The d and f-block of elements

The d-block elements: The elements in which the last electrons enters in the penultimate (n-1)d subshell
are called as the d-block of elements.
The transition elements: The d-block of elements which exhibit transitional behavior between highly
reactive ionic-compound-forming s-block elements (electropositive elements) on one side, and mainly the
covalent-compound-forming p-block elements (electronegative elements) on the other side. They have
incompletely filled (n-1)d subshell electronic configuration in their ground state or in their most stable
common oxidation states

Electronic configuration: The d-block of elements have partially filled d-orbitals in their neutral atoms or in
their common ions. Thus, the outer electronic configuration of the transition elements is (n – 1)d1–10 ns1–2,
where n is the outermost shell, and (n – 1) stands for the penultimate shell. Very little energy difference
between (n-1)d and ns orbital leads to this unusual electronic configuration. All d-block elements are
classified into four series as follows.
(i) First transition series (or 3d-series) consists of elements from Sc (at no. 21) to Zn (at. no. 30).
These elements lie in the 4th period of the periodic table.
(ii) Second transition series (or 4d-series) consists of elements from Y (at. no. 39) to Cd (at. no.
48). These elements lie in the 5th period of the periodic table.
(iii) Third transition series (or 5d-series) consists of elements La (at. no. 57) and from Hf (at. no.
72) to Hg (at. no. 80). These elements lie in the 6th period.
Element Symbol At.No Elec. Configuration Elec. Configuration (short)
2 2 6 2 6 2 1
Scandium Sc 21 1s 2s 2p 3s 3p 4s 3d [Ar] 3d1 4s2
Titanium Ti 22 1s2 2s22p6 3s23p64s23d 2 [Ar] 3d2 4s2
Vanadium V 23 1s2 2s22p6 3s23p64s23d 3 [Ar] 3d3 4s2
2 2 6 2 6 1 5
Chromium Cr 24 1s 2s 2p 3s 3p 4s 3d [Ar] 3d5 4s1
Manganese Mn 25 1s2 2s22p6 3s23p6 4s23d 5 [Ar] 3d5 4s2
Iron Fe 26 1s2 2s22p6 3s23p64s23d 6 [Ar] 3d6 4s2
2 2 6 2 6 2 7
Cobalt Co 27 1s 2s 2p 3s 3p 4s 3d [Ar] 3d7 4s2
Nickel Ni 28 1s2 2s22p6 3s23p64s23d 8 [Ar] 3d8 4s2
Copper Cu 29 1s2 2s22p6 3s23p64s13d 10 [Ar] 3d10 4s1
2 2 6 2 6 2 10
Zinc Zn 30 1s 2s 2p 3s 3p 4s 3d [Ar] 3d10 4s2
Transition elements resemble each other in many ways. These are,
(i) All transition elements are metals.
(ii) These elements are hard, high melting, and high boiling metals.
(iii) These elements form alloys among themselves and with other metals.
(iv) Many of the transition elements are sufficiently electropositive and get dissolved in mineral
acids.
(v) With very few exceptions, these elements exhibit variable valencies and their ions and com-
pounds are coloured in one or all the oxidation states.
(vi) Because of the partially-filled shells these elements form paramagnetic compounds.
(vii) Most of the d-block of elements form colored complexes.

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Variation in physical and chemical properties in d-block elements:
The atomic and ionic radii: The atomic radii and atomic volumes of d-block elements in any series decrease
with increase in the atomic number. The decrease however, is not regular. The atomic radii tend to reach
minimum near at the middle of the series, and increase slightly towards the end of the series.
EXPLANATION. When we go in any transition series from left to right, the nuclear charge increases gradually
by one unit at each element. The added electrons enter the same penultimate shell, (inner d-shell). These
added electrons shield the outermost electrons from the attraction of the nuclear charge. The increased
nuclear charge tends to reduce the atomic radii, while the added electrons tend to increase the atomic radii.

