal provides a suitable (iii) Except Zn2+, all other divalent gaseous ions of the first
large surface area with free valencies on which reactants
are adsorbed.
(b) Because they have strong metallic bonds due to greater
number of unpaired d electrons.
(c) this is due to d-d transition.
140
Example - 9
Describe the trends in the following properties of the
first series of the transition elements:
(i) Oxidation states
(ii) Atomic sizes
(iii) Magnetic behaviour of dipositive gaseous
2+
ions(M ).
As there is very little energy difference between 4s and
3d orbitals, electrons from both energy levels can be
used for chemical bond formation. Therefore all
elements except Sc and Zn, of the first transition series
show a number of oxidation states as shown in table.
2 2 2 2 2 2 2 1
3 3 3 3 3 3 3 3 2 2
4 4 4 4 4 4 4
5 5 5
6 6 6
7
Atomic radii of the first transition series decreases
fromSc to Cr, then reamins almost constant till Ni and
then increases from Cu to Zn.
The reason of this variation in atomic radii has been
attributed to the increase in nuclear charge in the
beginning of the series. But as the electrons continue to
be filled in d-orbitals, they screen the outer 4s electrons
from the influence of nuclear charge. When the
increased nuclear charge. When the increased nuclear
charge and the increased screening effect balance each
other in the middle of transition series, the atomic radii
becomes almost constant (Mn to Fe). Towards the end
of the series, the repulsive interaction between
electrons in d orbitals become very dominant. As a
result there is an expansion of the electron cloud;
consequently, the atomic size increases.
series of the transition elements contain unpaired
electrons in their 3d subshell and are therefore
paramagnetic in nature.
The magnetic moment ( ) of the elements of the first
transition series can be calculated with the unpaired
electrons (n) by the spin-only formula
d AND f BLOCK ELEMENTS
n 2
n Sol.
Ion
Mn
Cu d 4s
Example - 10
How would you account for the following :
(i) Many of the transition elements and their
compounds can act as good catalysts.
(ii) The metallic radii of the third (5d) series of
transition elements are virtually the same as those
of the corresponding members of the second series.
(iii) There is a greater range of oxidation states among
the actinoids than among the lanthanoids.
Sol.
(i) The catalytic activity of transition metals is attributed to
the following reasons:
(a) Because of their variable oxidation states transition
metals form unstable intermediate compounds and
provide a new path with lower activation energy for
the reaction.
(b) In some cases, the transition metal provides a
suitable large surface area with free vacancies on
which reactants are adsorbed.
(ii) This due to filling of 4f orbitals which have poor
shielding effect or due to lanthanoid contraction.
(iii) This is due to comparable energies of 5f, 6d and 7s
orbital in actinoids.
Example - 11
Decide giving reasons which one of the following pairs
exhibits the property indicated:
(i) Sc3+ or Cr3+ exhibits paramagnetism.
(ii) V or Mn exhibits more number of oxidation states.
141
(Atomic Numbers: Sc = 21; Cr = 24; V = 23; Mn = 25)
(i) The electronic configurations of Sc3+ and Cr3+ are given
below.
Sc3 : Ar 3d 4s 0 0
Cr3 : Ar 3d 4s 3 0
Because of the presence of three unpaired electrons in
the 3d subshell Cr3+ is paramagnetic. Sc3+ is diamagnetic
as it does not have any unpaired electrons.
(ii) The electronic configurations of V and Mn are given
below:
V : Ar 3d 4s 3 2
23
5 2
25Mn : Ar 3d 4s
Mn exhibits more number of oxidation states than V
because of the greater number of electrons in its
valence shell.
Example - 12
How would you account for the following :
(i) Cr2+ is reducing in nature while with the same
dorbital configuration (d4) Mn3+ is an oxidising
agent.
(ii) In a transition series of metals, the metal which
exhibits the greatest number of oxidation states
occurs in the middle of the series.
Sol.
(i) Eo value of Cr3+/Cr2+ is negative (–0.04V) while that of
Mn3+/Mn2+ is positive (1.5 V). This means Cr2+ can lose
electrons to form Cr3+ and thus is reducing in nature
while Mn3+ can gain electrons to form Mn2+ and is thus
oxidising in nature.
(ii) In a transition series maximum number of oxidation
states are shown by that element which has maximum
number of unpaired electrons. That is why the metal in
the middle of the series exhibits maximum number of
oxidation states. For example, manganese, present in
the middle of the first transition series exhibits
maximum oxidation states i.e., +2, +3, +4, +5, +6, +7.
d AND f BLOCK ELEMENTS
Example - 13
Assign reasons for each of the following :
(i) Transition metals generally form coloured
compounds.
(ii) Manganese exhibits the highest oxidation state of
+7 among the 3d series of transition elements.
Sol.
(i) Transition metals generally form coloured compounds.
The colour of compounds of transition metals may be
attributed to the presence of incomplete (n – 1) d
subshell. In the compounds of transition metals the d–
orbitals split
into two sets-t2g dx2 y2 ,dz 2 of lower energy and eg
dxy, dyz, dxz of high energy. The electron can jump
from lower energy t2g orbitals to higher energy eg
orbitals (d–d transition) by absorption of light of some
particular wavelength from visible light. The remainder
light is emitted as coloured light and the compound
appears coloured.
(ii) In a transition series the element with maximum
oxidation state occurs in or near the middle of the
transition series
and maximum oxidation state exhibited is equal to sum
of (n – 1) d and ns electrons. In Mn (3d5 4s2) the sum of
(n – 1) d and (ns) electron is 7 and therefore it exhibits
maximum o.s. of + 7. The lesser no. of oxidation states
on extreme ends are either due to too few electrons to
lose or share or too many d-electrons so that fewer
orbitals are available to share electrons with others.
Example - 14
Explain:
(i) CrO42– is a strong oxidizing agent while MnO42– is
not.
(ii) Zr and Hf have identical sizes.
(iii) The lowest oxidation state of manganese is basic
while the highest is acidic.
(iv) Mn (II) shows maximum paramagnetic
characteramongst the divalent ions of the first
transition series.
142
Sol.
(i) CuF2 and CCl2 compounds will be coloured because they
incompletely filled d-orbitals and unpaired electrons,
they can undergo d-d transition by absorbing colour from
visible region and radiating complementary colour.
(ii) Zr and Hf have identical sizes because paring of
electrons takes place in d-orbitals causing repulsion and
effective nuclear charge does not increase apprecialby.
or becaule of canthanoide contraction.
(iii) Manganese (Z = 25) exhibits the largest number of
oxidation states because its atoms has the maximum
number of unpaired electrons. The lowest oxidation state
of manganese is basic while the highest is acidic.
(iv) Mn(II) shows maximm paramagnetic character amongst
the divalent ions of the first transition series because it
has the largest number of unpaired electrons.
Example - 15
Explain the following facts :
(a) Transition metals acts as catalyst.
(b) Chromium group elements have highest
meltingpoints in their respectively series.
(c) Transition metals form coloured complexes.
Sol.
(a) Transition metals acts as catalyst due to the following
reasons :
(i) Their partially empty d-orbitals provide surface area for
reactant molecules.
(ii) They combine with reactant molecules to form
transitionstates and lowers their activation energy.
(iii) They show multiple oxidation states and by
givingelectrons to reactants they form complexes and
lower their energies.
(b) The melting point of chromium groups elements have
the highest melting points in their respective serves due
to presence of strong intermetallic bonds (formed by
valence electrons and covalent bonds formed due to d–
d overlapping of impaired d-elelctrons.)
(c) Their colour due to the presence of incomplete
dsubshell. The electrons can be excited from one energy
lavel to another with in the d-subshell. The energy
required to cause such d–d promotions or transition falls
d AND f BLOCK ELEMENTS
143
within the visible range for all transition elements. which
When white light falls on an ion or compound, some of counterbalances the increased nuclear charge. Hence,
its wave lengths are absorbed due to d–d transition and along a transition series the atomic radius does not
others are reflected. Therefore, colour of the transition change very much.
metal ion is that of the reflected light.
Example - 18

