d -BLOCK ELEMENTS

1. TRANSITION ELEMENTS AND COMPLEXES

(i) In the long form of periodic table elements are classified based on electronic configuration. The elements
which are classified between’s’ and ‘p’ block are ‘d’ block elements or Transition elements. In these
elements the differentiating electron enters in the ‘d’ orbitals of penultimate shell.
(ii) General configuration for ‘d’ block elements is ns1-2 (n-1)d1-10. i.e., in ‘d’ block elements the valence
shell has constant number of electrons whereas the number of electron in penultimate shell go on increas-
ing.
(iii) Elements which have atleast one unpaired electron in their ‘d’ orbital in atomic or any oxidation state are
called as Transition elements. Thus all transition elements are ‘d’ block elements but all ‘d’ block ele-
ments may not be transition elements or the elements having incompletely filled ‘d’ orbitals are called as
transition elements.
(iv) Transition elements are classified between’s’ and ‘p’ blocks from fourth period onwards. Series of
transition elements are four
The first transition series : (3d series) involves the filling of 3d orbitals and has 10 elements from
scandium (Z = 21) to zinc (Z = 30)

The second transition series : (4d series) involves the filling of 4d orbitals and has 10 elements from
ytterium (Z = 39) to cadium (Z = 48).

The third transition series : (5d series) involves the filling of 5d orbitals and has 10 elements. The first
element of this series is lanthanum (Z = 57). It is followed by 14 elements (lanthanides, involving filling of
4f orbitals). The next nine elements are from hafnium (Z = 72) to mercury (Z = 80)

The fourth transition series is incomplete and contains only three elements 89Ac, 104Rf, 105Ha.
(v) Zn (30) is [Ar] 4s23d10
Cd (48) is [Kr] 5s24d10
Hg (80) is [Xe] 6s2 4f 14 5d10
These elements have completely filled (n–1)d subshell in their elementary as well as ionic state and so are
not true transition metals. Their properties are quite different from those of transition metals.
Zn is used in galvanizing, in making alloys, in making white pigment and in rubber industry (ZnO acts as
filler). Cd is used in nuclear reactors as moderators, in making NiCd storage cells and in making paints.
Mercury is used in scientific equipments and in electrolytic cells. Several compounds of Hg are used in
making antiseptics.

d- and f-Block [1]

2. GENERAL CHARACTERISTICS
(i) The properties of d-block elements of any given period are not so much different from one
another as those of the same period of non transition elements.
(ii) It is due to the fact that, in transition series, there is no change in number of electrons of outermost
shell and only change occur in ( n– 1) d electron from member to member in a period.
(a) Metallic Character
(i) All the transition elements are metals, since the number of electrons in the outermost shell is very
small being equal to 2.
(ii) They are hard, malleable and ductile, except Hg which is liquid and soft.
(iii) They exhibit all the three types of structures. Face Centred Cubic ( fcc), Hexagonal Close
packed (hcp) and Body Centred Cubic ( bcc).
(iv) Covalent and Metallic bonding both exist in the atom of transition metals.
(v) The presence of unfilled d- subshell favour covalent bonding, and metallic bonding is due to
possession of one or two electron inoutermost energy shell.
(vi) These metals are good conductors of heat and electricity.
(b) Melting and Boiling Points :
(i) The transition elements have very high melting & boiling points as compared to those of s & p
block elements.
(ii) The high melting and boiling point of transition metals are attributed to the stronger force that
bind their atoms together.
(iii) As the number of d- electron increases the number of covalent bond between the atoms are
expected to increase up to Cr- Mo- W family where each of the d- orbital has only unpaired
electrons and the opportunity for covalent sharing is greatest.
(iv) Inspite of presence of five unpaired electrons in Mn, the unexpected low melting and boiling is
due to its complex structure it is unable to form metallic and covalent bonds.
(v) The absence of unpaired electron [ ( n– 1) d10 4s2] in Zn, Cd, & Hg is responsible for its low
melting & boiling point.

