CLASS XII

Detailed Notes As Per BOARD Examination

CHEMISTRY

CHAPTER-8
d- & f- Block Elements

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 d- & f - Block Elements

d & f - Block Elements

d-block elements
The elements in which the last electron enters the d-orbital of the the atom are called d-block elements. The
d-block element are called transition elements.
The transition elements are those elements which have pmally filled d-subshellsin their elementcy form or in
their common occuring oxidation states.

Note
 Although all elements are transition elements but Zn, Cd and Hg do not exhibit characteristic properties
of transition elements as they do not have partly filled d-subshells in their elementcy state or in their
common occuring oxidation states.

st nd rd th
I Series 2 Series 3 Series 4 Series

E Z E.C. E Z E.C. E Z E.C. E Z E.C.

2 1 2 1 2 1 2 1
Sc 21 4s 3d Y 39 5s 4d La 57 6s 5d Ac 89 7s 6d

2 2 2 2 2 2 2 2
Ti 22 4s 3d Zr 40 5s 4d Hf 72 6s 5d Rf 104 7s 6d

2 3 1 4 2 3 2 3
V 23 4s 3d Nb 41 5s 4d Ta 73 6s 5d Db 105 7s 6d

1 5 1 5 2 4 2 4
Cr 24 4s 3d Mo 42 5s 4d W 74 6s 5d Sg 106 7s 6d

2 5 1 6 2 5 2 5
Mn 25 4s 3d Tc 43 5s 4d Re 75 6s 5d Bh 107 7s 6d

2 6 1 7 2 6 2 6
Fe 26 4s 3d Ru 44 5s 4d Os 76 6s 5d Hs 108 7s 6d

2 7 1 8 2 7 2 7
Co 27 4s 3d Rh 45 5s 4d Ir 77 6s 5d Mt 109 7s 6d

2 8 0 10 1 9 2 8
Ni 28 4s 3d Pd 46 5s 4d Pt 78 6s 5d Ds 110 7s 6d

1 10 1 10 1 10 1 10
Cu 29 4s 3d Ag 47 5s 4d Au 79 6s 5d Rg 111 7s 6d

2 10 2 10 2 10 2 10
Zn 30 4s 3d Cd 48 5s 4d Hg 80 6s 5d Uub 112 7s 6d

E - Element
Z - Atomic Number
E.C. - Electronic Configuration

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d- & f - Block Elements
1. Electronic Configuration of Transition Elements
1 -10 1-2
The general electronic configuration for the atom of d-block is (n-1) d ns .
5 1 10 1
It may be noted that the configuration of Chromium (3d 4s ) and copper (3d 4s ) are anomalous
due to following reasons-
(i) Half filled and completely filled electronic configuration have extra stability associated
with them.
(ii) There is negligible energy difference between 3d and 4s subshells.
2. Atomic and Ionic radius
It is defined as the distance between nucleus of atom or ion and outer most shell electron. For the
elements of first transition series, the atomic radii decreases gradually from scandium to chromium
but from chromium to copper it remains practically constant. However we know that the electrons
enter the penultimate (last but one) shell and the added d-electrons screen the outermust s-
electrons. As the number of d-electrons increases, the screening effect increases. This neutralises
the effect of increased nuclear charge due to increase in atomic number and consequently, atomic
radius remains almost unchanged.
3. Ionisation Energy
It is defined as the energy required to remove and electron from outer most shell of an atom. As the
transition elements involve the gradual filling of (n-1) d-orbitals, the effect of 170 increase in nuclear
charge is partly cancelled by the increase in screening effect. Consequently the increase in
ionisation energy along period of dblock element is very small. The lowest common oxidation state of
3d series transition metals is +2. The unusual high value of second ionzation energy for Cr and Cu is
5 10
due to extra stability of half-filled (d ) and compeletely filled (d ) electronic configurations of these
elements.
4. Metallic Nature
The transition metals (with the exception of Zn, Cd and Hg) are very much hard and have low
volatility. Their melting and boiling points are high. The high melting points of these metals are
attributed to the involvement of greater number of electrons from (n-1)d in addition to the ns
electrons in the interatomic metallic bonding.
5
In any row the melting points of these metals rise to a maximum at d except for anomalous values
of Mn and Tc and fall regularly as the atomic number increases. They 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.
These elements are harder and more brittle than s-block elements. They have simple hexagonal
close packed (hcp), cubic close packed (ccp) or body centred cubic (bcc) lattices which are
characteristic of other metals.

Note
 Greater the number of valence electrons, stronger is the resultant bonding.