The Eo (M2+/M) value for copper is positive (+0.34 V).

Example - 16 What is the possibility reason for this ?
Give reasons : Sol. Copper has high Ho and low Ho.
a hyd

(i) Among transition metals, the highest oxidation state

is exhibited in oxoanins of a metal. Example - 19

(ii) Ce4+ is used as an oxidising agent in volumetric

Explain why Cu+ ion is not stable in aqueous solutions
analysis.
?
(iii) Transition metals form a number of
interstitialcompounds. Sol. Cu+ in aqueous solution undergoes disproportionation
i.e.,
(iv) Zn2+ salts are white while Cu2+ salts are blue.

Sol. 2Cu aq Cu2 aq Cu s

(i) Highest oxidation state is shown in flourides and oxides The Eo, value for this is favourable.
because F2 and O2 are strong oxidising agents.
(ii) Ce4+ = [Xe], 4f0, 5d0, 6s0 Example - 20

Ce4+ has the tendency to accept one electron to get the For M2+/M and M3+/M2+ systems the Eo values for some
+3 oxidtion state, hence Ce4+ is a good oxidising agent. metals are as follows :
Cr2+/Cr – 0.9 V Cr3+/Cr2+ – 0.4 V
(iii) In these compounds small size atoms like hydrogen,
carbon, nitrogen, boron, etc. occupy the empty space of Mn2+/Mn – 1.2 V Mn3+/Mn2+ +
metal lattice (interstices). The small entrapped atom in 1.5
V
the interstices form the bonds with metals due to which Fe2+/Fe – 0.4 V Fe3+/Fe2+ + 0.8 V
mobility and ductility of the metals decrease, when as Use this data to comment upon
tensile strength increases. Example : steel is the
(a) The stability of Fe3+ in acid solution as compared
interstitial compound of iron and carbon.
to that of Cr3+ or Mn3+ and
(iv) In Cu2+ salts (3d9) d–d transition is possible. Therefore
Cu2+ salts are coloured. (b) In case with which iron can be oxidised as
In Zn2+ salts (3d10) no. d–d transition is possible due to compared to the similar process for either
completely filled d-orbitals. Hence Zn2+ salts are white. chromium or manganese metal.

Sol.
Example - 17
(a) We know that higher the reduction potential of a
In transition series, with an increase in atomic number,
species, there is larger tendency for its reduction to take
the atomic radius does not change very much. Why is
place. Let us represent the reduction potential i.e., Eo
it so ?
values of three M3+/M2+ systems on number line.
Sol. With the increase in atomic number along a transition Cr3+ / Cr2+ F3+/Fe2+ Mn3+/Mn2+
series the nuclear charge increases which tends to
decrease the size of the atom. But the addition of
electrons in the d subshell increases the screening effect
d AND f BLOCK ELEMENTS
144
From values of reduction potentials, it is clear that the your
stability of Fe3+ in acid solution is more than that Cr3+ answer. (Atomic numbers ; Sc = 21; Ce = 58; Eu = 63).
but less than that of Mn3+.
Sol. The electronic configurations of given species
(b) Mn2+/Mn Cr2+/Cr Fe2+/Fe
are: 21 18 Sc3 Sc

– 1.2 V 0.9 V –0.4 V 0V 1

Ar 3d 4s
The lower the reduction potential of a species, its
oxidation will take place more readily. 2 Ar
Mn is oxidised most readily to Mn2+ and Fe is oxidised
0 0 58
least readily among given metals Mn, Cr and Fe. 3d 4s

54 Ce4 Ce
Example - 21
[Xe] 4f1 3d1 6s2 [Xe]
Which is a stronger reducing agent Cr2+ or Fe2+ and why?
63 61 Eu2 Eu

Sol. Cr2+ is strong reducing agent than Fe2+.

Reason : d4 d3 occurs in case of Cr2+ to Cr3+. 7 2 7

Xe 4f 6s Xe 4f
But d6 d5 occurs in case of Fe2+ to Fe3+. In a medium
Ce4+ is a good oxidising agent because it can readily
(like water) d3 is more stable as compared to d5.
change to the most stable +3 oxidation state by gaining
Example - 22 one electron.

