Transition Elements Including Lanthanides and Actinides

18.1 Transition elements.

A transition element may be defined as an element whose atom in the ground state or ion in common oxidation state has
incomplete sub-shell, has electron 1 to 9. It is called transition element due to fact that it is lying between most electropositive (s-
block) and most electronegative (p-block) elements and represent a transition from them. The general electronic configuration of
these element is (n  1)1 to 10 ns 0 to 2 .

The definition of transition metal excludes Zn, Cd and Hg because they have complete d- orbital. Their common oxidation
state is Zn   , Cd   , Hg   . They also do not show the characteristics of transition element. Zn , Cd , Hg are called non typical
transition element. Some exceptional electronic configuration of transition element are : Cr  3 d 5 4 s 1 ,
Nb  4 d 4 5 s 1 , Pb  4 d 10 5 s 0 , Ag  4 d 10 5 s 1 , Cu  3d 10 4 s 1 , Mo  4 d 5 5 s 1 , Ru  4 d 7 5 s 1 , Pt  5 d 0 6 s 1 ,
Au  5 d 10 6 s 1 . These irregularities can be explain on the basis of half filled and full filled stability of d-orbital.
Classification : Transition element are classified in following series :
(1) First transition series (3d)  21 to 30 i.e. Sc to Zn .

(2) Second transition series (4 d )  39 to 48 i.e. Y to Cd .

(3) Third transition series (5 d )  57 La and 72 – 80 Hf to Hg .

(4) Fourth transition series or 6d series  89 Ac and 104 – 112 Rf .

So there are 39 transition element at present in the periodic table.
General characteristics (physico-chemical properties)
(1) The atomic and ionic radii : The atomic radii of transition element show following trends :
(i) They lie between those of ‘s’ and ‘p’ block element.
(ii) In a series the atomic radii first decrease up to middle then become constant and the end of the series show a slight
increase.
Firstly moving L-R effective nuclear charge predominates, up to middle it is counter balanced by shielding and after due to
electron - electron repulsion slight increase take place.
(iii) Down the group atomic radii increases down the 2 nd transition series only then constant up to 3rd transition series then
decreases due to lanthanide contraction.
(2) Metallic character : All transition elements are metals. The element having maximum unpaired electron, stronger is
metallic bonding as Cr, Mo and W . They have relatively high densities they are malleable, ductile and have high tensile strength,
thermal and electrical conductivity and lusture. The metal having filled d-orbital are soft metal due to weak metallic bonding
Zn, Cd and Hg .
 (3) Melting and Boiling Point : They have strong metallic bonding and hence having high melting point. The m.pt first rises
to a maximum and then fall as atomic number increases. W has highest melting point (3683 K) among transition element Zn, Cd
and Hg having low melting point due to paired electron in a subshell. Hg is liquid at ordinary temperature.
(4) Density : Transition metals having high density due to strong metallic bonding. ' Os ' having density 22.6 gm Cm 3
where as Sc has lowest density i.e. 3.2 gm/c.c.
(5) Ionization energies : The first ionisation energy of d-block element is higher than those of s-block element and lower than
that of p-block element. The ionisation energy of 3d and 4d series is irregular due to irregular size. But due to poor shielding of 4f
electron the ionisation energy across 5d series increase rapidly.
Element Sc Ti V Cr Mn Fe Co Ni Cu Zn
IE1 (kj / mol ) 631 656 650 652 717 762 758 736 745 905

(6) Oxidation states : Except first member (Sc ) and last member of series Zn all metals show variable oxidation state due
to vacant d- orbital.
Element Outer electronic configuration Oxidation state
Sc 3d 1 4 s 2 + 2, + 3
Ti 3d 2 4 s 2 + 2,+ 3,+ 4
V 3d 3 4 s 2 + 2,+ 3,+ 4,+ 5
Cr 3d 5 4 s1 + 1,+ 2,+ 3,+ 4,+ 5,+ 6
Mn 3d 5 4 s 2 + 2,+ 3,+ 4,+ 5,+ 6,+ 7
Fe 3d 6 4 s 2 + 2,+ 3,+ 4,+ 5,+ 6
Co 3d 7 4 s 2 + 2,+ 3,+ 4
Ni 3d 8 4 s 2 + 2,+ 3,+ 4
Cu 3d 10 4 s 1 + 1,+ 2
Zn 3 d 10 4 s 2 +2