Cr
2000 V 1900
Ti 1710
Melting Point t/ºC

1530
1672 Fe 1495Ni
1500 Sc
1397 Co 1455
Mn Cu
1244 1083
1000

500 420
Zn
IA II A IIIB IVB VB VIBVIIBVIII IA IIB

Graphic representation m.p. of 3d - series elements

d- and f-Block [2]

(c) Atomic and Ionic Radii
Elements Sc Ti V Cr Mn Fe Co Ni Cu Zn

Atomic Radii (Aº) 1.44 1.32 1.22 1.18 1.14 1.17 1.16 1.15 1.27 1.25
Ionic radii (Aº)
for M2+ 0.95 0.90 0.88 0.74 0.80 0.76 0.74 0.72 0.69 0.74
for M3+ 0.81 0.68 0.73 0.69 0.66 0.64 0.63 0.62 - -
Metallic
radii (Aº) 1.62 1.47 1.34 1.27 1.26 1.26 1.25 1.24 1.28 1.38

The value of these radii decreases generally, on moving from left to right in the period.
Reason :
(i) This is due to the fact that an increase in the nuclear charge tends to attract the electron cloud
inwards.
(ii) The radii for the elements from Cr to Cu are however very close to one another.
(iii) The simultaneous addition of electron of 3d- level exercises the reverse effect by screening the
outer 4s - electron from the inward pull of the nucleus.
(iv) As a result of these two opposing effects, the atomic radii do not alter much on moving from Cr
to Cu.
(v) The radii of M2+ ions, although some what smaller than that of Ca2+ ion ( = 0.99 Aº) are
comparable with it.
Oxides :
(i) Thus Mo oxides of transition element should be similar to CaO in many ways, although some
what less basic and less soluble in water.
(ii) Similarly the Hydration energy of M2+ ion [Ti2+  Cu2+] are between 446 KCal to 597 KCal is
some what greater than that of Ca2+ ion [ 395 K cal].
Oxides of first row transition metals
(i) Basic Oxides : Sc2O3, TiO2, Ti2O3, VO, V2O3, MnO, FeO, Fe2O3, Fe3O4, CoO, NiO, Cu2O.
(ii) Acidic oxides : V2O5, CrO3, Mn2O7.
(iii)Amphoteric oxides : TiO2, VO3, Cr2O3, CrO2, Mn2O3, Mn3O4, MnO2, CuO.
(d) Ionisation Potential
(i) The first ionisation potential of transitional elements lie between those of s & p block elements.
(ii) The first ionization potential of all the transition elements lie between 6 to 10 ev.
(iii) In case of transition elements the addition of the extra electron in the ( n– 1) d provides a
screening effect which shields the outer ns electron from the inward pull of positive nucleus.
(iv) Thus the effect of increasing nuclear charge & the shielding effect created due to the expansion
of ( n– 1) d orbital oppose each other.
(v) On account of these counter affects, the ionisation potentials increases rather slowly on the
moving in a period of the first transition series.
(vi) The IE1 for the first four 3d - block elements ( Sc, Ti, V & Cr) differ only slightly from one
another.
(vii) Similarly the value of Fe, Co, Ni & Cu also are fairly close to one another.
Ionisation Sc Ti V Cr Mn Fe Co Ni Cu Zn
Potential (ev.)
IE1 6.56 6.83 6.74 7.43 7.43 7.90 7.86 7.63 7.72 9.39
IE2 12.91 13.69 14.26 16.95 15.69 16.21 17.08 18.21 20.34 18.00
IE3 24.79 27.52 29.35 31.0 23.34 30.69 33.54 35.21 36.88 39.78

d- and f-Block [3]

(e) Oxidation State
(i) One of the most important property that distinguishes transition element from s & p block element
is that they show variable oxidation states.
(ii) This unique property is due to the fact that the energy levels of 3d, 4d and 5d orbitals are fairly
close to those of 4s, 5s and 6s respectively.
(iii) Therefore, in addition to ns electron, variable number of ( n– 1) d electron are also lost in getting
various oxidation states.
Different oxidation states exhibited by ‘Transitional Metals’

III B IV B VB VI B VII B VIII IB II B

Elements of 3d- series ( Period 4)

Sc21 Ti22 V23 Cr24 Mn25 Fe26 Co 27 Ni28 Cu29 Zn30

+1 +1
+ 2* + 2* +2 +2 (+ 2) (+ 2) (+ 2) (+ 2) (+ 2) (+ 2)
(+ 3) +3 +3 (+ 3) + 3* (+ 3) (+ 3) + 3
(+ 4) +4 (+ 4) (+ 4) + 4* + 4* + 4*
(+ 5) + 5* + 5* + 5* + 5*
(+ 6) +6 (+ 6)
(+ 7)

Note : I – Most stable oxidation states are in brackets.