At the beginning of the series, due to smaller number of electrons in the d-orbitals, the effect of increased
nuclear charge predominates, and the atomic radii decrease. Later in the series, when the number of d-
electrons increases, the increased shielding effect and the increased repulsion between the electrons tend
to increase the atomic radii. Somewhere in the middle of the series, therefore the atomic radii tend to have
a minimum value as observed.
The atomic radii increase while going down in each group. However, in the third transition series from
hafnium (Hf) and onwards, the elements have atomic radii nearly equal to those of the second transition
series elements.
EXPLANATION. The atomic radii increase while going down the group. This is due to the introduction of an
additional shell at each new element down the group. Nearly equal radii of second and third transition series
elements is due to a special effect called lanthanide contraction.
The decrease in metallic radius coupled with increase in atomic mass results in a general increase in the
density of these elements.

Ionisation enthalpy: The ionisation energies of these elements are high, and in most cases lie between those
of s-and p-block elements. This indicates that the transition elements are less electropositive than s-block
elements.
EXPLANATION. Transition metals have smaller atomic radii and higher nuclear charge as compared to the
alkali metals. Both these factors tend to increase the ionisation energy, as observed. The ionisation energy in
any transition series increases with atomic number; the increase however is not smooth and as sharp as
seen in the case of s- and p-block elements.
Ionisation enerty increases in the beginning of the series but then gradually decreases.

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EXPLANATION. The ionisation energy increases due to the increase in the nuclear charge with atomic
number at the beginning of the series. Gradually, the shielding effect of the added electrons also increases.
This shielding effect tends to decrease the attraction due to the nuclear charge.

The melting and boiling point: The melting and boiling points of transition elements except Cd and Hg, are
very high as compared to the s-block and p-block elements. The melting and boiling points first increase,
pass through maxima and then steadily decrease across any transition series. The maximum occurs around
middle of the series. Atoms of the transition elements are closely packed and held together by strong
metallic bonds.

The strength of the metallic bonds depends upon the number of unpaired electrons in the outermost shell
of the atom. Thus, greater is the number of unpaired electrons stronger is the metallic bonding. In any
transition element series, the number of unpaired electrons first increases from 1 to 5 and then decreases
back to zero. The maximum five unpaired electrons occur at Cr (3d series). As a result, the melting and
boiling points first increase and then decrease showing maxima around the middle of the series.
The low melting points of Zn, Cd, and Hg may be due to the absence of unpaired d-electrons in their atoms.

Enthalpies of Atomization: Transition metals exhibit high enthalpies of atomization.

EXPLANATION. This is because the atoms in these elements are closely packed and held together by strong
metallic bonds. The metallic bond is formed as a result of the interaction of electrons in the outermost shell.
Greater the number of valence electrons, stronger is the metallic bond.

Oxidation States: Most of the transition elements exhibit several oxidation states, i.e., they show variable
valency in their compounds.
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Element Outer electronic configuration Oxidation states
Sc 3d1 4s2 + 2, + 3
2 2
Ti 3d 4s + 2, + 3, + 4
3 2
V 3d 4s + 2, + 3, + 4, + 5
Cr 3d5 4s1 + 1, + 2, + 3, + 4, + 5, + 6
5 2
Mn 3d 4s + 2, + 3, + 4, + 5, + 6, + 7
6 2
Fe 3d 4s + 2, + 3, + 4, + 5, + 6
Co 3d7 4s2 + 2, + 3, + 4
8 2
Ni 3d 4s + 2, + 3, + 4
10 1
Cu 3d 4s + 1, + 2
Zn 3d10 4s2 +2
The outermost electronic configuration of the transition elements is (n – 1) d1– 10 ns2. Since, the energy
levels of (n – 1)d and ns-orbitals are quite close to each other, hence both the ns- and (n – 1) d-
electrons are available for bonding purposes. Therefore, the number of oxidation states shown by
these elements depends upon the number of d-electrons it has. For example, Sc having a configuration
3d1 4s2 may show an oxidation state of + 2 (only s-electrons are lost) and + 3 (when d-electron is also
lost). The highest oxidation state which an element of this group might show is given by the total
number of ns- and (n – 1) d-electrons. The lesser number of oxidation states at the extreme ends
stems from either too few electrons to lose or share (Sc, Ti) or too many d electrons (hence fewer
orbitals available in which to share electrons with others) for higher valence (Cu, Zn).