The highest oxidation state : The highest oxidation states are formed in fluorides and oxides, since fluorine and oxygen are
the most electronegative element
(i) The highest oxidation state shown by any transition element is +8. Both Os and Ru show +8 oxidation state but the
most stable oxidation state is Os is OsO 4 .
(ii) The most common oxidation state of 3d transition metal is +2 (except Sc ) which show +3.
(iii) Mostly ionic bonds are formed in +2 and +3 oxidation state. But higher oxidation states give covalent bonds.
(iv) Higher oxidation state are stabilized by atom of high electronegativity like O or F where as lower oxidation state are
stabilized by ligands which can accept electrons from the metal through  bonding.
(v) Down the group stability of higher oxidation state increases while that of lower oxidation state decreases.
(vi) The relative stability strength can be estimated by sum of different ionisation energies. Least the sum more will be
stability.
(7) Coloured ions : Transition metal exhibit colour due to d-d transition accordance to crystal field splitting. The electron of
d xy , d yz or d zx orbital absorbs some energy and reflected back rest colour which is the cause of crystal or aq. solution. The ion

which has unpaired electron can show its characteristics colour e.g. Cu    Blue colour due to absorption of red colour
Te    is purple it absorbs yellow wavelength.
 (8) Magnetic property : Due to presence of unpaired electron in (n  1) d-orbital the most of transition metals are
paramagnetic in nature. The magnetic moment of transition metal is expressed in B.M. i.e. Bohr magnetons

 eff  n (n  2) B.M. where n = number of unpaired electron  = effective is called as spin only moment. On the basis of

this formula Sc   , Ti 4  are diamagnetic while Mn   having highest  effective =5.92 B.M.
(9) Complex formation : Transition metal ion form a large number of complexes in which central metal ion is linked to a
number of ligands. A ligand may be a neutral molecule such as NH 3 , or an ion such as Cl  or CN  .

Co 3   6 NH 3  [Co ( NH 3 )6 ]3  ; Fe 2  6CN   [F (CN )6 ]4 ; Cr 3  6H 2O  [Cr (H 2O )6 ]3

This is because of the following characteristics properties of transition metals :
(i) They have high nuclear charge and small size i.e. charge / size ratio is large.
(ii) They have empty d-orbitals to accept the lonepairs of electron donated by ligands. The stability of complexes is increases
with increase in atomic number of the element in a series and with decrease size of its atom.
(10) Interstitials compound : Transition metals have capability to form alloy in which it forms bond with non metal atom like
K, H, C, B, N, situated in its interstitial space in their crystalattice. There alloys are hard, rigid, less ductile & malleable. Steel and
cast iron are the example.
(11) Alloy formation : Due to similar size they are able to form alloy with each other. They are easily miscible and forms alloy.
Alloy with Hg are termed as amalgams, Fe and Pt do not form amalgams.
(12) Non stoichiometric compounds : Non stoichiometric compounds are those in which the chemical composition does not
correspond to their ideal chemical formulae. The compounds of transition metals with O, S, Se, Te, are generally non stoichiometric
and have indefinite composition. The non stoichiometry is due to :
(i) Variable valency of transition metal
(ii) Presence of defects in their solid state (structure). F0.84 O and F0.94 O and it is written as FeO.
(13) Catalytic property : Many transition metals and their compounds show catalytic properties. The most common being Fe,
Pt, Ni, V 2O 5 etc. This property is either due to their variable valency (incompleted orbitals) which enables them to form unstable
interminate compounds or due to the fact that they can provide a suitable reaction surface.
Transition metals and their compounds as catalyst
Catalyst Function
TiCl 4 Used as Natta catalyst in the production of polythene

FeSO 4  H 2 O 2 Used as Fenton’s reagent in the oxidation of alcohols to aldehydes.

Ni Raney nickel in reduction processes : manufacture of hexamethylenediamine, production of

H 2 from NH 3 , reducing anthraquinone to anthraquinol in the production of H 2 O 2
Ni complexes Reppe synthesis (polymerisation of alkynes to give benzene, cyclooctatetraene).
Cu Used in manufacturing of (CH 3 ) 2 SiCl 2 used to make silicones.
Cu/V Used in the oxidation of cyclohexanol/cyclohexanone mixture to acidic acid which is used to
prepare Nylon–66.
CuCl 2 Decon process of making Cl 2 from HCl

MnO 2 Used in the decomposition of KClO 3 to KCl and O 2 .

V2 O 5 Used in contact process of H 2 SO 4 .

Fe Promoted Fe used in the Haber-Bosch process of NH 3
 FeCl 3 Used in the production of CCl 4 from CS 2 and Cl 2 .

PdCl 2 Wacker process for coverting C 2 H 4 into CH 3 CHO .