II – Very rare oxidation states are shown by *.
(iv) All the transition elements with exception of Cr, Cu, Ag, Au & Hg (which have a minimum
oxidation state of +1) exhibit a minimum oxidation state of + 2.
(v) Each of the elements in groups II B to VII B can show maximum oxidation state equal to its
group number. Example Cr in group VI B show maximum oxidation state equal to + 6 in
Cr2O72– ion.
(vi) Most of the elements of VIII group show a maximum oxidation state equal to + 6.
(vii) However, Ru (RuO4) & Os (OsO4) have a maximum oxidation state equal to + 8 which is the
highest oxidation state shown by any element.
(viii) There is an increase in number of oxidation states in going from left to right in a period.
(ix) Maximum number of oxidation state is reached somewhere in the middle of a series.

(f) Relative stability of various oxidation states :

(i) The relative stabilities of various oxidation states of 3d- series element can be correlated with
the extra stability of 3dº, 3d5 & 3d10 configuration to some extent.
Example - Ti4+ ( 3dº) is more stable than Ti 3+ ( 3d1)
Mn2+ ( 3d5) is more stable than Mn3+ ( 3d4).
(ii) The higher oxidation state of 4d and 5d series element are generally more stable than those of
the element of 3d series.

d- and f-Block [4]

Example - (a) MoviO42–,TcviiO4–(4d- series element) & Wvi O42–, ReviiO4– ( 5d - series elements)
are more stable and in which the transition element concerned show their maximum
oxidation state.
(b) Crvi O42– & Mnvii O4– ( 3d - series) are strong oxidizing agents.

(iii) Strongly reducing states probably do not form fluorides or oxides, but may well form the heavier
halides. Conversely, strong oxidizing state form oxides & fluoride, but not Bromide and Iodide.
Example -
(a) V react with halogens to form VF5, VCl4, VBr3, but doesn’t form VBr5 or VI5 because in + 5
oxidation state V is strong oxidizing agent thus convert Br– & I– to Br2 & I2 respectively, So
VBr3 & VI3 are formed but not VBr5 & VI5.
(b) On the other hand VF5 is formed because V5+ ion unable to oxidize highly electronegative &
small anion F–.
(c) Similarly highly electronegative and small O2–ion formed oxides eg. VO43–, CrO42– & MnO4–
etc.
(iv) All transition elements in their lower oxidation state like to form ionic compounds. Whereas in
their higher oxidation state they generally formed covalent compound.
Example-
+2 +3 +4 +5 +6 +7
TiCl2 TiCl3 TiCl4
VCl2 VCl3 VCl4 VOCl3
(Ionic, Less ionic basic) Amphoteric Covalent & Acidic, (Strong Lewis acid)
TiO Ti2O3 TiO2
VO V2 O 3 V2O5
CrO Cr2O3 CrO3
MnO Mn2O3 MnO2 MnO3 Mn2O7

Ionic Less Ionic Acidic

(Basic) (Amphoteric) (Covalent)

Formation of Complexes :
By virtue of their small size, comparatively high nuclear or ionic charge and availability of vacant
d-orbitals of suitable energy, these metals exert strong electrostatic attraction on the ligands. The species
formed on interaction of metal and the ligand (or ligands) is known as a complex.
The transition metal ions form complexes because of the following reasons :
(a) Their small cation size
(b) High effective nuclear charge
(c) Availability of vacant (n-1) d-orbitals of appropriate energy
(d) The structure commonly found in such complex are linear (i.e. co-ordination number, C.N.=2),
square planer (C.N. =4), tetrahedral (CN = 4) or octahedral (CN = 6).
(e) Cobalt form more complex than any other elements
Co3+ + 6NH3  [Co(NH3)6]3+
Fe2 + 6CN–  [Fe(CN)6]4–
Co3+ + 6H2O  [Co(H2O)6]3+

d- and f-Block [5]