Ionisation energies and the stability of oxidation states. The values of the ionisation energies can be used in
estimating the relative stability of various transition metal compounds (or ions). For example, Ni2+
compounds are found to be thermodynamically more stable than Pt 2+, whereas Pt4+ compounds are more
stable than Ni4+ compounds. The relative stabilities of Ni2+ relative to Pt2+, and that of Pt4+ relative to Ni4+
can be explained as follows. The first four ionisation energies of Ni and Pt are as follows:
Metal (IE1 + IE2), kJ mol–1 (IE3 + IE4), kJ mol–1 Etotal, kJ mol–1 (= IE1 + IE2 + IE3 + IE4)
Ni 2490 8800 11290
Pt 2660 6700 9360
Thus, the ionisation of Ni to Ni requires lesser energy (2490 kJ mol–1) as compared to the energy required
2+

for the production of Pt2+ (2660 kJ mol–1). Therefore, Ni2+ compounds are thermodynamically more stable
than Pt2+ compounds. On the other hand, formation of Pt4+ requires lesser energy (9360 kJ mol–1) as
compared to that required for the formation of Ni4+ (11290 kJ mol–1). Therefore, Pt4+ compounds are more
stable than Ni4+ compounds. This is supported by the fact that [PtCl6]2– complex ion is known, while the
corresponding ion for nickel is not known.
However, other factors which affect the stability of a compound are, enthalpy of sublimation of the metal
lattice and the solvation energies of the compound or ion.

Formation of Coloured Ions:

Most of the compounds of the transition elements are coloured in the solid state and/or in the solution
phase. The compounds of transition metals are coloured due to the presence of unpaired electrons in their
d-orbitals. This occurs as follows.

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EXPLANATION. In an isolated atom or ion of a transition element, all the five d-orbitals are of the same
energy (they are said to be degenerate). Under the influence of the combining anion(s), or electron-rich
molecules, the five d-orbitals split into two (or some time more than two) levels of different energies. The
difference between the two energy levels depends upon the nature of the combining ions. The d-d
transitions in the coloured complexes corresponds to the energy released in the form of radiations in the
visible region, (λ= 380 nm – 760 nm).

Magnetic Properties
Most of the transition elements and their compounds show paramagnetism. The paramagnetism first
increases in any transition element series, and then decreases. The maximum paramagnetism is seen around
the middle of the series. The paramagnetism is described in Bohr Magneton (BM) units.
EXPLANATION: A substance which is attracted by magnetic field is called paramagnetic substance. The
substances which are repelled by magnetic field are called diamagnetic substances. Paramagnetism is due to
the presence of unpaired electrons in atoms, ions or molecules. The magnetic moment of any transition
element or its compound/ion is given by (assuming no contribution from the orbital magnetic moment),
µB = [n(n +2)]1/2 BM
where, n is the number of unpaired electrons.

Formation of Complex Ions

Transition metals and their ions show strong tendency for complex formation. The cations of transition
elements (d-block elements) form complex ions with certain molecules containing one or more lone-pairs of
electrons, viz., CO, NO, NH3 etc., or with anions such as, F–, Cl–, CN– etc. A few typical complex ions are,
[Fe(CN)6]4–, [Cu(NH3)4]2+, [Y(H2O)6]2+, [Ni(CO)4], [Co(NH3)6]3+, [FeF6]3–
This complex formation tendency is due to,
(a) small size and high nuclear charge of the transition metal cations.
(b) the availability of vacant inner d-orbitals of suitable energy.

Formation of Interstitial Compounds

Transition elements form a few interstitial compounds with elements having small atomic radii, such as
hydrogen, boron, carbon and nitrogen. The small atoms of these elements get entrapped in between the
void spaces (called interstices) of the metal lattice. Some characteristics of the interstitial compounds are,
(a) These are non-stoichiometric compounds and cannot be given definite formulae.