Pt/PtO Adams catalyst in reduction.
Pt In three stage convertors for cleaning car exhaust fumes.
Pt/Rh In Ostwald process for HNO 3 from NH 3 .
ZnO/CuO In synthesis of CH 3 OH from CO and H 2 .
Co/Fe In synthesis of hydrocarbons by CO and H 2 in Fishcher-Tropsch
Nickel Boride (P-2 Browris catalyst
catalyst)
TiCl 4  (C 2 H 5 ) 3 Al Zeigler Natta catalyst

Pd / BaSO 4 Lindlar’s catalyst

[Ph 3 P]3 RhCl Wilkinson’s catalyst

(14) Reactivity : The d-block elements are unreactive due to the following facts :
(i) On account of small size of their atoms, ionisation energies of d-block elements are fairly high.
(ii) The transition metal ions are not hydrated easily.
(iii) Due to presence of covalent bonding. These have high heats of sublimation.
(iv) The tendency to remain unreactive is more pronounced in platinum and gold in the third transition series.
(15) Standard electrode potential : The standard reduction potential of all the transition elements (except Cu and Hg in 3d
series etc) is lower (negative) than that of hydrogen (taken as zero). Thus all the transition elements with negative reduction
potential librate hydrogen from dilute acids, M  2 H   M 2   H 2 
(16) Reducing properties : Transition metals having negative standard reduction potential should be good reducing agents i.e.
they should be oxidised easily to their ions.
Some important reagents of transition elements
Baeyer’s reagent : Dilute alkaline KMnO 4 Sehueitger reagent : [Cu (NH 3 )4 ] SO 4

Barfoed’s reagent : Cu (CH 3 COO )2  CH 3 COOH Nessler’s reagent : Alkaline solution of K 2 HgI 4

Benedict’s solution : Sodium citrate + Na 2 CO 3 Fehling solution A : CuSO 4 solution

Lucas reagent : HCl (conc.) + anhydrous ZnCl 2 Fenton’s reagent : FeSO 4  H 2 O 2

Etard’s reagent : CrO 2 Cl 2 Milon’s reagent : Solution of mercuric and mercurous nitrate

Tollen’s reagent : Ammonical solution of AgNO 3 ;[ Ag (NH 3 )2 ] OH

18.2 Lanthanides and actinides.

Lanthanides and actinides are collectively called f-block elements because last electron in them enters into f- orbitals of the
antepenultimate (i.e., inner to penultimate) shell partly but incompletely filled in their elementary or ionic states. The name inner
transition, elements is also given to them because they constitute transition series with in transition series (d-block elements) and
the last electron enters into antepenultimate shell (n-2) f. In addition to incomplete d-subshell, their f-subshell is also incomplete.
Thus, these elements have three incomplete outer shells i.e., (n–2), (n–1) and n shells and the general electronic configuration of f-
block elements is (n–2) f 114 (n  1)d 0 10 ns 2
 (1) Lanthanides : The elements with atomic numbers 58 to 71 i.e. cerium to lutetium (which come immediately after
lanthanum Z = 57) are called lanthanides or lanthanones or rare earths. These elements involve the filling of 4 f-orbitals. Their
general electronic configuration is, [ Xe ]4 f 114 5 d 0 10 6 s 2 . Promethium (Pm), atomic number 61 is the only synthetic (man made)
radioactive lanthanide.
Properties of lanthanides
(i) These are highly dense metals and possess high melting points.
(ii) They form alloys easily with other metals especially iron. e.g. misch metal consists of a rare earth element (94–95%), iron
(upto 5%) and traces of S, C, Ca and Al, pyrophoric alloys contain Ce (40–5%), La + neodymium (44%), Fe (4–5%), Al (0–5%)
and the rest is Ca, Si and C. It is used in the preparation of ignition devices e.g., trace bullets and shells and flints for lighters.
(iii) Oxidation state : Most stable oxidation state of lanthanides is + 3. Oxidation states + 2 and + 4 also exist but they revert
to + 3 e.g. Sm 2  , Eu 2  , Yb 2  lose electron to become + 3 and hence are good reducing agents, where as Ce4+, Pr4+, Tb4+ in
aqueous solution gain electron to become + 3 and hence are good oxidizing agents. There is a large gap in energy of 4 f and 5 d
subshells and thus the number of oxidation states is limited.
(iv) Colour : Most of the trivalent lanthanide ions are coloured both in the solid state and in aqueous solution. This is due to
the partly filled f-orbitals which permit f–f transition. The elements with xf electrons have a similar colour to those of (14 – x)
electrons.
(v) Magnetic properties : All lanthanide ions with the exception of Lu3+, Yb3+ and Ce 4+ are paramagnetic because they
contain unpaired electrons in the 4 f orbitals. These elements differ from the transition elements in that their magnetic moments
do not obey the simple ‚spin only‛ formula  eff  nn  2  B.M. where n is equal to the number of unpaired electrons. In
transition elements, the orbital contribution of the electron towards magnetic moment is usually quenched by interaction with
electric fields of the environment but in case of lanthanides the 4 f-orbitals lie too deep in the atom for such quenching to occur.
Therefore, magnetic moments of lanthanides are calculated by taking into consideration spin as well as orbital contributions and a
more complex formula

 eff  4 S S  1  LL  1 B.M.

