UNIT-08: THE d- and f-BLOCK ELEMENTS

d-BLOCK ELEMENTS:
The elements in which the differentiating electron enters (n–1) d-orbital are called d-block
elements. Properties of these elements are intermediate between those of s and p block elements and
hence they are called transition elements.
Their general outer electronic configuration is (n–1) d1–10 ns1–2.
d-block elements are classified into four series namely 3d-series, 4d-series, 5d-series and 6d-
series. Each of 3d, 4d, and 5d series contains ten elements and the 6d-series is an incomplete series
with only 8 elements.
3d-series contains elements from Scandium (Z = 21) to Zinc (Z = 30)
4d-series contains elements from Yttrium (Z = 39) to Cadmium (Z = 48)
5d-series contains Lanthanum (Z = 57) and Hafnium (Z = 72) to mercury (Z = 80)
6d-series contains Actinum (Z = 89) as the first member and the remaining elements are synthetic
elements from Z = 104 to 112.
Note: Zinc, Cadmium, Mercury are not regarded as transition metals due to completely filled d-
orbitals.

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GENERAL CHARACTERISTICS OF TRANSITION ELEMENTS
(i) They show variable oxidation states
(ii) They exhibit paramagnetism
(iii) They show catalytic behavoiur
(iv) Formation of coloured ions
(v) Formation of interstitial compounds and complexes.

1. Electronic configuration:
General electronic configuration of d-block elements is [noble gas] (n–1) d1–10 ns1–2.
Electronic configuration of 3d series elements
E Sc Ti V Cr Mn Fe Co Ni Cu Zn
Z 21 22 23 24 25 26 27 28 29 30
4s 2 2 2 1 2 2 2 2 1 2
3d 1 2 3 5 5 6 7 8 10 10
Electronic configuration of 4d series elements

E Y Zr Nb Mo Tc Ru Rh Pb Ag Cd
Z 39 40 41 42 43 44 45 46 47 48
5s 2 2 1 1 1 1 1 0 1 2
4d 1 2 4 5 6 7 8 10 10 10
Electronic configuration of 5d series elements
E La Hf Ta W Re Os Ir Pt Au Ag
Z 57 72 73 74 75 76 77 78 79 80
6s 2 2 2 2 2 2 2 1 1 2
5d 1 2 3 4 5 6 7 9 10 10
Electronic configuration of 6d series elements
E Ac Rf Db Sg Bh Hs Mt Ds Rg Uub
Z 89 104 105 106 107 108 109 110 111 112
7s 2 2 2 2 2 2 2 2 1 2
5d 1 2 3 4 5 6 7 8 10 10
However general electronic configuration has several exceptions because of very little
differences between (n–1) and ns orbitals.

Examples:
(i) Electronic configuration of Cr is [Ar] 4s1 3d5 but not [Ar] 4s2 3d4 because of extra stability of
half-filled d orbitals.
(ii) Electronic configuration of Cu is [Ar] 4s 1 3d10 but not [Ar] 4s2 3d9 because of extra stability of
completely filled d orbitals.

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2. Atomic size and ionic size:
The atomic size of 3d series elements first decreases from Sc to Cr and then remains constant
and finally increases from Cu to Zn. This is because in the beginning effective nuclear charge is
higher than screening effect. In the middle these two balances with each other and finally increases.
Elements Sc Ti V Cr Mn Fe Co Ni Cu Zn
Atomicradius(pm) 144 132 122 117 117 117 116 115 117 125
But the variation of atomic size of 4d, 5d and 6d series is same as that of 3d series but their
atomic size are generally higher than that of 3d series.
Atomic radius of 5d series are virtually same as that of 4d series due to intervention of the 4f
orbitals, which must be filled before 5d series.
Lanthanoid contraction: The filling of 4f before 5d-orbital results in a ‘regular decrease
(contraction) in the atomic and ionic radii of lanthonoid series’ is known as Lanthanoid contraction.
Consequences: The net result of the lanthanoid contraction is that the second and the third d-series
exhibits similar radii (Examples: Zr, 160pm and Hf 159 pm) and have very similar physical and
chemical properties.
3. Ionization enthalpy:
Ionization enthalpy increases along a series due to increase in nuclear charge.
(i) First ionization enthalpy of these elements do not increases steeply but the magnitude of second
and third ionization enthalpy of these elements in general much higher.
(ii) The first ionization enthalpy of Zn, Cd and Hg are very high because of the fully filled (n-1) d 10
ns2 configuration.
(iii) Second ionization energy is unusually high for Cu and Cr because of d 5 and d10 configurations.
But second ionization energy of Zn is low because to attain d10 configuration.
(iv) Third ionization energy is unusually high for Mn 2+, Zn2+, Fe3+ because of d5 and d10
configurations.