5
 (b) These compounds show essentially the same chemical properties as the parent metals, but
differ in physical properties such as density and hardness. Steel and cast iron are hard due to
the formation of interstitial compound with carbon.
EXPLANATION. Interstitial compounds are hard and dense. This is because, the smaller atoms of lighter
elements ocupy the interstices in the lattice, leading to a more closely packed structure. Due to greater
electronic interactions, the strength of the metallic bonds also increases.
The principal physical and chemical characteristics of these compounds are as follows:
(i) They have high melting points, higher than those of pure metals.
(ii) They are very hard, some borides approach diamond in hardness.
(iii) They retain metallic conductivity.
(iv) They are chemically inert.

Catalytic Properties: Most of the transition metals and their compounds particularly oxides have good
catalytic properties. Platinum, iron, vanadium pentoxide, nickel, etc., are important catalysts. Platinum is a
general catalyst. Nickel powder is a good catalyst for hydrogenation of unsaturated organic compounds such
as, hydrogenation of oils. Some typical industrial catalysts are:
(a) Vanadium pentoxide (V2O5) is used in the Contact process for the manufacture of sulphuric
acid,
(b) Finely divided iron is used in the Haber’s process for the synthesis of ammonia.
EXPLANATION. Most transition elements act as good catalyst because of,
(a) the presence of vacant d-orbitals.
(b) the tendency to exhibit variable oxidation states.
(c) the tendency to form reaction intermediates with reactants.
(d) the presence of defects in their crystal lattices.
For example, iron(III) catalyses the reaction between iodide and persulphate ions.
2 I– + S2O82– → I2 + 2 SO42–
An explanation of this catalytic action can be given as:
2 Fe3+ + 2 I– → 2 Fe2+ + I2
2 Fe2+ + S2O82– → 2 Fe3+ + 2SO42–

Alloy Formation
Transition metals form alloys among themselves. The alloys of transition metals are hard and high melting as
compared to the host metal. Various steels are the alloys of iron with metals such as chromium, vanadium,
molybdenum, tungsten, manganese etc.
EXPLANATION. The atomic radii of the transition elements in any series are not much different from each
other. As a result, they can very easily replace each other in the lattice and form solid solutions over an
appreciable composition range. Such solid solutions are called alloys.

Potassium Dichromate,(K2Cr2O7)
Manufacture from chromite ore: K2Cr2O7 is generally manufactured from chromite ore (FeCr2O4). The
process involves the following steps.
(a) Preparation of sodium chromate. Finely powdered chromite ore is mixed with soda ash and
quicklime. The mixture is then roasted in a reverberatory furnace in the presence of air. Yellow mass
due to the formation of sodium chromate is obtained.
4FeCr2O4 + 8Na2CO3 + 7O2 → 2Fe2O3 + 8CO2(g) + 8Na2CrO4
(sodium chromate)
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 The yellow mass is extracted with water, and filtered. The filtrate contains sodium chromate.
(b) Conversion of chromate into dichromate. Sodium chromate solution obtained in step (a) is treated
with concentrated sulphuric acid when it is converted into sodium dichromate.
2Na2CrO4 + H2SO4 → Na2Cr2O7 + Na2SO4 + H2O
sodium chromate sodium dichromate
(c) Conversion of sodium dichromate to potassium dichromate. Hot concentrated solution of sodium
dichromate is treated with a calculated amount of potassium chloride, when potassium dichromate
being less soluble crystallizes out on cooling.
Na2Cr2O7 + 2KCl →K2Cr2O7 + 2NaCl
The chromates and dichromates are interconvertible in aqueous solution depending upon pH of the
solution. The oxidation state of chromium in chromate and dichromate is the same.
2 CrO42– + 2H+ → Cr2O7 2– + H2O
Cr2O7 2– + 2OH- → 2 CrO4 2– + H2O
Oxidising nature. In neutral or in acidic solution, potassium dichromate acts as an excellent oxidising agent,
and Cr2O72– gets reduced to Cr3+. The standard electrode potential for the reaction,
Cr2O72– + 14H+ + 6e– → 2Cr3+ + 7H2O
is + 1.31 V. This indicates that dichromate ion is a fairly strong oxidising agent, especially in strongly acidic
solutions. That is why potassium dichromate is widely used as an oxidising agent, for quantitative estimation
of the reducing agents such as, Fe2+.
a) Cr2O72– + 14H+ + 6Fe2+ →2Cr3+ + 6Fe3+ + 7H2O
b) Oxidation of Sulphites to sulphates and arsenites to arsenates.
Cr2O72– + 8H+ + 3SO32– →2Cr3+ + 3SO42– + 4H2O
Similarly, arsenites are oxidised to arsenates.
Cr2O72– + 8H+ + 3AsO33– →2Cr3+ + 3AsO43– + 4H2O
c) Oxidation of Hydrogen halides to halogens.
Cr2O72– + 8H+ + 6HX →2Cr3+ + 3X2 + 7H2O
d) Oxidation of Iodides to iodine
Cr2O72– + 14H+ + 6I– →2Cr3+ + 7H2O +3I2
Thus, when KI is added to an acidified solution of K2Cr2O7 iodine gets liberated.
e) It oxidises H2S to S.
Cr2O72– + 8H+ + 3H2S → 2Cr3+ + 3S + 7H2O
Chromates and dichromates are the salts of chromic acid (H2CrO4). In solution, these ions exist in equilibrium
with each other. Chromate ion has four oxygen atoms arranged tetrahedrally around Cr atom. Dichromate
ion involves a Cr – O – Cr bond.