What may be the stable oxidation state of the transition Ce4 e Ce3
element with the following d electronic configurations
in the ground state of their atoms : 3d3, 3d5, 3d8 and 3d4? Because of their stable configuration Sc3+ and Eu2+
cannot gain electrons.
Sol. The stable oxidation state of transition element with the
d electron configuration in ground state of atoms are as Example - 24
follows :
Silver atom has a completely filled d orbitals (4d10) in
S. No. d-electron Symbol of Stable oxidation
its ground state. How can you say that it is a transition
configuration element states element ?
2 3
1. 3d3 +2, +3, +5
V(4s 3d ) Sol. Silver (Z = 47) can exhibit +2 oxidation state wherein it
2. 3d4 +2, +3, +6
2 4
3. +2, +7 will have incompletely filled d-orbitals (4d), hence a
3d5 Cr(4s 3d )
4. 2 5 +2, +4 transition metal.
3d8 Mn(4s 3d )
2 8
Example - 25
Ni(4s 3d )
It should be noted that lower stable oxidation state On what ground can you say that scandium (Z = 21) is a
generally leads to ionic bond and higher oxidation state transition element but zinc (Z = 30) is not ?
corresponds to covalent bond.
Sol. On the basis of incompletely filled 3d orbitals in case of
Example - 23 scandium atom is its ground state (3d1), it is regarded as
a transition element. On the other hand, zinc atom has
Among the ionic species Sc3+, Ce4+ and Eu2+ which one
completely filled d orbitals (3d10) in its ground state as
is a good oxidising agent? Give a suitable reason for
well as in its oxidised state, hence it is not regarded as
a transition elements.
d AND f BLOCK ELEMENTS
Example - 26
In the series Sc (Z = 21) to Zn (Z = 30), the enthalpy of
atomisation of zinc is the lowest i.e., 26, kJ mol. Why ?
Sol. In the formation of metallic bonds no electrons from
3dorbitals are involved in case of zinc, while in all other
metals of the 3d series, electrons from the d-orbitals are
always involved in the formation of metallic bonds.
Example - 27
Calculate the ‘spin only’ magnetic moment of M(aq)2+ ion
(Z = 27).
Sol. Atomic number (27) = [Ar]3d7 4s2
M aq2 Ar 3d 7
n=1
nn 2 13 1.73 BM.
Example - 28
What are alloys ? Mention an important alloy which
contains some of the lanthanoid metals. Mention its
uses.
Sol. An alloy is a mixture of a metal with other metals or
nonmetals.
An important alloy which contains some of the
lanthanoid is mischmetall. Mischmetall consists of a
lanthanoid metal (~95%) and iron (~5%) and traces of
S, C, Ca and Al.
Uses : (i) Mischmetall is used in Mg based alloy to
produce bullets, shell and lighter flint.
Some individual Ln oxides are used as phosphorus in
television screens and similar fluorescing surfaces.
Example - 29
What are interstitial compounds ? Why are such
compounds well known for transition metals ?
Sol. Interstitial compounds are those which are formed when
small atoms like H, C, N, B etc. are trapped inside the
crystal lattices of metals. They are generally
nonstoichiometric and neither typically ionic nor
covalent.
145
Most of
transition metals form interstitial compounds with small
non-metal atoms such as hydrogen, boron, carbon and
nitrogen. These small atoms enter into the void sites
between the packed atoms of crystalline transition
metals. For Example, steel and cast iron become hard by
forming interstitial compound with carbon.
The existence of vacant (n – 1) d orbitals in transition
elements and their ability to make bonds with trapped
small atoms in the main cause of interstitial compound
formation. Other examples are : VH0.56, TiH1.7. Some
main characteristics of these compounds are :
(i) They have high melting and boiling points, higher than
those of pure metals.
(ii) They are very hard. Some borides of transition elements
approach diamond in hardness.
(iii) They are chemically inert but retain metallic
conductivity.
Example - 30
How would you account for the irregular variation of
ionisation enthalpies (first and second) in the first series
of the transition elements ?
Sol. Irregular variation of ionisation enthalpies in mainly
attributed to varying degree of stability of different
3dconfigurations (e.g., d0, d5, d10 are exceptionally
stable).
Example - 31
Assign a reason for each of the following :
(i) The third ionization energy of Mn(Z = 25) is higher
than that of either Cr (Z = 24) or Fe (Z = 26).
(ii) Simple copper (I) salts are not stable in aqueous
solutions.
Sol.
(i) This is because Mn2+ is more stable as it has exactly half
filled configuration 3d5 4s0.
(ii) Cu2+ (aq) is much more stable than Cu+ (aq). This is
because, although second ionization enthalpy of copper
is large but for Cu2+ (aq) is much more negative than that
of Cu+ (aq) and therefore, it more compensate for the
d AND f BLOCK ELEMENTS
second ionisation enthalpy of copper. Therefore, Cu +
ion aqueous solution undergoes disproportionation.
2Cu2 aq Cu2 aq Cu s
Example - 32
Explain giving reasons :
(i) Transition metals and their compounds generally
exhibit a paramagnetic behaviour.
(ii) The Chemistry of actinoids is not so smooth asthat
of lanthanoids.
Sol.
(i) Paramagnetism is a property due to presence of unpaired
electrons. In case of transition metals, as they contain
unpaired electrons in (n – 1) d orbitals, most of the
transition metal ions and their compounds are
paramagnetic.
(ii) The general electronic configuration of lanthanoids is
[Xe]54 4f0–4 5d0–1 6s2 and that of actinoids is [Rn]86 5f1–
14 6d0–1 7s2. Unlike 4f orbitals, 5f orbitals are not deeply
burried and participate in bonding to a greater extent.
In actinoids due to poor shielding effect of 5f orbitals,
the effective nuclear charge experienced by valence
shell electrons is more than those in lanthanoids. As a
result the Chemistry of actinoids is not so smooth as
that of lanthanoids.
Example - 33
Which of the 3d series of the transition metals exhibits
the largest number of oxidation states and why ?
Sol. Manganese (Z = 25), as its atoms has the maximum
number of unpaired electrons.
Example - 34
Explain briefly how +2 state becomes more and more
stable in the first half of the first row transition
elements with increasing atomic number ?
Sol. In transition elements, there are greater horizontal
similarities in the properties in constrast to the main
group elements because of similar ns 2 common
configuration of the outermost shell.
An examination of common oxidation states reveals that
excepts scandium, the most common oxidation state of
146
first row
transition elements is +2 which arises from the loss of
two 4s electrons. This means that after scandium, d-
orbitals become more stable than the s-orbital.
Further, +2 state becomes more and more stable in the
first half of first row transition elements with increasing
atomic number because 3d orbitals acquire only one
electron in each of five 3d orbitals (i.e. remains half
filled) and electronic repulsion is the least and nuclear
charge increases. In 2nd half of first row transition
elements, electrons starts pairing up in 3d orbitals.
(Ti2+ to Mn2+ electronic configuration changes from 3d2
to 3d5 but in 2nd half i.e. Fe2– to Zn2+ it changes from d6
to d10).
Example - 35
To what extent do the electronic configurations decide
the stability of oxidation states in the first series of the
transition elements ? Illustrate your answer with
example.
Sol. One of the main characteristic of a transition element is
that it can show large variety of oxidation states in its
compounds. It is due to its characteristic electronic
configuration i.e., (n – 1) d and ns electrons take part in
bond formation either by loosing or by sharing of
electrons with other combining atoms.
The stability of oxidation state depends mainly on
electronic configuration and also on the nature of other
combining atom.
The elements which show largest number of oxidation
states occur in or near the middle of series (i.e., 4s23d3 to
4s23d7 configuration). For example, Mn exhibits all
oxidation states from +2 to +7 as it has 4s 23d5
configuration. The lesser number of oxidation states at
extreme ends arise from either too few electrons to loose
or share (e.g. Sc and Ti) or too many d electrons (hence
fewer orbitals available in which to share electrons with
others) for higher elements at upper end of first
transition series (i.e., Cu and Zn). Thus electronic
configuration, to large extent, the existence and stability
of oxidation states.
The other factors which determine stability of oxidation
state are:
(i) Enthalpy of atomisation (ii) Ionisation energy (iii)
Enthalpy of solvation (iv) E.N. of other element.
d AND f BLOCK ELEMENTS
147
Example - 36 e.g., cuprous
oxide (Cu2O), cuprous sulphide (Cu2S); cuprous
How is the variability in oxidation states of transition chloride (Cu2Cl2) etc. The electronic configuration of
metals different from that of the non-transition metals Cu+ is [Ar] 3d10 4s0.
? Illustrate with examples
This configuration is very stable as all five 3d orbitals
Sol. The variability in oxidation states is a fundamental are fully filled.
characteristic of transition elements and it arises due to
incomplete filling of d-orbitals in such a way that their Example - 39
oxidation states differ from each other by unity. For
example, vanadium, V show the oxidation states of +2, Why is the highest oxidation state of a metal exhibited
+3, +4 and +5. Similarly, Cr shows oxidation states of in its oxide or fluoride only ?
+2, +3, +4, +5 and +6; Mn shows all oxidation states
Sol. Because of small size and high electronegativity oxygen
from +2 to +7.
or fluorine can make the metal to exhibit its highest
This is contrasted with variability of oxidation states of oxidation state.
non-transition element where oxidation states generally
Example - 40
differ by units of two. For example, S shows oxidation
states of –2, +2, +4, +6 while P shows +3 and +5 Name the oxometal anions of the first series of the
oxidation states. Halogenes like Cl, Br and I show transition metals in which the metal exhibits the
oxidation states of –1, +1, +3, +5 and +7 states. In non- oxidation state equal to its group number.
transition elements variability of oxidation states is
caused due to unpairing of electrons in ns or np orbitals Sol.
Name of oxometal Name of metal with Group no. to which
and their promotion to np or nd vacant orbitals.
anion oxidation state metal belong
Example - 37 1. CrO42– 6th group of
Cr in +6 state of
Discuss the relative stability in aqueous solutions of (chromate ion) oxidation periodic table
+2 oxidation state among the elements: Cr, Mn, Fe 2. MnO4– 7th group
and Co. How would you justify this situation ? Mn in +7 state
(permanganate ion)
(At. Nos. Cr = 24, Mn = 25, Fe = 26, Co = 27) Example - 41