 Metal ion Ligand C.N. Complex ion
Ag+ NH3 2 [Ag(NH3)2]+
Ni+2 CN – 4 Ni(CN)4]–2
Cu2+ NH3 4 [Cu(NH3)4]+2
Fe+2 CN – 6 [Fe(CN)6]–4
(g) Magnetic properties
* As is evident most of the transition metal ions have unpaired electrons in their ‘d’ orbitals. Hence most of
the transition metal ions are paramagnetic in nature. Transition metal ions having 3d0 and 3d10 configura-
tion exhibit diamagnetic nature.
* The magnetic moment () created due to spinning of unpaired electrons can be calculated by using
 = n(n  2) : Where ‘n’ is the number of unpaired electrons in the metal ion.
 = Magnetic moment in Bohr Magnetons (B.M.)
* The magnetic moment of diamagnetic substances will be zero.
* As the number of unpaired electrons increase the magnetic moment created goes on increasing and
hence the paramagnetic nature also increases.
* Transition metal ions having d5 configuration will have maximum number of unpaired electrons therefore
they will be maximum paramagnetic in nature.
Variation of Magnetic moment of 3d- series
Ions Outer Number of Magnetic Moment  B.M.
with most unpaired
configuration configuration electron
Sc3+ 3dº 0 0
3+
Ti , V 4+ 3d 1 1 1.75
2+ 3+ 2
Ti , V 3d 2 2.86
V2+, Cr3+ 3d3 3 3.86
3+
Cr , Mn 3+ 3d 4 4 4.80
2+
Mn , Fe 3+ 3d 5 5 5.95
2+
Fe ,Co 3+ 3d 6 4 5.0 – 5.5
2+ 7
Co 3d 3 4.0 – 5.2
Ni 2+ 3d 8 2 2.9 – 3.4
2+ 9
Cu 3d 1 1.4– 2.2
2+ 10
Zn 3d 0 0
(h) Formation of Coloured Compounds :
The transition metal ions have unpaired d-electrons, which on absorbing visible light can jump from one
d-orbital to another i.e. intra d-d- transition take place. Thus when light falls certain visible wavelengths
are absorbed. The reflected light appears coloured and gives the colour of compound. The ions having
no d-d transitions are colourless.
A - Factors affecting the colour of complex.
The colour of a transition metal complex depend on-
(i) The magnitude of energy difference between the two d- levels (),
(ii) An increase in the magnitude of  decreases the wave length (  ) of the light absorbed by the
complexes.
(iii) Thus with a decrease in the  the colour of complex changes from Red Violet.

d- and f-Block [6]

 Sc Ti V Cr Mn Fe Co Ni Cu Zn
Oxidation
Potential value
(v) for M  - 1.60 1.20 0.91 1.18 0.44 0.28 0.25 0.34 0.76
2+
M + 2e –

M  M3+ +
3 e– 2.10 - - 0.74 - - - - - -

(i) Formation of interstitial compounds

(i) Small non metallic atom such as H,B,C,N etc. are able to occupy interstitial space of the lattice
of the d- block elements to form combinations which are termed interstitial compounds.
(ii) These are non-stoichiometric in nature and do not follow the common rule of valency.
(iii) These interstitial compounds have similar chemical properties as the parent metal but differ
appreciably in their physical properties such as density, hardness and conductivity.
(j) Catalytic properties
Many transition metals & their compounds have catalytic properties. Some common examples
are-
(a) In some cases the transition metals with their variable valency may form unstable intermediate
compounds.
(b) In other cases the transition metal provide a suitable reaction surface.
(c) Enzymes are catalyst that enhance the rate of specific reactions. Some enzymes require the
presence of metal ions as cofactors and these are called metalloenzymes.
(i) TiCl3 - Used as Ziegler - Natta catalyst in the production of polyethene.
(ii) V2O5 - Convert SO2 to SO3 in the contact process for making H2SO4.
(iii) MnO2 - Used as a catalyst to decompose KClO3 to give O2.
(iv) Fe - promoted iron is used in Haber- Bosch process for making NH3.
(v) FeCl3 - Used for making CCl4 from CS2 & Cl2.
(vi) FeSO4 & H2O2 - Used as Fenton's reagent for oxidizing alcohol to aldehyde.
(vii) Pt.- used as a catalyst in the manufacture of H2SO4.
(viii) Ni - used as a catalyst in the hydrogenation of oils.
(ix) PdCl2 -Wocker process for converting C2H4 + H2O + PdCl2 to CH3CHO + 2HCl + Pd.
(x) Pt/ PtO- Adams catalyst, used for reduction.
(k) Alloy formation
(i) Transition metals form a large number of alloys.
(ii) d- block elements are quite similar in atomic size, the atom of one metal can substitute the atoms
of other metal in its crystal lattices.
(iii) Thus, on cooling a mixture solution of two or more transition metals, smooth solid, alloys are
formed.
(iv) Alloy containing mercury as one of the constituent elements are called amalgams.
(v) The purpose of making alloy is to develop some useful properties which are absent in constituent
element