Structure of Chromate and Dichromate Ions

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Pottassium Permanganate, (KMnO4)
Preparation of potassium permanganate:
a) Conversion of pyrolusite to potassium manganate. When manganese dioxide is fused with potassium
hydroxide in the presence of air or an oxidising agent such as potassium nitrate or chlorate,
potassium manganate is formed,
2MnO2 + 4KOH (fused) + O2 → 2K2MnO4 + 2H2O
pyrolusite potassium manganate(dark-green mass)
b) Oxidation of potassium manganate to potassium permanganate. This produces the dark green
K2MnO4 which disproportionates in a neutral or acidic solution to give permanganate.
3MnO42– + 4H+ → 2MnO4– + MnO2 + 2H2O
Oxidising action. KMnO4 is a powerful oxidising agent in neutral, acidic and alkaline media. The nature of
reaction is different in each medium. The oxidising character of KMnO 4 (to be more specific, of MnO4–) is
indicated by high positive reduction potentials for the following reactions.
Acidic medium:
MnO4– + 8H+ + 5e– Mn2+ + 4H2O E° = 1.51 V
Alkaline medium:
MnO4– + 2H2O + 3e–  MnO2 + 4OH– E° = 1.23 V
Some typical reactions are
(a) In the presence of excess of reducing agent in acidic solutions permanganate ion gets reduced to
manganous ion, e.g.,
5Fe2+ + MnO4– + 8H+ →5Fe3+ + Mn2+ + 4H2O
(b) An excess of reducing agent in an alkaline solution reduces permanganate ion only to manganese
dioxide, e.g.,
3NO2– + MnO4 – + 2OH– →NO3 – + MnO2 + H2O
(c) In acidic medium, KMnO4 oxidises,
(i) Ferrous salts to ferric salts
2MnO4– + 16H+ + 10Fe2+ →2Mn2+ + 10Fe3+ + 8H2O
This reaction forms the basis of volumetric estimation of Fe2+ in any solution by KMnO4.
(ii) Oxalic acid to carbon dioxide
2MnO4– + 6H+ + 5(COOH)2 →2Mn2+ + 10CO2 + 8H2O
(iii) Sulphites to sulphates
2MnO4– + 6H+ + 5SO32– →2Mn2+ + 5SO42– + 3H2O
(iv) Iodides to iodine in acidic medium
2MnO4– + 16H+ + 10I– →2Mn2+ + 5I2 + 8H2O
(v) Hydrogen peroxide to oxygen
2MnO4– + 6H+ + 5H2O2 →2Mn2+ + 5O2 + 8H2O
Uses. KMnO4 is used,
(i) as an oxidising agent.
(ii) as a disinfectant against disease-causing germs.
(iii) for sterilizing wells of drinking water.
(iv) in volumetric estimation of ferrous salts, oxalic acid etc