Sol. On the basis of electrochemical series the standard Why are Zn, Cd and Hg softer and volatile metals ?
electrode potential shows the following order
Sol. Due to their completely filled d-orbitals, they have weak
EoMn2 /Mn EoCr 2 /Cr EoFe 2 / Fe EoCo
2 / Co metallic bonding and least compact packing therefore
they all are volatile in nature.
Therefore Co2+ gets easily reduced to metallic cobalt
while it is difficult to reduce Mn2+. Hence Mn2+ will be Example - 42
most stable and the increasing stability order will be
Describe the preparation of potassium dichromate
Co2+ < Fe2+ < Cr2+ < Mn2+ from iron chromite one. What is the effect of
increasing pH on a solution of potassium dichromate ?
Example - 38
Sol. The following steps are involved in preparation of
Which metal in the first series of transition metals K2Cr2O7 from iron chromite (FeCr2O4) ore :
exhibits +1 oxidation state most frequently and why ?
(i) Preparation of sodium chromate : The chromite ore
Sol. Copper metal (Cu, at, no. 29) shows + 1 oxidation state (FeO.Cr2O3) is finely powdered and mixed with sodium
i.e., it exists as Cu+ in large number of copper carbonate and quick lime and then heated to redness in a
compounds reverberatory furnace with free supply of air.
4FeO.Cr2O3 + O2 2Fe2O3 + 4Cr2O3
[4Na2CO3 + 2Cr2O3 + 3O2 4Na2CrO4 + 4CO2] × 2
d AND f BLOCK ELEMENTS
148
The green
4FeO.Cr2O3 + 8Na2CO3 + 7O2 8Na2CrO4 + 2Fe2O3 + 8CO2 mass is dissolved in water to obtain aqueous solution of
potassium manganate. The insoluble impurities of sand
The mass is then extracted with water, when sodium and other metal oxides are removed by filtration.
chromate is completely dissolved while Fe2O3 is left
behind. (ii) Oxidation of manganate into permanganate : The
aqueous solution of K2MnO4 is oxidised electrolytically
(ii) Conversion of sodium chromate into sodium dichromate or by using ozone or Cl2 to obtain potassium
(NaCr2O7) : The sodium chromate extracted with water permanganate. The process is carried out till green
in previous step is acidified. colour disappear and solution acquires distinct pink
colour.
3Na2CrO4 + H2SO4 Na2Cr2O7 + Na2SO4 + H2O