Note: The first ionization enthalpies of 5d elements are higher as compared to those of 3d and 4d
elements. This is because of weak shielding of nuclear by 4f electrons in 5d elements results in
greater effective nuclear charge acting on the outer valence electrons.
Physical properties:
 Transition metals have tensile strength, ductility & malleability
 They have thermal & electrical conductivity, metallic lustre.
 They are hard and low volatility, high melting point and boiling point (except Zn, Cd & Hg).
 High melting points of these metals rise to a maximum at d 5 except the anomalous values of
Mn &Tc and then decreases as atomic number increases.
 High melting point of the elements due to high enthalpy of atomization due to strong
interatomic attraction between more numbers of valence electrons. But enthalpies of
atomization of 4d and 5d series elements are higher than 3d series elements due to much more
frequent metal-metal bonding.
4. Oxidation states:
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 Transition elements shows variable oxidation states because
(i) Energy differences between (n–1) d and ns orbitals are less
(ii) Both (n–1)d and ns electrons involved in bonding. Minimum oxidation state is equal to number
of ‘s’ electrons and maximum oxidation state is equal to number of ‘s’ electrons and number of
unpaired electrons in d orbitals.
Example: Manganese exhibits oxidation states from 2 to 7
In ‘p’ block elements, lower oxidation state are favoured by heavier elements but opposite is true in
the group of d- block.
Examples: In group 6, Mo (VI) and W(VI) are more stable than Cr(VI). So ‘Cr’ of dichromate in
acidic medium is strong oxidizing agent but not MoO3 and WO3.
In some complex salts, transition elements form low oxidation states.
Examples: In Ni (CO)4 and Fe(CO)5 oxidation state of Ni and Fe is zero.
Note:
(i) d block elements which shows maximum oxidation state are Mn(+7), Os(+8) and Ru (+8)
(ii) d block elements which does not shows variable oxidation state is Sc.
iii) d block elements shows lesser number of oxidation states at extreme ends, because they lose or
share too few electrons.

Standard electrode potential of electrodes (trends) EΘ:

(i) M2+/M type: In general less negative electrode potentials across the series depends on sum of the
first and second ionization enthalpies. Therefore E Θ for Mn, Ni and Zn are more negative than the
expected value because of half-filled d-sub shell in Mn 2+, completely filled d-sub shell in Zn++,
whereas highest hydration enthalpy of Ni2+ ion.
But in Cu, the unique behavior of positive potential account inability to liberate H 2 from acids, but
only oxidizing acids being reduced by Cu (HNO3.hot conc.H2SO4). The high energy of
is not balanced by its hydration enthalpy.

(ii) M3+/M2+ type: EΘ potential values for M3+/M2+shows variation i.e., low value of Sc reflects
stability of Sc3+, high value of Zn is due to the removal of an electron from the stable
d10configuration of Zn2+. High value of Mn is due to d5 configuration, low value of Fe shows the
extra stability of Fe3+ (d5). Low value for V due to stability of V2+ (half filled t2g set).