The f-block elements: The elements which in their elemental or ionic form have partly filled f-orbitals are
called f-block elements. As the f-orbitals lie inner to the penultimate (second outermost) shell, therefore
these elements having partially filled f-orbitals are also known as inner-transition elements.
8
There are two series of inner-transition elements, each having 14 elements. The elements in which 4f
orbitals are progressively filled are called lanthanides. The elements in which 5f orbitals are progressively
filled are termed actinides. All these elements closely resemble one another in their properties. Because of
their limited availability, these are also known as the rare earth elements.
The outer-electronic configurations of the lanthanides are given in the following Table
Name Symbol Atomic number Outer electronic configuration
Cerium Ce 58 4f 1 5d1 6s2
Praseodymium Pr 59 4f 3 5d0 6s2
Neodymium Nd 60 4f 4 5d0 6s2
Promethium Pm 61 4f 5 5d0 6s2
Samarium Sm 62 4f 6 5d0 6s2
Europium Eu 63 4f 7 5d0 6s2
Gadolinium Gd 64 4f 7 5d1 6s2
Terbium Tb 65 4f 9 5d0 6s2
Dysprosium Dy 66 4f 10 5d0 6s2
Holmium Ho 67 4f 11 5d0 6s2
Erbium Er 68 4f 12 5d0 6s2
Thulium Tm 69 4f 13 5d0 6s2
Ytterbium Yb 70 4f 14 5d0 6s2
Lutetium Lu 71 4f 14 5d1 6s2