On cooling Na2SO4 separates out as Na2SO4. 10H2O and MnO at anode4 2 MnO4 e (oxidation at
Na2Cr2O7 is remains in solution. anode)
pink
greencoloure
(iii) Conversion of Na2Cr2O7 into K2Cr2O7 : The solution
containing Na2Cr2O is treated with KCl H2O + e– 1/2H2 + (OH)– (reduction at cathodes)

Na2Cr2O7 + KCl K2Cr2O7 + 2NaCl (at cathode)

Sodium chloride (NaCl) being less soluble separates
out on cooling. On crystallising the remaining solution, or 2K MnO2 4 CI2 2KMnO4 2KCI
greencolour pinkcolour
orange coloured crystals of K2Cr2O7 separate out.

Effect of Change of pH : When pH of solution of
K2Cr2O7 is increased slowly the medium changes from
acidic to basic. The chromates and dichromates are
interconvertible in aqueous solution depending upon
pH of solution.
Potassium permanganate is crystallised out from the
solution.
Oxidising Properties : It acts as a powerful oxidising
agent in different media differentily. In acidic medium,
it oxidises iron(II) salts to iron(III) salts, SO 2 to H2SO4
and oxalic acid to CO2 and H2O.

(a) It oxidises iron(II) salt to iron(III) salts.

2MnO42- + 16+ + 10Fe2+ 2Mn2+ + 8H2O + 10Fe3+

7
At low pH (acidic medium), K2Cr2O solution is
oranged coloured while at higher pH (alkaline medium) (b) It oxidise sulphur dioxide to sulphuric acid.
it changes to yellow due to formation of chromate ions.
2MnO4– + 5SO2 + 2H2O 5SO42– + 2Mn2+ 4H+
Example - 43

Describe the preparation of potassium permanganate. (c) It oxidises oxalic acid to CO2 and H2O
How does the acidified permanganate solution reacts
2MnO4– + 16H+ + 5C2O42– 2Mn2+ + 8H2O + 10CO2
with (a) iron(II) ions (b) SO2 and (c) oxalic acid ?
Write the ionic equations for the reactions.
Example - 44
Sol. Preparation of KMnO4 from pyrolusite ore (MnO2) Indicate the steps in the preparation of :
involves the following steps :
(a) K2Cr2O7 from chromite ore
(i) Fusion of ore with alkali in presence of air : Pyrolusite
ore is fused with alkali in the presence of air when (b) KMnO4 from pyrolusite ore.
potassium manganate is obtained as green mass.
Sol.
2MnO2 + 4KOH + O2 2K2MnO4 + 2H2O
(green mass)
d AND f BLOCK ELEMENTS
149
(a) The preparation of potassium dichromate from chromite (ii) 2MnO4– +
involves the following main steps : 3S2O32– + H2O 2MnO2 + 3SO42– +
3S + 2OH–.
(i) The chromate ore is finely ground and heated strongly
with molten alkali in the presence of air. Example - 46
2FeCr O2 4 8NaOH 7/2O2 4Na Cr O2 2 4 Fe O2 Complete the following chemical equations :
3 4H O2
Chromite Sodium chromate

(ii) The solution of sodium chromate is filtered and (i) MnO 4 aq S O 2 32 aq H O2

acidified with dilute sulphuric acid so that sodium
dichromate is obtained. (ii) Cr O2 72 aq Fe2 aq H aq

2Fe Cr O2 2 4 H SO3 4 Na Cr O2 2 7 Na Or
SO2 4 H O2
Sodium Chromate Sodium dichromate State reasons for the following :
(iii) A calculated quantity of potassium chloride is added toa
(i) Cu (I) ion is not stable in an aqueous solution.
hot concentrated solution of sodium dichromate.
Potassium dichromate is less soluble therefore it (ii) Unlike Cr3+, Mn2+, Fe3+ and the subsequent other
crystallizes out first. M2+ ions of the 3d series of elements, the 4d and
the 5d series metals generally do not form stable
Na Cr O2 27 2KCl K Cr O2 2
cationic species.
7 2NaCl
Sodium Potassium dichromate dichromate
Sol.
(b) (i) Pyrolusite ore is fused with alkali in the presence of air
when potassium manganate is formed.
(i) 8MnO 4 aq 3S O2 32 aq H O2 6
2
2MnO2 4KOH O2 2K MnO24 2H O2 SO 4

(aq) + 8MnO2 + 2OH– (aq)

Potassium manganate

2
(ii) Cr O2 7 aq 6Fe2 aq 14H aq 2
(ii) Potassium manganate is oxidised by using either
CO2, ozone or chlorine to potassium permanganate. Cr3

2K MnO24 Cl2 2KMnO4 2KCl (aq) + 6 Fe3+ (aq) + 7H2O (l)

Potassium Or
permanganate

(iii) Potassium permanganae is crystallized from (i) Cu2+ (aq) is much more stable than Cu+ (aq. This is due
thesolution. to more negative hydH more than compensates for
H
i 2. As a result Cu(I) is unstable in aqueous solution
Example - 45
and undergoes disproportionation as below :
Write complete chemical equations for :
2Cu Cu2 Cu
(i) Oxidation of Fe2+ by Cr2O72– in acid medium.
(ii) The valence shell electronic configuration of Cr3+, Mn2+,
Fe3+ is d3, d5 respectively. Due to symmetrical
(ii) Oxidation of S2O32– by MnO 4 in neutral aqueous
distribution
solution. e
of electrons (Either t32g or t32g g2 ) they form stable
Sol. (i) 6Fe2+ + Cr2O72– + 14 H+ 6Fe3+ + 2Cr3+ + 7H2O cationic complexes. The atomic radii of 4d and 5d
d AND f BLOCK ELEMENTS
150
transition metal at elements are more than those of 3d Reactions :
series. Hence. they generally do not form stable cationic
complexes. FeSO .7H O4 2