Trends in Stability of higher oxidation states: Higher oxidation state of 3d series elements can be
stabilized by both oxygen and fluorine by forming oxides and fluorides. But the ability of oxygen
exceeds that of fluorine because oxygen forms multiple bonds to metals, but fluorine by lattice
enthalpy and bond enthalpy.
Examples: TiX4, VF5, CrF6, Mn2O7, Sc2O3 etc….
Fluorides of the metals exhibits instability in low oxidation state but Cu(II) halides are known,
except iodides.
Note: The stability of Cu2+(aq) is more than Cu+(aq) due to high hydration enthalpy of Cu2+, which
more than compensates second ionization enthalpy of Cu.
E° values and chemical reactivity:

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 Metals of the 3d series except Cu, which have negative standard electrode potentials. So they
are more reactive and they are oxidized by 1M H+.
The E° values for M2+/M indicate a decreasing reducing tendency to form divalent cations. This trend
is due to increase in the sum of first and second ionization energy.
The E° value for the redox couple M 3+/M2+ shows that, M3+ are strong oxidizing agents in aqueous
solutions [Mn3+ and Co3+]. M2+ ions are strong reducing agents (Ti2+, Cr2+ and V2+) and liberate
hydrogen from a dilute acid.

5. Magnetic properties:
(i) Paramagnetism: Paramagnetic substances are attracted by magnetic field. Those substances
which have unpaired electrons are paramagnetic in nature.
Example: Co, Ni, Cr, Mn etc.
(ii) Diamagnetism: Diamagnetic substances are repelled by an applied magnetic field. Those
substances which do not have unpaired electrons are diamagnetic in nature.
Example: Zn, Cd, Hg etc.
(iii) Ferromagnetism: Substances which are attracted strongly are said to be ferromagnetic. It is
extreme form of paramagnetism. They have maximum number of unpaired electrons. Many of the
transition metal ions are paramagnetic. Paramagnetism arises from the presence of unpaired
electrons.Each such electron having a magnetic moment associated with its spin angular momentum
and orbital angular momentum. The contribution of the orbital angular momentum is effectively
quenched and hence is of no significance. Magnetic moment calculated by using spin only formula

Where, n = number of unpaired electrons.

μ = magnetic moment (it increase with the increasing number of unpaired electrons).
Calculated magnetic Moments (BM)
Ion Electronic No. of unpaired Magnetic
configuration electrons moments
Sc3+ 3d0 0 0
Ti3+ 3d1 1 1.73
Ti2+ 3d2 2 2.84
V 2+ 3d3 3 3.87
Cr 2+ 3d4 4 4.90
Mn2+ 3d5 5 5.92
Fe2+ 3d6 4 4.90
Co2+ 3d7 3 3.87
Ni2+ 3d8 2 2.84
Cu2+ 3d9 1 1.73
Zn2+ 3d10 0 0

Calculate the magnetic moment of Sc2+ and Mn2+ and Fe2+ ions.
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For Sc2+, => [Ar] 3d1 4s0, μ = √ n(n+ 2) = √ 1(1+2) = 1.73 B.M.
For Mn2+ => [Ar] 3d5 4s0, μ = √ n(n+ 2) = √ 5(5+2) = 5.92 B.M.
For Fe2+, => [Ar] 3d6 4s0, μ = √ n(n+ 2) = √ 4 (4 +2) = 4.89 B.M.

6. Formation of coloured ions:

Most of the transition metal ions are coloured both in the solid state and aqueous solutions.
This is because they have partially filled d- orbitals (d 1– d9). When visible light falls on the
transition metal ions, the unpaired electrons present in the lower energy d-orbitals (t 2g) get promoted
to the higher energy d-orbitals (eg). This is called d-d transition. During this process, a part of the
visible light is absorbed and the remaining part is transmitted as colour. The observed colour is
complementary to the absorbed colour.
Light absorbed Complementary colour
Violet yellow
Blue Orange red
Green Red
Examples:
a) Copper sulphate (CuSO4) solution is blue in colour because it absorbs red colour from white light
and transmits blue colour.
b) Cobalt chloride (CoCl3) solution in water absorbs blue colour from white light and transmits red
colour.
The transition metal ions with completely filled d-orbitals or completely empty d-orbitals are
colourless due to the absence of unpaired electrons.