The fourteen elements (atomic number 90–103) after actinium are called actinides. These are also called
second series of inner-transition elements. The general electronic configuration of actinides is 5f1–14 6d0–1
7s2.
General Characteristics of Lanthanides
(1) Electronic configuration. The 5d and 4f energy levels are very close-by in lanthanoids. It is not always
possible to decide with certainty whether the electron has entered 5d or 4f level. Due to the extra-stability
of half-filled and completely filled orbitals, there is a tendency to acquire f 7 and f 14 configurations
wherever possible. The general electronic configuration of lanthanides may be described as 4f 1–14 5d 0–1 6s2.
(2) Oxidation states. Lanthanides in aqueous solution and in the solid state exhibit oxidation
states of + 2, + 3 and + 4. The trivalent state (+ 3) being more stable.
(3) Magnetic properties. La3+ and Lu3+ are diamagnetic, while the trivalent ions of the rest of the
lanthanides are paramagnetic in nature. The paramagnetic moment values of the lanthanide ions are higher
than those expected on the basis of the number of unpaired electrons. This occurs due to an appreciable
contribution from orbital angular momentum.
(4) Reduction potentials and metallic character. The standard electrode (reduction) potentials of the
lanthanide ions become less negative across the series. Thus, their reducing power decreases in going from
Ce to Lu. The highly negative E° values indicate these elements to be highly electropositive metals capable of
displacing hydrogen from water.
2M + 6H2O→ 2M(OH)3 + 3H2(g)
The M(OH)3 are ionic and basic in character. These hydroxides are stronger than Al(OH) 3 and weaker than
Ca(OH)2. The basic strength decreases in going from La to Lu.
(5) Atomic and ionic size: Lanthanide contraction. The atomic and ionic sizes decrease steadily in going
from Ce to Lu. In the atoms of lanthanides, the nuclear charge increases with atomic number, and the added
electrons go to the inner 4f orbitals. The shielding effect of 4f electrons from the increased nuclear charge, is
poor. Thus, as the atomic number increases, the effective nuclear charge experienced by each 4f electron
9
increases. This causes a slight reduction in the entire 4f shell. The successive contractions accumulate and
the total effect for all the lanthanides is called lanthanide contraction. The 4f electrons also shield the
valence shell from contracting appreciably.
Consequences of lanthanide contraction. The lanthanide contraction has a highly significant effect on the
relative properties of the elements which precede and follow lanthanides in the periodic table. Some
important consequences of lanthanide contraction are:
(i) Hf 4+ and Zr 4+ have almost equal radii, being 80 and 81 pm respectively. The pairs of elements
after lanthanum such as, Zr – Hf, Nb – Ta, Mo – W, etc., have almost the same size. The prop-
erties of these elements are also very similar. It is thus a direct consequence of lanthanide
contraction that the elements of the second and third transition series resemble each other
much more closely than do the elements of the first and second transition series.
(ii) Due to lanthanide contraction, i.e., decrease of ionic size on moving from La3+ to Lu3+, the
covalent character in bonding increases in the direction La3+ → Lu3+. As a result, the basic
character of the lanthanide hydroxides (M(OH)3) decreases with increase in atomic number.
Thus, La(OH)3 is the most basic, while Lu(OH)3 is the least basic. This aspect has been utilized
in the separation of lanthanides from each other.
(6) Formation of complex salts and ions. Lanthanide ions (M3+) have high charge, but due to their larger
size, these cannot polarize the neighbouring anion/molecule. As a result, these lanthanides do not show a
strong tendency towards complex formation.
(7) Colour of the salts and ions in solution. Most of the lanthanide trivalent ions are coloured in solid as
well as in the solution phase. The ions containing x and (14 – x) electrons show the same colour. The colour
of the salts or ions is due to the f – f transition of electrons.
Uses of Lanthanoids and actinoids: Due to their alloy-forming tendencies, actinides and lanthanides form
many alloys particularly with iron. These elements improve the workability of steel. A well known alloy
is ‘misch-metal’ which consists of a rare earth element (94 – 95%), iron (up to 5%) and traces of sulphur,
carbon, calcium and aluminium. The pyrophoric alloys containing rare-earth metals are used in the
preparation of ignition devices, e.g., tracer bullets and shells and flints for lighters. This alloy has normally
the composition: cerium 40.5%, lanthanum + neodymium 44%, iron 4.5%, aluminium 0.5% and the
remainder calcium, silicon and carbon.
Property Lanthanides actinides
1 Binding energy Binding energies of 4f are higher. Binding energies of 5f are lower.
2 Shielding effect. 4f electrons have greater shielding f electrons have poor shielding
effect. Therefore, the contraction in effect. Therefore, the contrac-
their ionic radii is less tion in their sizes radii is more.
3 Tendency to form The tendency to form complexes is They have greater tendency to
complexes less. form complexes.
4 Basic character. Lanthanide compounds are less Actinide compounds are more
basic. basic.
5 Tendency to form oxoions. They do not form oxoions. They form oxo ions such as
U02+, NpO2+, PuO2+, UO22+.
6 Radioactivity. Except promethium these are non All the actinides are radioactive
- radioactive
7 Colours. Most of their Ions are colourless. Most of the actinide ions are
coloured.
8 Paramagnetic character. They are paramagnetic and their They are also paramagnetic
magnetic properties can be easily but their magnetic properties
10
 explained. cannot be easily explained.

Similarities between lanthanides and actinides

1. Both exhibit oxidation state of +3 predominantly.
2. In both the series, f-orbitals are being progressively filled.
3. Actinides and lanthanides having same number of unpaired electrons have quite similar spectra. In
the absorption spectra of the elements of both the series, sharp line like bands appear due to f-f
transitions.
4. Both are electropositive and have high reactivity.
5. Like lanthanide contraction, there is actinide contraction. These contractions are due to poor
shielding of 5f and 4f electrons in actinides and lanthanides respectively.
6. The nitrates, perchlorates and sulphates of trivalent actinides and lanthanides are soluble whereas
the hydroxides, fluorides and carbonates of the elements of both the series are insoluble
7. Actinides like lanthanides show ion exchange behaviour.

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