d- and f-Block [7]

 f - BLOCK ELEMENTS
They were earlier called as rare earth metals as it was believed that they exist in earth’s crust to a very
less extent for e.g. : Pm, does not exist in the earth’s crust. But this terminology is now not applicable as
they exist in earth’s crust to a sufficient extent.
(A) INNER TRANSITION ELEMENTS
The elements in which the additional electron enters in (n – 2) f orbitals are called inner transition
elements. or f-block elements.
(a) Position in the periodic table
The lanthanides resemble yttrium in most of their properties. So it became necessary to accomodate all
the fifteen elements together at one place. This has been done by placing the first element, lanthanum
below yttrium and placing the remaining fourteen elements separately in the lower part of the periodic
table.
Lanthanide series (Z = 58 - 71) (Ce – Lu)
Actinide series (Z = 90 - 103) (Th – Lw)

(b) LANTHANIDES (4f - BLOCK ELEMENTS)

Lanthanides are reactive elements so do not found in free state in nature. Most important minerals for
lighter Lanthanides are - Monazite, cerites and orthite and for heavier lanthanides - Gadolinite and
Xenotime
(c) Electronic configuration
The general configuration of lanthanides may be given as 4f2-145s25p65d0/16s2. Lanthamide have outer
three shells incomplete.

Some properties of Lanthanoids

Element Symbol Atomic number Outer configuration Oxidation states M3+ radius
(pm)
Lanthanum La 57 [Xe] 5d1, 6s2 +3 106
Cerium Ce 58 [Xe] 4f2, 6s2 +3, +4 103
Praseodymium Pr 59 [Xe] 4f3, 6s2 +3, +4 101
Neodymium Nd 60 [Xe] 4f4, 6s2 +2, +3, +4 100
Promethium Pm 61 [Xe] 4f5, 6s2 +3 98
Samarium Sm 62 [Xe] 4f6, 6s2 +2, +3 96
Europium Eu 63 [Xe] 4f7, 6s2 +2, +3 95
Gadolinium Gd 64 [Xe] 4f7, 5d1, 6s2 +3 94
Terbium Tb 65 [Xe] 4f9, 6s2 +3, +4 92
Dysprosium Dy 66 [Xe] 4f10, 6s2 +3, +4 91
Holmium Ho 67 [Xe] 4f11, 6s2 +3 89
Erbium Er 68 [Xe] 4f12, 6s2 +3 88
Thulium Tm 69 [Xe] 4f13, 6s2 +2, +3 87
Ytterbium Yb 70 [Xe] 4f14, 6s2 +2, +3 86
Lutetium Lu 71 [Xe] 4f14, 5d1, 6s2 +3 85

d- and f-Block [8]

(i) It is to be noted here that filling of 4f orbitals in the atoms is not regular. A 5d electron appears in
gadolinium (z = 64) with an outer electronic configuration of 4f75d16s2 (and not 4f86s2). This is because
the 4f and 5d electrons are at about the same potential energy and that the atoms have a tendency to
retain stable half filled configuration.
(ii) On the other hand, the filling of f orbitals is regular in tripositive ions.
(iii) After losing outer electrons, the f orbitals shrink in size and became more stable. Pm is the only synthetic
radioactive lanthanide.