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 d- & f - Block Elements

5. Oxidation States
The transition metals exhibit a large number of oxidation states. The existence of the transition
elements in different oxidation state means that their atoms can lose different number of electrons.
This is due to the participation of inner (n-l)d electrons in addition to outer ns electrons because the
energies of the ns and (n-l)d subshells are almost equal.
The common oxidation states shown by different transition metals reveal the following facts:
+3 +2
(i) Sc and Zn exhibit +3 and +2 oxidation state as in Sc and Zn ions show stable inert
gas configuration and pseudo inert gas configuration.
(ii) Except Cu and Cr, the most common oxidation state of first row transition elements is +2
2
due to ns configurations.
(iii) In each group, the highest oxidation state increases with increase in atomic number,
reaches a maximum in the middle and then starts decreasing. For example, for the
first transition series the maximum oxidation state is shown by Mn. is+7
(iv) Generally transition elements are more stable in higher oxidation state mainly in fluorides
and in oxides. It is due to lower atomic size and higher electro negativity.
(v) In the +2 and +3 oxidation states, the bonds formed are mostly ionic. In the
compounds of higher oxidation states, the bonds are essentially covalent.
(vi) The reactivity and acidity of compounds increases with increasing oxidation state.
The oxides are ionic and basic in lower oxidation states. Example-
+2 +3 +4 +6 +7
TiO V2O3 CrO3
MnO Mn2O3 MnO2 MnO3 Mn2O7
basic amphoteric acidic acidic

(vi) Transitition metals also form compounds in low oxidation states such as zero (0) oxidation
state. The common examples are – [Ni (CO)4], [Fe(CO)5], [Co(CO)6]. where, oxidation state
of Ni, Fe and Co is zero.

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d- & f - Block Elements
6. Catalytic Properties
Many transition metals and their compounds act as good catalysts for various reactions. Of these,
the use of Fe, Co, Ni, V, Cr, Mn, Pt. etc. are very common. The main reasons for the catalytic activity
of transition metals are:
(i) The catalytic property of transition metals is due to their tendency to form reaction
intermediates with suitable reactants. These intermediates provide reaction paths of lower
activation energy and, therefore, increases the rate of the reaction. These reaction
intermediates readily decompose yielding the products and regenerating the original
substance. The transition metals form these reaction intermediates due to the presence of
vacant oribitals or their tendency to form variable oxidation states.
(ii) In some cases, the transition metals provide a suitable large surface area on which
the reactants may be adsorbed and, therefore, come closer to one another for the
reaction.
Examples
(a) Formation of vegetable fats:
Ni
R  CH CH  COOR H2  R  CH2  CH2  COOR
vegetable oil (unsaturated) vegetableghee (saturated)

(b) Synthesis of ammonia by Haber's process:

Fe
N2  3H2 
Mo
 2NH3

(c) Ostwald's process

Pt
4NH3  5O2 
800ºC
 4NO  6H2O
part of manufacturing of
HNO3 in Ostwald's method

7. Colour
The compounds of transition elements are usually coloured both in solid state and in aqueous
solution. In the transition elements which have partly filled d-oribtals and transfer of electrons can
take place from t2g orbitals to eg orbitals within the same subshell. The energy required for this
transition falls in the visible region. So when visible light falls on these compounds they absorb a
particular colour from the radiation for the promotion of unpaired electron and the remaining colours
are emitted.
Note
 The ions in which all the d-oribtals are fully filled or empty are colourless due to absence of unpaired
electron.

8. Interstitial Compounds
The transition elements are capable of entrapping smaller atoms of other elements such as H, C and
N in the interstitial sites in their crystal lattices. These trapped atoms get bonded to the atoms of
transition elements. The presence of these atoms results in decrease in malleability and ductility of
the metals, but increases their tensile strength. For example, steel and cast iron are hard due to
presence of trapped carbon in the interstitial spaces.

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 d- & f - Block Elements
9. Alloy Formation
An alloy is a blend of metals prepared by mixing the components. Alloys may be homogeneous solid
solutions in which the atoms of one metal are distributed randomly among the atoms of the other.
Such alloys are formed by atoms with metallic radii that are within about 15 percent of each other.
Because of similar radii and other characteristics of transition metals, alloys are readily formed by
these metals. The alloys so formed are hard and have often high melting points. The best known are
ferrous alloys: chromium, vanadium, tungsten, molybdenum and manganese are used for the
production of a variety of steels and stainless steel. Alloys of transition metals with non transition
metals such as brass (copper-zinc) and bronze (copper-tin), are also of considerable industrial
importance.