Examples: a) Cu+ (3d10), Zn2+ (3d10) ions have completely filled d-orbitals are colourless.
b) Sc3+ (3d0), Ti4+ (3d0) ions have completely empty d-orbitals are also colourless.

7. Formation of complex compounds: The transition metals form a large number of complex
compounds. This is due to the comparatively smaller size of the metal ions and their high ionic
charges and the availability of d-orbital for bond formation.Because of the above properties,
transition metal atoms or ions accept pair of electrons from ligands and forms complex salts.
Example: a) Chromium forms [Cr (H2O) 6] Cl3, hexaaqua chromium (III) chloride
b) Iron forms K4 [Fe (CN) 6], potassium hexacyanoferrate (II)
K3 [Fe (CN) 6], potassium hexacyanoferrate (III)
c) Cobalt forms [Co (NH3)6] Cl3, hexammine cobalt (III) chloride.
d) Copper forms [Cu (NH3)4] SO4, tetrammine copper (II) sulphate
e) Nickel forms [Ni (CO) 4], tetra carbonyl nickel (0).
Note: A complex compound of a metal ion in its higher oxidation state is more stable than a
complex compound in its lower oxidation state.
8. Catalytic properties: Transitions metals and their compounds act as catalyst because
(i) They have large surface area.
(ii) They have partially filled d-orbitals.
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(iii)They exhibit variable oxidation states.
(iv) They have ability to form chemical bonds with reactants adsorbed on their surface.
Examples:
(a) iron (III) catalyses the reaction between iodide and persulphate ions.

An explanation of catalytic action can be given as:

b) Finely divided iron acts as a catalyst in the manufacture of ammonia by Haber’s process.
c) Finely divided nickel acts as a catalyst in the hydrogenation of oils.
d) Vanadium pentoxide (V2O5) acts as a catalyst in the manufacture of H2SO4 by contact process.
e) Titanium tetra chloride (TiCl4) acts as a catalyst in the manufacture of high density polythene.
f) Pt / Rh is used as a catalyst in the manufacturing of HNO3 by Ostwald’s process.

9. Formation of interstitial compounds:

Interstitial compounds in which small atoms like H, C or N are trapped inside the crystal
lattices of metals. They are usually non-stoichiometric and are neither typically ionic nor covalent.
Examples: TiC, Mn4N, Fe3H, VH056, Ti H1.7 etc.
Properties:
a. They have high melting point than pure metals.
b. They are very hard (borides), hardness almost equal to diamond.
c. They retain metallic conductivity and they are chemically inert.

10. Alloy formation: Alloys are homogeneous solid solutions of two or more metals obtained by
melting the components and then cooling the melt. They form alloys due to similar ionic sizes. The
alloys formed are hard and have high melting points.
The most commonly used ferrous alloys: Chromium, Vanadium, tungsten, molybdenum. Some
alloys of transition metals with non-transition metals such as brass (copper-zinc), bronze (copper-tin)
are very common.

Oxides and oxoanions of metals: The metals of the first transition series form oxides with oxygen
at high temperature. All the metals except scandium form monoxides, which are ionic.
As the oxidation number of a metal increases, ionic character decreases.
Example: In MnO, Mn3O4, Mn2O3, MnO2, Mn2O7.
The oxides in higher oxidation states of the metals exhibit acidic character. Example: Mn2O7, CrO3,
V2O5 etc.
The oxides in lower oxidation states of the metals exhibit basic character. Example: CrO
The oxides in the intermediate oxidation states of the metals are amphoteric.Example:Cr2O3
Important compounds of transition elements:
Potassium Dichromate (K2Cr2O7):