7HeatH O2 FeSO4
(A)
Example - 47

Complete the following chemical reaction equations: Heat Fe O23 SO SO2 3

(B) (C) (D)
Blackish
2 brown powder
(i) MnO 4 aq C O2 4 aq H
aq
Fe O2 3 6HCl 2FeCl3 3H O2
(B) (E)
Yellow solution
2 2
(ii) Cr O2 7 aq Fe aq H aq

2FeCl3 H S2 2FeCl2 2HCl S

Sol. (i) MnO 4 8H 5e Mn2 4H O2 ] 2 (G) (F)
Apple White green solution
turbidity
C O242 2CO2 2]5

2
2MnO 5C O 4 24 16H 2Mn2 10CO 8H O2 FeCl3 3CNS Fe(CNS)3 3Cl
2 (E) Blood red coloured
solution

Example - 49
(ii) Cr O272 14H 6e 2Cr3 7H O2
(i) A black mineral (A) on treatment with dilute
Fe 2 Fe 3 e]6 sodium cyanide solution in presence of air gives
a clear solution of (B) and (C).
2 2 3 3

Cr O2 7 6Fe 14H 2Cr 6Fe 7H O2 (ii) The solution (B) on reaction with zinc gives
precipitate of a metal (D).
(iii) (D) is dissolved in dilute HNO3 and the resulting
Example - 48
solution gives a white precipitate (E) with dilute
A certain inorganic compound (A) on heating loses its HCl.
water of crystallisation. On further heating, a blackish
(iv) (E) on fusion with sodium carbonate gives (D).
brown powder (B) and two oxides of sulphur (C and
D) are obtained. The powder (B) on boiling with (v) (E) dissolves in ammonia solution giving a
hydrochloric acid gives a yellow solution (E). When colourlesssolution of (F). Identify (A) to (F) and
H2S is passed in (E), a white turbidity (F) and apple give chemical equations for reactions at steps (i)
green solution (G) are obtained. The solution (E) on to (v).
treatment with thiocyanate ions gives a blood red Sol. On the basis of the given data, the black mineral (A) is
coloured compound (H). Identify the compounds from silver glance, Ag2S. It is confirmed by the following :
(A) to (H).
(i) It dissolves in sodium cyanide solution in
presence of air.
Sol. The compound (A) on strong heating gives two oxides of
sulphur, it may be a sulphate. The solution (E) on Ag2S + 4NaCN + 2O2 2[NaAg(CN) ]2 Na SO24
treatment with thiocyanate ions gives blood red Sodium Sodium argento cyanide
sulphate
coloured compound (H) indicates that the solution (E) (B) (C)

consists Fe3+ ions. Thus, the compound (A) is ferrous

sulphate, FeSO4.7H2O.
(ii) Iron reacts with cold dilute nitric acid.
2[NaAg(CN) ] Zn Na Zn(CN) 2Ag
(ii) 2 2 4 (D)
(B)
d AND f BLOCK ELEMENTS
151
(iii) Potassium ferricyanide is added to ferrous sulphate.
3Ag 4HNO 3AgNO NO 2H O
3 3 2
(iii) (D) (iv) Excess of potassium iodide is added to mercuric
chloride.
AgNO3 HCl AgCl HNO3
(E) (v) Green vitriol is strongly heated.

(iv) 2AgCl Na CO 2 3 2Ag 2NaCl CO2 O2 (vi) Silver chloride is treated with
aqueous sodium
(E) (D)
cyanide and the product thus formed is allowed to
react with zinc in alkaline medium.
AgCl 2NH OH4 Ag(NH ) Cl3 2 2H O2
(v) (E) (F)
Colourless solution (vii) Zinc oxide is treated with excess of sodium
(A) = Silver glance, Ag2S hydroxide solution.

(B) = Sodium argentocyanide, NaAg(CN)2 (viii) Ammonium thiocyanate is added to ferric chloride

(C) = Sodium sulphate, Na2SO4 solution.

(D) = Silver metal, Ag
(E) = Silver chloride, AgCl Sol. (i) Prussian blue is formed.
(F) = Diamminsilver (I) chloride, Ag (NH3)2Cl
4FeCl 3K Fe(CN) Fe [Fe(CN) ] 12KCl

(Ferri ferrocyanide)
Example
Write the main differences in lanthanides and actinides.
- 50 3
4
Sol. (ii) Ammonium nitrate is formed. 6
4Prussian blue6 3
Lanthanides Actinides

1. Actinides show [Fe + 2HNO3 Fe(NO3)2 + 2H] × 4

1. Lanthanides shows higher oxidation states
+3 oxidation state only such as +4, +5, +6, +7
except in few cases where also in addition to +3. HNO3 + 8H NH3 + 3H2O
it is +2 or +4. Oxidation
states exhi bited by NH3 + HNO3 NH4NO3
lanthanides is never more
than +4. 2. Paramagnetic
2. Paramagnetic 4Fe + 10HNO3 4Fe(NO3)2 + NH4NO3 + 3H2O
proper-
properties of lanthanides ties are difficult to
can be easily explained. interpret. (iii) Ferrous ion is first oxidised to ferric ion whileferricyanide ion
3. Lanthanides do not 3. They have a greater is reduced to ferrocyanide ion. Then, ferric ions react with
form form complexes. tendency to complex ferrocyanide ions to form potassium ferric ferrocyanide
formation. Even p - (Turnbull’s blue).
complexes are formed
by actinides.
54.. Lanthanides do not 54.. These in higher Fe2+ + K3 [Fe (CN)6]3– KFe [Fe(CN) ]6
(Turnbull's Blue)
form axo ions. oxidation states form axo
ions.
65.. Except promethium,
these are ion-radioactive 65.. Such as Uo22+, NbO ,+
PuO22+ etc.
d AND f BLOCK ELEMENTS
152

(iv) First scarlet precipitate is formed which then dissolvesin

excess of potassium iodide forming a complex.