Magnetic Properties
Magnetic properties of transition element compound is mainly due to unpaired ct-electrons. The origin of
magnetic properties in a substance is due to two types of motion of electron.
(i) orbital motion (ii) spin motion.
The magnetic moment (μ) of a compound is the addition of these two.

    s B.M.

Where  is orbital magnetic moment and  s is spin magnetic moment.

The total magnetic moment of a species depends upon the number of unpaired electrons and is given by the
following expression.

 n  n  2  where n is the number of unpaired electrons.

Based on the behaviour of substances when placed in the magnetic field, they are classified into three
classes.
Properties Description Orientation Examples Application
Diamagnetic Replled by the All paired e– TiO2, V2O5. Insulator
magnetic field. They
contains paired
electron and unpaired
electrons are absent.
Non metallic elements
(excepts O2,S).
Paramagnetic
Attracted by the At least unpaired Electronic
O2, Cu2+, Fe3+, VO2,
magnetic field due to electron. appliances
the presence of CuO
permanent magnetic
dipoles
Ferromagnetic
Permanent magnetism Dipoles are aligned Fe, Ni, CO, CrO2 CrO2 is used
even in the absence of in the same in audio and
magnetic field. direction video tapes

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d- & f - Block Elements

f-Block elements
The elements in which the last electron enters the f-orbital of the atoms are called f-block elements. In these
elements, the last electron is added to the third to the outer most (called antepenultimate) energy level
i.e (n-2)f. The general configuration of f-block elements is-
1 -14 0-1 2
(n-2)f (n-1)d ns
These elements are also called inner-transition elements. They consists of two series of elements placed at
the bottom of the periodic table. These two series are generated by the filling of characteristic electrons in
the 4f and 5f orbitals.
The series involving the filling of 4f-orbitals following lanthanum is called lanthanide series. The series
involving the filling of 5f-orbitals is called actinide series. Both series consists of 14 elements.

At. Name E.C At. Name E.C

No. No.
1 2 1 2
57 Lanthanum (La) 5d 6s 89 Actinium (Ac) 6d 7s
1 1 2 2 2
58 Cerium (Ce) 4f 5d 6s 90 Thorium (Th) 6d 7s
3 2 2 1 2
59 Praseodymium (Pr) 4f 6s 91 Protactinium (Pa) 5f 6d 7s
4 2 3 1 2
60 Neodymium (Nd) 4f 6s 92 Uranium (U) 5f 6d 7s
5 2 4 1 2
61 Promethium (Pm) 4f 6s 93 Neptunium (Np) 5f 6d 7s
6 2 6 2
62 Samarium (Sm) 4f 6s 94 Plutonium (Pu) 5f 7s
7 2 7 2
63 Europium (Eu) 4f 6s 95 Americium (Am) 5f 7s
7 1 2 7 1 2
64 Gadolinium (Gd) 4f 5d 6s 96 Curium (Cm) 5f 6d 7s
9 2 9 2
65 Terbium (Tb) 4f 6s 97 Berkelium (Bk) 5f 7s
10 2 10 2
66 Dysprosium (Dy) 4f 6s 98 Californium (Cf) 5f 7s
11 2 11 2
67 Holmium (Ho) 4f 6s 99 Einstenium (Ef) 5f 7s
12 2 12 2
68 Erbium (Er) 4f 6s 100 Fermium (Fm) 5f 7s
13 2 13 2
69 Thulium (Tm) 4f 6s 101 Mendelevium (Md) 5f 7s
14 2 14 2
70 Ytterbium (Yb) 4f 6s 102 Nobelium (No) 5f 7s
14 1 2 14 1 2
71 Lutetium (Lu) 4f 5d 6s 103 Lawrencium (Lr) 5f 6d 7s
At.No. - Atomic Number
E.C. - Electronic Configuration

Lanthanoides
The series involving the filling of 4f orbitals is called lanthanoids. There are fourteen elements in this series
starting with cerium Ce (58) and ending with lutetium Lu (71 ). These elements occur very rarely and therf
ore, these elements have also been called rare earth elements. All Lanthanide elements colletively
represented by the symbol 'Ln'.
0-14
The lanthanoids involve the gradual filling of 4f-orbitals. The general electronic configuration is [Xe]4f ,
0-1 2 0-14 0-1 2
5d , 6s means the valence shell configuration of these elements is 4f , 5d , 6s .