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Preparation: Dichromates are prepared from chromates which are obtained by the fusion of
chromite ore [Fe Cr2 O4] with sodium (or potassium) carbonate in free access of air.
4FeCr2O4 + 8Na2CO3 + 7O2 → 8Na2CrO4 + 2Fe2O3 + 8CO2 ↑
The yellow solution of sodium chromate is filtered and acidified with sulphuric acid to get
sodium dichromate.
2Na2CrO4 + 2H+ → Na2Cr2O7 + 2Na+ + 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 + 2KCl → K2Cr2O7 + 2NaCl
Orange crystals of Potassium dichromate crystallize out.
Physical properties:
(i) It is orange coloured solid.
(ii) It is highly soluble in water.
(iii) The colour of potassium dichromate depends upon pH of solution. The chromate and
dichromate are interconvertible in aqueous solution depending upon pH. In acidic pH, chromate ions
get converted into dichromate ions and the colour of the solution becomes orange.
2CrO42 – + 2H+ → 2Cr2O72 – + H2O
In basic pH, in presence of OH- orange coloured dichromate ion gets converted into chromate ion
(yellow)
Cr2O72 – + 2OH – → 2CrO42 – + H2O
Structure of chromate and dichromate ions:
The chromate ion is tetrahedral whereas dichromate ion consists of two tetrahedral sharing
one corner with Cr – O – Cr bond angle of 126°.

Chemical properties:
Oxidizing properties: In acidic solution, the oxidizing action of potassium dichromate can be
represented as follows.
Cr2O72 –+14H+ + 6e2 – → 2Cr3+ + 7H2O (EΘ = 1.33V)
Examples:

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Uses:
(i)It is used as oxidant for preparation of many azo compounds.
(ii) It is used for tanning of leather.
(iii) It is used in volumetric analysis as primary standard.
(vi) It is used in chromyl chloride test.

Potassium permanganate (KMnO4):

Preparation: When MnO2is heated with an alkali metal hydroxide and an oxidising agent like
KNO3 produces the dark green K2MnO4, which disproportionate in a neutral or acidic solution to give
permanganate.

Commercial method of preparation: Commercially it is prepared by the alkaline oxidative fusion

of MnO2 followed by the electrolytic oxidation of manganate (VI).

Laboratory method of preparation: It is prepared in the laboratory by the oxidation of Mn2+ ion by
peroxodisulphate to permanganate.

Physical properties:
(i) It is dark purple coloured crystalline solid which are isostructural with those of KClO4.
(ii) It is not very soluble in water.
(iii) It is stored in dark coloured bottles because it gets decomposed in presence of sunlight.
(iv) It is paramagnetic in nature.
Structure of manganate and permanganate:
The manganate and permanganate ions are tetrahedral. The green manganate is paramagnetic
with one unpaired electron but the permanganate is diamagnetic. The π-bonding takes place by the
overlap of p-orbitals of oxygen with d-orbitals of manganese.

Chemical properties:

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 Oxidizing reactions in
(i) Acid medium
(i) Iodine is liberated from potassium iodide.

(ii) Ferrous ion (green) is converted to ferric (yellow).

(iii) Oxalate ion or oxalic acid is oxidized at 333K.

(iv) It oxidizes hydrogen sulphideto sulphur.

(v) Sulphurous acid or sulphite is oxidized to a sulphate or sulphuric acid.

(vi)
(ii) In neutral or faintly alkaline solutions:
(i) It oxidises iodide to iodate.

(ii) Thiosulphate is oxidized almost quantitatively to sulphate.

(iii) Manganous salt is oxidized to MnO 2. The presence of zinc sulphate or zinc oxide
catalyses the oxidation.

Uses of potassium permanganate (KMnO4)

(i) It is used as oxidizing agent.
(ii) It is used for bleaching of wool, cotton, silk and other textile fibres.
(iii) For the decolourisation of oils.