(d) Oxidation states

Lanthanides Ce58 Pr59 Nd60 Pm61 Sm62 Eu63 Gd64 Tb65 Dy66 Ho67 Er68 Tm69 Yb70 Lu71
Oxidation +3 +3 +3 +3 (+2) +2 +3 +3 +3 +3 (+2) (+2) +2 +3
States +4 (+4) +3 +3 +4 (+4) +3 +3 +3
(i) Oxidation states in brackets are unstable states
(ii) The lanthanides contains two s electrons in the outermost shell, they are therefore expected to exhibit a
characteristic oxidation state of +2. But for the lanthanides, the +3 oxidation is common.
(iii) This corresponds to the use of two outermost electrons (6s2) alongwith one inner electron. The inner
electron used is a 5d electron (in La, Gd and Lu), or one of the 4f electron if no 5d electrons present.
(iv) All the lanthanides attains +3 oxidation state and only cerium, Praseodymium, and terbium exhibit higher
oxidation state (+4).
Oxidation states + 2 and +4 occur particularly when they lead to
(i) A noble gas configuration e.g. Ce4+ (f0)
(ii) A half filled ‘f ‘ orbital e.g. Eu2+, Tb4+, (f7)
(iii) A completely filled ‘f ‘ orbital e.g. Yb2+ (f14)
Therefore, in higher oxidation state, they act as oxidising while in lower state as reducing agents.
(e) Magnetic properties
In tripositive lanthanide ions the number of unpaired electrons regularly increases from lanthanum to
Gadolinium (0 to 7) and then continuously decreases upto lutecium (7 to 0). So lanthanum and lutecium
ions which are diamagnetic, all other tripositive lanthanide ions are Paramagnetic.
Colour - The lanthanide ions have unpaired electrons in their 4f orbitals. Thus these ions absorbs visible
region of light and undergo f-f transition and hence exhibit colour. The colour exhibited depends on the
number of unpaired electrons in the 4f orbitals. The ions often with 4fn configuration have similar colour
to those ions having 4f14–n configuration.
Lanthanide ions having 4f0, 4f7,4f14 are colourless. Lanthanide ions 4f1 and 4d13 are also colourless.
(f) Other Properties :
(a) Highly dense metals with high m.pts. (do not show any regular trend).
(b) lonisation Energies - Lanthanides have fairly low ionisation energies comparable to alkaline
earth metals.
(c) Electro positive Character - High due to low I.P.
(d) Complex formation - Do not have much tendency to form complexes due to low charge density
because of their large size.
Lu+3 is smallest in size can only form complex.

d- and f-Block [9]

 (e) Reducing Agent - They readily lose electrones so are good reducing agent.
(i) In +3 oxidation states, nitrates, perchlorates and sulphates of lanthanides and actinides
are water soluble, while their hydroxides, fluorides and carbonates are water insoluble.
(ii) Alloys of lanthanides with Fe are called misch metals.
(iii) La(OH)3 is most basic in nature while Lu(OH)3 least basic.
(iv) Lanthanides form MC2 type carbide with carbon, which on hydrolysis gives C2H2.
(B) LANTHANIDE CONTRACTION
(i) In the lanthanide series with increasing atomic number, there is a progressive decrease in the size
from lanthanum to lutecium or from La+3 to Lu+3. This contraction in size is known as lanthanide
contraction.
(ii) The general electronic configuration of these elements is 4f 0–145s2p6d0-16s2. In these elements
the added electron enters the deep seated f-orbitals and therefore experiences considerable pull
by the nucleus.
(iii) Such an electron cannot add to the size of the element and also because the intervening 5s2p6d1
electronic shells, it is very little screening effect on the outermost 6s2 electrons.
Hence with increasing atomic number, the enhanced nuclear charge leads to contraction in the
size of atoms and ions.
(iv) The atomic volumes of europium and ytterbium are unexceptedly large. The large atomic size of
Eu and Yb suggest weaker bonding in the solid elements. Both these elements have only two
electrons extra than the stable configurations (half filled, f7, and completely filled, f14), hence they
utilise two electrons in metallic bonding as in the case with barium.