Oxidation State
All lanthanoids exhibit a common stable oxidation state of +3. In addition, some lanthanoids show +2 and +4
0 7 14
oxidation states also. These are shown by those elements which by doing so attain the stable f , f and f
4+ 4+ 2+ 2+
configurations. Example: Ce , Tb , Eu , Yb

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 d- & f - Block Elements

Chemical Reactivity:

Note
 Basicity of hydroxides decreases from Ce to Lu.

Lanthanide Contraction
In the landthanide series, with increasing atomic number, the atomic and ionic radii decrease from one
element to another but the decrease is very small. The steady decrease in atomic and ionic sizes of
lanthanide elements with increasing atomic number is called lanthanide contraction.
In the lanthanide series, as we move from one element to another, the nuclear charge increases by one unit
and one electron is added. The new electrons are added to the same inner 4f-subshells. However, the 4f-
electrons shield each other from the nuclear charge quite poorly because of the very diffused shapes of the
f-orbitals. The nuclear charge however increases by one at each step. Hence with increasing atomic number
and nuclear charge, the effective nuclear charge experienced by each 4f-electron increases. As a result, the
whole of 4f-electron shell contracts at each successive element, though the decrease is very small. This
results in gradual decrease in size of lanthanoids with increase in atomic number. The sum of the successive
reductions gives the total lanthanide contraction.

Consequences of lanthanide contraction

(1) Resemblance of second and third transition series after the lanthanoids, the increase in radii
from second to third transition series almost vanishes. The pairs of elements : Zr-Hf, Nb-Ta, Mo-W,
etc., possess almost the same size. The properties of these elements are also very similar.
(2) Similarity among lanthanoids because of very small change in radii of lanthanoids, their chemical
properties are quite similar. Thus, it is very difficult to separate the elements in pure state.
(3) Basicity difference due to lanthanide contraction, covalent character between lanthanide ions and
–
OH ions increases so basic strength decrease from La(OH) 3 to Lu(OH)3.

Application of lanthanide elements

The best single use of the lanthanoids is for the production of alloy steels for plates and pipes. A well known
alloy is mischmetall which consists of a lanthanoid metal (~ 95%) and iron (~ 5%) and traces of S, C, Ca
and Al. A good deal of mischmetall is used in Mg-based alloy to produce bullets, shell and lighter flint. Mixed
oxides of lanthanoids are employed as catalysts in petroleum cracking. Some individual Ln oxides are used
as phosphors in television screens and similar fluorescing surfaces.

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d- & f - Block Elements
Actinoids
The series of elements involving the filling of 5f-orbital is called actinoids series. They come just after
actinium (Ac -89) and include 14 elements from Th(90) to Lr(103).
After uranium (92) all elements are unstable and does not found in nature. These are also called transuranic
elements or super heavy elements.
All actinoids are radioactive generally represented by the symbol An and their stability decreases with
increasing atomic number.
Difference between Lanthanoids and Actinoids
Lanthanoids Actinoids
1. Lanthanoids show mainly +3 oxidation state 1. In addition to +3 oxidate state, actinoids also
except in few cases where it is +2 and +4 show higher oxidation state such as +4, +5, +6, +7.
2. Except promethium, these are non radioactive 2. All the actinoids are radioactive
+ +
3. They do not form oxo ions 3. They do form oxo ions. Example UO , UO2 ,
+
PuO2 etc.
4. The tendency to form complex is less 4. They have greater tendency to form complexes
5. Lanthanide compounds are less basic 5. Actinoids compounds are more basic
6. Most of their trivalent ions are colourless 6. Most of their trivalent and tetravalent ions are
coloured.

Potassium dichromate K2Cr2O7

Dichromates are generally prepared from chromate, which in turn are obtained by the fusion of chromite ore
(FeCr2O4) with sodium or potassium carbonate in free access of air. The reaction with sodium carbonate
occurs as follows:
4 FeCr2O4 + 8 Na2CO3 + 7 O2 → 8 Na2CrO4 + 2 Fe2O3 + 8 CO2
The yellow solution of sodium chromate is filtered and acidified with sulphuric acid to give a solution from
which orange sodium dichromate, Na2Cr2O7. 2H2O can be crystallised.
+ +
2Na2CrO4 + 2 H → Na2Cr2O7 + 2 Na + H2O
Sodium dichromate is more soluble than potassium dichromate. The latter is therefore, prepared by treating
the solution of sodium dichromate with potassium chloride.
Na2Cr2O7 + 2 KCl → K2Cr2O7 + 2 NaCl
Orange crystals of potassium dichromate crystallise out.
Note The chromates and dichromates are interconvertible in aqueous solution depending upon pH of the
solution. The oxidation state of chromium in chromate and dichromate is the same.
2– + 2–
2CrO4 + 2H → Cr2O7 + H2O
2– – 2–
Cr2O7 + 2 OH → 2 CrO4 + H2O

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 d- & f - Block Elements
Structure of Chromate ion and Dichromate ion
2– 2–
The structures of chromate ion, CrO4 and the dichromate ion, Cr2O7 are shown below. The chromate ion
is tetrahedral whereas the dichromate ion consists of two tetrahedra sharing one corner with Cr–O–Cr bond
angle of 126°.