THE INNER TRANSITION ELEMENTS (f-BLOCK)

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General introduction: The f-block consists of two series, lanthanoids (the fourteen elements
following lanthanum) and actinoids (the fourteen elements following actinium).
General electronic configuration of f-block elements is (n – 2) f1 – 14 (n – 1) 6d 0 – 1 ns2
THE LANTHANOIDS:
Lanthanoids include fourteen elements from Ce to Lu : Cerium(Ce), Praseodymium(Pr),
Neodymium(Nd), Promethium(Pm), Samarium(Sm), Europium(Eu), Gadolinium(Gd), Terbium(Tb),
Dysprosium(Dy), Holmium(Ho), Erbium(Er), Thulium(Tm), Ytterbium(Yb), Lutetium(Lu).
1. Electronic configuration: Lanthanoids have the electronic configuration with 6s 2 common but
with variable occupancy of 4f level. However, the electronic configuration of all the tripositive ions
(most stable oxidation state of lanthonoids) are of the form 4f n (n=1to14) with increasing atomic
number.
General electronic configuration of lanthanoids is[Xe] 4f1 – 14 5d 0 – 1 6s2
2. Atomic and ionic Sizes: The atomic and ionic radii of lanthanoid elements gradually decrease
from Lanthanum to Lutetium. The gradual decrease in atomic and ionic radii of Lanthanoid
series is known as the lanthanoid contraction. The decrease in size from one element to the
other is smaller than that observed in the cases of transition series elements.
Cause for lanthanoid contraction:
This is due to the poor shielding effect from 4f-electrons in the second inner shell.
Consequences of lanthanoid contraction:
1. Due to Lanthanoid contraction both 4d and 5d series elements have similar radii
Example: Zr (l60pm) and Hf (159pm)
2. Both 4d and 5d series elements occurs together in nature and difficulty in their separation.

3. Oxidation states: The typical oxidation state of the lanthanoids is +3. They can also exhibit +2
and +4 state in solution or in solids. It is due to extra stability of f, f7 and f14configurations.
Example: Ce (IV) is favoured by its noble gas configuration. It is strong oxidant and so then become
Ce (III) EΘ value of Ce4+/Ce3+is 1.74v. So Ce (IV) can oxidise water. Eu 2+ and Yb2+ are favoured by
their f7 and f14 configurations, which acts as reducing agents.
Note: Tb4+ is favoured by its f7 configuration and it is strong oxidant.

GENERAL CHARACTERISTICS OF LANTHONOIDS

Physical properties:
(i) All the Lanthanoids are silvery white soft metals and tarnish rapidly in air.
(ii) The hardness increases with increasing atomic number.
(iii) Their melting point range between 1000 to1200 K but samarium melts at 1623 K.
(iv) They have metallic structure and are good conductors of heat and electricity.
(v) Many trivalent lanthanoid ions are coloured both in the solid state and in aqueous solutions.
(vi) Neither La3+ nor Lu3+ ion shown any colour but the rest do so.
(vii) The Lanthanoid ions other than f 0, type (La3+ and Ce4+) and the f 14 type (yb2+ and Cu3+] all are
paramagnetic. The paramagnetism rises to maximum in neodymium.

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(viii) The first ionization enthalpies of the Lanthanoids are round 600 kJ mol –1 and second about
1200kJ mol–1 comparable with those of calcium.

CHEMICAL PROPERTIES OF LANTHANOIDS

In general, the earlier members of the series are quite reactive similar to calcium but, with
increasing atomic number they behave more like aluminum.
Values of E0 for the half reaction: are in the range of – 2.2 to –
2.4V (except for Eu (– 2.0V)).

Lanthanoids reacts with-

(a) Hydrogen forms hydride: (Ln + H2  LnH3)
(b) Oxygen forms oxides: (4Ln + 3O2  2Ln2O3)
(c) Carbon gives carbides: (Ln + C  Ln4C3)
(d) Water forms hydroxides: (2Ln + 6H2O  2Ln(OH)3 + 3H2)
(e) Dilute acids liberating hydrogen: (2Ln + 6HCl  2LnCl3 + 3H2)
(f) Nitrogen forms nitrides: (2Ln + N2  2LnN)
(g) Halogens form halides: (2Ln +3 X2  2LnX3)
(h) Sulphur forms sulphides; (2Ln +3 S  Ln2S3)
Note: Hydroxides of Lanthanoids are basic like alkaline earth metals.