HgI
HgCl2 + 2KI 2 + 2KCl
Example - 51
HgI2 + 2KI K2HgI4
What happens when ?
Potassiumtetraiodomercurate(II) (i)
Ferric chloride is added to potassium ferrocyanide.
(colourless)

(v) When heated strongly, a mixture of gases consisting

of SO2 and SO3 is evolved and a red residue, Fe2O3 (i) Acidified K2Cr2O7 solution turns green when
is formed. sodium sulphite is added to it. (ii) Zinc becomes dull in
[FeSO4.7H2O FeSO4 + 7H2O] × 2 moist air.
(iii) A little acid is always added in the preparationof
2FeSO4 Fe2O3 + SO2 + SO3
aqueous ferrous sulphate solution.
SO3 + H2O H2SO4 (iv) The addition of NaOH solution to a solution of
zincchloride produces a white precipitate which
2FeSO4.7H2O Fe2O3 + SO2 + H2SO4 + 13H2O dissolves on further addition of NaOH.
Green vitriol Red
(v) The addition of NH4OH to ZnSO4 solution
(vi) AgCl dissolves in KCN forming a complex, produces white precipitate but no precipitate is
potassiumargentocyanide. The addition of zinc formed if it contains NH4Cl.
precipitates silver.
(vi) Zinc and not copper is used for the recovery
AgCl + 2KCN KAg(CN)2 + KCl
ofsilver from complex [Ag(CN)2]–.
2KAg(CN)2 + Zn K2Zn(CN)4 + 2Ag
(vii) Copper sulphate dissolves in NH4OH solution but
Potassium zincocyanide
FeSO4 does not.
(vii) ZnO dissolves in NaOH forming sodium zincate.
(viii) Copper hydroxide is soluble in
ZnO + 2NaOH Na2ZnO2 + H2O ammoniumhydroxide but not in sodium
hydroxide.
(viii) Deep red colouration due to the formation of
acomplex is developed. Na
Sol. (i) 2SO3 is a reducing agent. It reduces acidified K2CrO7
FeCl3 + NH4CNS Fe(CNS)Cl2 +
to chromic sulphate which is green in colour.
NH4Cl or FeCl3 + 3NH4CNS Fe(CNS)3 +
K2Cr2O7 + 4H2SO4 K2SO4 + Cr2(SO4)3 + 4H2O + 3 [O]
3NH4Cl
[Na2SO3 + [O] Na2SO4] × 3

K2Cr2O7 + 3Na2SO3 + 4H2SO4 K2SO4 + Cr2(SO4)3

Example - 52
Green
Explain the following :

+ 3Na2SO4 + 4H2O
d AND f BLOCK ELEMENTS
153
(ii) When zinc is exposed to moist air, the surface is FeSO4 + 2NH4OH Fe(OH)2 + (NH4)2SO4
affected with the formation of a film of basic zinc Insoluble

carbonate on it. Due to this zinc becomes dull. [2Zn

(viii) Cu(OH)2 dissolves in NH4OH by forming a
+ 2H2O + O2 2Zn (OH)2] × 2 Zn(OH)2 +
complex.
CO2 ZnCO3 + H2O
Cu(OH)2 + 4NH4OH [Cu(NH3)4] (OH)2 +
ZnCO3 + 3Zn(OH)2 ZnCO3.3Zn (OH)2 4H2O Cu(OH)2 is insoluble in NaOH as no such
complex is formed.
4Zn + 3H2O + CO2 + 2O2 ZnCO3.3Zn(OH)2
Basic zinccarbonate
Example - 53
(iii) Ferrous sulphate is a salt of a weak base and a A metal chloride (x) shows the following reactions :
strongacid. Thus, its hydrolysis occurs when it is (a) When H2S is passed in an acidified solution of (x)
dissolved in water and solution becomes turbid due a black precipitate is obtained.
to formation of ferrous hydroxide.
(b) The black precipitate is not soluble in
FeSO4 + 2H2O Fe(OH)2 + H2SO4 ammoniumsulphide.
Addition of a small amount of acid shifts the (c) The solution of stannous chloride is added to an
equilibrium towards left and thus prevents aqueous solution of (x), a white precipitate is
hydrolysis. obtained which turns grey on addition of more
(iv) On addition of NaOH, a white precipitate of Zn stannous chloride.
(OH)2 is formed which dissolves in excess of NaOH (d) When aqueous solution of KI is added to
forming sodium zincate. anaqueous solution of (x), a red precipitate is
ZnCl2 + 2NaOH Zn(OH)2 + 2NaCl obtained which dissolves on addition of excess of
Zn (OH)2 + 2NaOH Na2ZnO2 + 2H2O KI.
Soluble Identify (x) and write down the equations for the
(v) NH4OH is a weak hydroxide. It ionises slightly reactions.
furnishing OH– ions. However, the OH– ions are
Sol. The acidified solution of (x) gives a black sulphide with
sufficient to cause the precipitation of Zn(OH)2 as
H2S indicates that the chloride is of a basic cation of
its solubility product is exceeded.
second group. The sulphide is insoluble in ammonium
ZnSO4 + 2NH4OH Zn(OH)2 + (NH4)2SO4 sulphide, hence, the cation belongs to IIA group of
white ppt. mixture analysis.
In presence of NH4Cl, the ionisation of NH4OH is It gives white precipitate with SnCl2 which turns to
further suppressed and sufficient OH– ions are not
grey in excess of SnCl2 suggests that (x) is HgCl2. It is
available to cause precipitation as the solubility
product is not exceeded. further confirmed by the reaction with KI.
(vi) Zinc is cheaper as well as stronger reducing agent Reactions :
incomparison to copper. HgCl2 + H2S HgS + 2HCl
– 2–
Zn + 2[Ag(CN)2] 2Ag + [Zn(CN)4] Black

(vii) Copper sulphate dissolves in the 2HgCl2 + SnCl2 Hg2Cl2 + SnCl4

ammoniumhydroxide due to formation of a copper white
complex. Ferrous sulphate reacts with NH4OH to
form insoluble Fe(OH)2. It does not form any Hg2Cl2 + SnCl2 2Hg + SnCl4
complex with Grey
NH4OH.
HgI
HgCl2 + 2KI 2 + 2KCl
CuSO4 + 4NH4OH [Cu(NH3)4]SO4 + 4H2O Red ppt.
Deep blue solution
d AND f BLOCK ELEMENTS
154
HgI2 + 2KI K2HgI4 The no. of unpaired electron = 1
Soluble
‘Spin only’ formula for magnetic moment of a specie,
Example - 54

Describe the oxidising action of potassium dichromate nn 2 B.M.

and write the ionic equations for its reaction with : Magnetic moment of Ce3+
(a) iodide (b) iron (II) solution and (c) H2S.