Sodium and potassium dichromates are strong oxidising agents.

In acidic solution, oxidising action can be represented as follows:
2– + – 3+ 0
Cr2O7 + 14H + 6e → 2Cr + 7H2O (E = 1.33V)
Thus, acidified dichromate will oxidise iodides to iodine, sulphides to sulphur, tin(II) to tin(IV) and iron(II) salts
to iron(III). The half-reactions are noted below:

6I  3I2  6e

3Sn2  3Sn4  6e

3H2S  6H  3S  6e

6Fe2  6Fe3  6e 
Potassium permanganate KMnO4
Potassium permanganate is prepared by fusion of MnO2 with an alkali metal hydroxide and an oxidising
agent like KNO3. This produces the dark green K2MnO4 which disproportionates in a neutral or acidic
solution to give permanganate.
2MnO2 + 4KOH + O2 → 2K2MnO4 + 2H2O
2– + –
3MnO4 + 4H → 2MnO4 + MnO2 + 2H2O
Commercially it is prepared by the alkaline oxidative fusion of MnO 2 followed by the electrolytic oxidation of
manganate (Vl).
Fused with KOH, oxidised Electrolytic oxidation in
with air or KNO3 alkaline solution
MnO2  MnO24 ; MnO24   MnO 4
Manganate ion manganate permanganate ion

In the laboratory, a manganese (II) ion salt is oxidised by peroxodisulphate to permanganate.

2+ 2– – 2– +
2Mn + 5S2O8 + 8H2O → 2MnO4 + 10SO4 + 16H
Potassium permanganate forms dark purple (almost black) crystals which are isostructural with those of
KClO4. The salt is not very soluble in water (6.4 g/100 g of water at 293 K), but when heated it decomposes
at 513 K.
2KMnO4 → K2MnO4 + MnO2 + O2

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d- & f - Block Elements
Structure of manganate and permanganate ion
The manganate and permanganate ions are tetrahedral; the green manganate is paramagnetic with one
unpaired electron but the permanganate is diamagnetic. The  -bonding takes place by overlap of p orbitals
of oxygen with d orbitals of manganese.

O O

Mn Mn
O O O O
O O
Tetrahedral Tetrahedral
manganate permanganate
(green) ion (purple) ion
Chemical Properties
In acidic medium (in presence of dilute H2SO4)
Manganous sulphate is formed. The solution becomes colourless.

MnO4   5Fe2  8H  5Fe3   Mn2  4H2O

or MnO4   8H  5e –  Mn2  4H2O

This medium is used in quantitative (volumetric) estimations. The equivalent mass of KMnO 4 in
Molecular mass
acidic medium is =
5
(a) Ferrous salts are oxidised to ferric salts.

MnO4   5Fe2  8H  5Fe3   Mn2  4H2O

(b) Iodine is evolved from potassium iodide.

2MnO4   10I  16H  2Mn2  5I2  8H2O

(c) H2S is oxidised to sulphur:

2MnO4 –  16H  5S2–  2Mn2  8H2O  5S

(d) Oxalic acid is oxidised to CO2:

60ºC
2MnO4   16H  5C2O42–   2Mn2  8H2O  10CO2

(e) H2O2 is oxidised to O2.

2MnO4 –  6H  5H2O2  5 O2  Mn2  8H2O

In neutral or faintly alkaline solutions

(a) A notable reaction is the oxidation of iodide to iodate:

2MnO4 –  H2O  I–  2MnO2  2OH–  IO3 –

(b) Thiosulphate is oxidised almost quantitatively to sulphate:

8MnO4 –  3 S2O32–  H2O  8MnO2  6 SO 42–  2OH–

(c) Manganous salt is oxidised to MnO2; the presence of zinc sulphate or zinc oxide catalyses the
oxidation:

2MnO4 –  3Mn2  2H2O  5MnO2  4H

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