Uses of Lanthanoids:
(i) It is used for the production of alloy steels for plates and pipes.
(ii) A well- known alloy is mischmetal (It consists of a lanthanoids metal (94-95%) + iron (5%) +
traces of S, C, Si& Al).
Mischmetal is used in Mg-based alloy to produce bullets, shell and lighter flint.
(iii) Mixed oxides of Lanthanoids are employed as catalyst in petroleum cracking.
(iv) Some individual lanthanoids oxides are used as phosphors in colour television screens and
similar fluorescing surfaces.

THE ACTINOIDS:
The actinoids include fourteen elements from Th to Lr: (Thorium(Th),
Protactinium(Pa), Uranium(U), Neptunium(Np), Plutonium(Pu), Americium(Am), Curium(Cm),
Berkelium(Bk), Californium(Cf), Einstenium(Es), Fermium(Fm), Mendelevium(Md),
Nobelium(No), Lawrencium(Lr).
1. Electronic configuration: Actinoids have the electronic configuration of 7s2 and variable
occupancy of 5f and 6d sub shells. The irregularities in the electronic configurations of actinoids like
those in the Lanthanoids are related to the stabilities of the f 0, f7and f14, occupancy of the 5f orbitals.
Thus the configurations of Am and Cm are [Rn] 5f77s2 and [Rn] 5f76d17s2.

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2. Ionic sizes: There is a gradual decrease in the size of atoms or M 3+ ions across the series. This
may be due to the actinoid contraction.
Note: The contraction is however, greater from element to element in this series resulting from poor
shielding by 5 f electrons.
3. Oxidation states: The common oxidation state of actinoids is +3. However they also exhibit
oxidation state of +4, +5, +6 and +7. Thus actinoids show greater range of oxidation states. The
elements in the first half of the series frequently exhibit higher oxidation states, but decreases in
succeeding elements.

GENERAL CHARACTERISTICS OF ACTINOIDS IN COMPARISION WITH

LANTHANOIDS
1. Similarites: As both lanthonoids and actanoids involve filling of f-orbitals they show similarities
in many respect as follows:
(i) Both show mainly an oxidation state of +3.
(ii) Both are electropositive and very reactive.
(iii) Both exhibit magnetic and spectral properties.
(iv) Actinoids exhibits actinoid contraction like Lanthonoid contraction shown by lanthonoids.

Chemical properties: Actinoids are very reactive metals in finely divided state. So actinoids reacts
with
1. Most of the non-metals and forms respective compounds
2. Boiling water gives a mixture of oxide and hydrides
3. HCl forms respective chloride with the liberation of H 2 gas, but they are slightly affected by
HNO3due to the formation of oxide layer.

2. Differences between lanthonoids and actinoids:

Lanthanoids Actinoids
1. Besides +3 oxidation state, they show +2 1. Besides +3 oxidation state, they show
and +4 oxidation states in few cases. higher oxidation states of +4, +5, +6 +7 also
2. Most of their ions are colourless 2. Most of their ions are coloured.
3. They have less tendency towards complex 3. They have greater tendency towards
formation. complex formation.
4. Lanthanoid compounds are less basic 4. Actinoid compounds are more basic.
5. Do not form oxocation 5. For oxocations e.g., UO22+, PuO22+ and
6. Except promethium these are non- UO+
radioactive. 6. These are radioactive.
7. The magnetic properties can be explained 7. The magnetic properties are more complex
easily. and hence cannot be explained easily.

APPLICATIONS OF d-AND f-BLOCK ELEMENTS

(i) Iron and steel are important construction materials.

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(ii) CrO2 is used in magnetic tapes.
(iii) Ni is used in hydrogenation.
(iv) W (Tungsten) is used in making electrical filaments.
(v) Ni, Cd and Zn are used in battery cells.
(vi) Nb alloys are used in jet engines.
(vii) Tantalum (Ta) is used in making analytical weights.
(viii) AgBr is used in Photography.
(ix) V2O5 is used as catalyst.
(x) Titanium is used in nuclear reactors.
(xi) PdCl2 is used as catalyst in Wacker process for the oxidation of ethyne.

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