(C) EFFECTS OF LANTHANIDE CONTRACTION

(i) Close resembalace of Lanthanides :- The general decrease in the sizes of the lanthanides
with an increase in their nuclear charges result in a small increase in their ionisation energies.
Hence their basic and ionic nature gradually decreases from La to Lu.
This also explains the variations in properties such as increased tendency for hydrolysis and
formation of complex salts and decreased thermal stability. solubility of their salts.
(ii) Similarity of yttrium with lanthanides :- The properties of yttrium are so similar to the lan-
thanides that it is considered more a member of the lanthanide series than a congener of scan-
dium.
(iii) Anomalous behaviour of post-lanthanides :- The following anomalies may be observed in
the behaviour of post-lanthanide elements.
(a) Atomic size - The ionic radii of Zr+4 is about 9% more than Ti+4. Similar trend is not
maintained on passing from the second to third transition series. The ionic radius of Hf+4, instead
of increasing (because of inclusion of one more electronic shell). decreases (or is virtually equal
to Zr+4) as a consequence of the lanthanide contraction.
This explains the close similarities between the members of the second and third transition series
than between the elements of the first and second series.
(b) lonisation potential and electronegativity :- The effect of lanthanide contraction is
also seen in the increase in the ionisation potential values and electronegativities of the elements
of the third transition series, contrary to the general trend.
Because of the lanthanide contraction, the post-lanthanide elements have stronger positive field
and thus the electrons are held more tightly.
The greater effective nuclear charge of the former make them more electronegative than the
latter.
d- and f-Block [10]
 (c) High density :- Because of lanthanide contraction the atomic sizes of the post lan-
thanide elements become very small. consequently, the packing of atoms in their metallic crystals
become so much compact that their densities are very high.
The densities of the third transition series elements are almost double to those of the second
series elements.
(D) APPLICATION OF LANTHANIDES
Cerium is most useful element in the lanthanides
(a) Ceramic application - CeO2, La2O3 ' Nd2O3 and Pr2P3 are used as decolourizing agents for
glasses.
(b) CeS (m.p. - 2000°C) is used in the manufacture of a special type of crucibles and refractories.
(c) Lanthanide compounds like cerium molybdate, cerium tungstate are used as paints and dyes.
(d) In textile and leather industries (Ce salts).

(E) ACTINIDES (5f - BLOCK ELEMENTS)

(i) The elements in which the extra electron enters 5f-orbitals of (n - 2)th main shell are known as
actinides.
(ii) The man.made eleven elements Np93 - Lr103 are placed beyond uranium in the periodic table
and are collectively called trans-uranic elements.
(iii) Th, Pa and U first three actinides are natural elements.
(a) Electronic configuration :-
The general configuration of actinides may be given as 5f1–14 6d0/1, 7s2.

Som e prope rtie s of a ctinoids

Ele me nt Sym bol Atomic num be r Configura tion Ox ida tion sta te s
1 2
Actinium Ac 89 [Rn] 6d , 7s +3
2 2
Thorium Th 90 [Rn] 6d , 7s +3,+4
2 1 2
Protactinium Pa 91 [Rn] 5f , 6d , 7s +3, +4, +5
3 1 2
Uranium U 92 [Rn] 5f , 6d , 7s +3, +4, +5, +6
Neptunium Np 93 [Rn] 5f4 , 6d1 , 7s 2 +3, +4, +5, +6, +7
6 2
Plutonium Pu 94 [Rn] 5f , 7s +3, +4, +5, +6, +7
7 2
Americium Am 95 [Rn] 5f , 7s +2,+3, +4, +5, +6
7 1 2
Curium Cm 96 [Rn] 5f , 6d , 7s +3,+4
8 1 2
Berkelium Bk 97 [Rn] 5f , 6d , 7s +3,+4
10 2
Californium Cf 98 [Rn] 5f , 7s +2,+3
Einsteinium Es 99 [Rn] 5f11 , 7s 2 +2,+3
12 2
Fermium Fm 100 [Rn] 5f , 7s +2,+3
13 2
Mendelevium Md 101 [Rn] 5f , 7s +2,+3
14 2
Nobelium No 102 [Rn] 5f , 7s +2,+3
14 1 2
Lawrencium Lr 103 [Rn] 5f , 6d , 7s +3

d- and f-Block [11]