which involves the orbital quantum number L and spin quantum number S.
(vi) Complex formation : Although the lanthanide ions have a high charge (+3) yet the size of their ions is very large yielding
small charge to size ratio i.e., low charge density. As a consequence, they have poor tendency to form complexes. They form
complexes mainly with strong chelating agents such as EDTA,  -diketones, oxine etc. No complexes with  -bonding ligands are
known.

(vii) Lanthanide contraction : The regular decrease in the size of lanthanide ions from La 3  to Lu 3  is known as
lanthanide contraction. It is due to greater effect of the increased nuclear charge than that of the screening effect.
Consequences of lanthanide contraction
(a) It results in slight variation in their chemical properties which helps in their separation by ion exchange
(b) Each element beyond lanthanum has same atomic radius as that of the element lying above it in the group (e.g. Zr 145
pm, Hf 144 pm); Nb 134 pm, Ta 134 pm ; Mo 129 pm, W 130 pm).

(c) The covalent character of hydroxides of lanthanides increases as the size decreases from La 3  to Lu 3  . However basic
strength decreases. Thus La (OH )3 is most basic whereas Lu (OH ) 3 is least basic. Similarly, the basicity of oxides also decreases
in the order from La 3  to Lu 3  .

(d) Tendency to form stable complexes from La 3  to Lu 3  increases as the size decreases in that order.
(e) There is a slight increase in electronegativity of the trivalent ions from La to Lu.
 (f) Since the radius of Yb 3  ion (86 pm) is comparable to the heavier lanthanides Tb, Dy, Ho and Er, therefore they occur
together in natural minerals.
(2) Actinides : The elements with atomic numbers 90 to 103 i.e. thorium to lawrencium (which come immediately after
actinium, Z = 89) are called actinides or actinones. These elements involve the filling of 5 f-orbitals. Their general electronic
configuration is, [Rn ] 5 f 114 6 d 0 1 7 s 2
They include three naturally occuring elements thorium, protactinium and uranium and eleven transuranium elements or
transuranics which are produced artificially by nuclear reactions. They are synthetic or man made elements. All actinides are
radioactive.
Properties of actinides
(i) Oxidation state : The dominant oxidation state of actinides is +3 which shows increasing stability for the heavier elements.
Np shows +7 oxidation state but this is oxidising and is reduced to the most stable state +5. Pu also shows states upto +7 and Am
upto +6 but the most stable state drops to Pu (+4) and Am (+3). Bk in +4 state is strongly oxidising but is more stable than Cm
and Am in 4 state due to f 7 configuration. Similarly, No is markedly stable in +2 state due to its f 14 configuration. When the
oxidation number increases to + 6, the actinide ions are no longer simple. The high charge density causes the formation of
oxygenated ions e.g., UO 22  , NpO 22  etc. The exhibition of large number of oxidation states of actinides is due to the fact that
there is a very small energy gap between 5f, 6d and 7s subshells and thus all their electrons can take part in bond formation.
(ii) Actinide contraction : There is a regular decrease in ionic radii with increase in atomic number from Th to Lr. This is
called actinide contraction analogous to the lanthanide contraction. It is caused due to imperfect shielding of one 5 f electron by
another in the same shell. This results in increase in the effective nuclear charge which causes contraction in size of the electron
cloud.
(iii) Colour of the ions : Ions of actinides are generally coloured which is due to f – f transitions. It depends upon the
number of electrons in 5 f orbitals.
(iv) Magnetic properties : Like lanthanides, actinide elements are strongly paramagnetic. The magnetic moments are lesser
than the theoretically predicted values. This is due to the fact that 5 f electrons of actinides are less effectively shielded which
results in quenching of orbital contribution.
(v) Complex formation : Actinides have a greater tendency to form complexes because of higher nuclear charge and smaller
size of their atoms. They form complexes even with -bonding ligands such as alkyl phosphines, thioethers etc, besides EDTA, -
diketones, oxine etc. The degree of complex formation decreases in the order.

M 4   MO 22   M 3   MO 2

where M is element of actinide series. There is a high concentration of charge on the metal atom in MO 22  which imparts
to it relatively high tendency towards complex formation.

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