Sol. Potassium dichromate, K2Cr2O7 is a strong oxidising agent

and is used as a primary standard in volumetric analysis 3
involving oxidation of iodides, ferrous ion and S2– ions
etc. In acidic solution, its oxidising action can be Example - 57
represented as follows :
What is lanthanoid contraction ? What are the
Cr2O72– + 14H+ + 6e– 2Cr3+ + 7H2O; (E+ = 1.33 V) consequences of lanthanoid contraction ?

(a) It oxidises potassium iodide to iodine. Sol. A group of fourteen elements following lanthanum i.e.
from 58Ce to71 Lu placed in 6th period of long form of
Cr2O72– + 14H+ 6I– 2Cr3 + 7H2O + 3I2 periodic talbe are known as lanthanoids (or lanthanide
series). These fourteen elements are represented by
(b) It oxidises iron(II) salt to iron (III) salt
common general symbol ‘Ln’. In these elements, the
last electron enters the 4f-subshells (pre penultimate
Cr2O72– + 14H+ + 6Fe2+ 2Cr3+ + 6Fe3+ + 7H2O
shell). It may be noted that atoms of these elements
have electronic configuration with 6s2 common but
(c) It oxidises H2S to S
with variable occupancy of 4f level. However, the
Cr2O72– + 8H+ + 3H2S 2Cr3+ + 7H2O + 3S electronic configuration of all the tripositive ions (the
most stable oxidation state of all lanthanoids) are of the
Example - 55 form 4f n(n = 1 to 14) with increasing atomic number).
These elements constitute one of the two series of inner
Write the electronic configurations of the elements with transition elements or f-block.
the atomic numbers 61, 91, 101 and 109.
Lanthanoid contraction : In the lanthanoide series with
Sol. Atomic number (61) = [Xe] 4f5 6s2. the increase in atomic number, atomic radii and ionic
Atomic number (91) = [Rn] 5f2 6d1 7s2 radii decrease from one elements to the other, but this
decrease is very small. the regular small decrease in
Atomic number (101) = [Rn] 5f14 7s1 atomic radii and ionic radii of lanthanides with
increasing atomic number along the series is called
Atomic number (109) = [Rn] 5f14 6d7 7s2.
lanthanoid contraction.
Example - 56 Cause of lanthanoid contraction: When one moves from
58Ce to 71Lu along the lanthanide series nuclear charge
Use Hund’s rule to derive the electronic configuration
of Ce3+ ion, and calculate its magnetic moment on the goes on increasing by one unit every time.
basis of ‘spin only’ formula. Simultaneously an electron is also added which enters
to the inner f subshell. The shielding effect of f-orbitals
Sol. The electronic configuratio of Ce and Ce3+ ion is : in very poor due to their diffused shape. It results in the
stronger force of nuclear attraction of the 4f electrons
Ce(Z = 58) = 54[Xe] 4f15d16s2 and the outer electrons causing decrease in size.

Ce3+ = 54[Xe] 4f1 Consequences of lanthanoid contraction:

d AND f BLOCK ELEMENTS
155
(i) Similarly in the properties of elements of second and stable due to half filled and full filled f-subshell.
third transition series e.g. Zr and Hf; Nb and Ta; Mo Samarium, Sm (62) 4f6 6s2 also shows both +2 and +3
and W. This resemblance is due to the similarity in size oxidation states like europium.
due to the presence of lanthanoids in between.
Example - 60
(ii) Similarity among lanthanoids : Due to the very small
change in sizes, all the lanthanoids resemble one Account for the following:
another in chemical properties.
(i) Cerium (atomic number = 58) forms tetra positive
(iii) Decrease in basicity : With the decrease in ionic ion, Ce4+ in aqueous solution.
radii,covalent character of their hydroxides goes on
(ii) The second and third members in each group
increasing from Ce(OH)3 to Lu(OH)3 and so base
oftransition element have similar atomic radii.
strength goes on decreasing.
Sol.
Example - 58
(i) The electronic configuration of Ce (Z = 58) is 58Ce = [Xe]
What is meant by ‘lanthanoid contraction’ ? 4f1 5d1 6s2
Sol. The regular decrease (contraction) in the atomic and ionic Cerium can lose four electrons (4f1 5d1 6s2) in aqueous
radii with increasing atomic number from lanthanum to solution to acquire stable configuration of rare gas
lutetium along the lanthanoid series is called lanthanoid
xenon. Moreover due to small size and high charge, Ce4+
contraction. ion has high hydration energy.
Example - 59
(ii) The second and third members in each group of
Name the members of the lanthanoid series which transition elements have very similar atomic radii due to
exhibit +4 oxidation states and those which exhibit +2 lanthanoid contraction. It arises due to poor shielding
oxidation state. Try to correlate this type of behaviour effect of electrons.
with the electronic configurations of these elements.

Sol. Cerium (Ce) and Terbium (Tb) show +4 oxidation state.

Their electronic configurations are given below :
Ce = [Xn] 4f1 5d1 6s2

Tb = [Xn] 4f0 6s2

It is clear from the configuration of Ce that Ce+4 is

favoured by its noble gas configuration i.e., [Xn] 4f0 5d0
5s0, but can be easily converted into Ce 3+ ([Xn]) 4f1 5d0
6s0). Due to this reason Ce+4 is an oxidising agent. Tb4+
ion is stabilized due to half filled f-subshell i.e., [Xn] 4f7.
It also acts as an oxidant.

Europium (63) and ytterbium (70) show +2 oxidation

state, this acts as reducing agents because they can be
converted into common oxidation state +3. The
electronic configuration of Eu and Y are as follows :
Eu = [Xn] 4f7 6s2

Y = [Xn] 4f14 6s2

Formation of Eu2+ ion leaves 4f7 configuration and Y2+

ion leaves 4f14 configuration. These configurations can