CHEM 419: CHEMISTRY OF TRANSITION METAL ELEMENTS (Jan -

April 2025)
1.0. INTRODUCTION

The chemical elements in the periodic table can be grouped together in

blocks depending on the occupancy of their outermost, or valence shell
atomic orbitals. Thus hydrogen and the alkali metals lithium to francium
with a half filled outer s subshell, together with helium and the alkaline earth
metals, beryllium to radium with a filled outer s subshell comprise the s block
elements. Similarly, elements with partially or fully filled outer p shell
comprise the p-block elements. That is elements from boron through to neon
down to thallium through radon. Between these two blocks of elements ,
there are two further blocks containing the transition elements. Transition
metals/elements are also called d-block metals/ elements because their
atoms receive the last electron or the last differentiating electron in the d –
subshell belonging to the penultimate or the (n-1) th shell. The term transition
elements (metals) is widely used, but d-block metals and transition elements
are not interchangeable. Strictly speaking the term transition element
applies to elements with partly filled d or f subshell and so excludes those
with d0 or d10 and f0 or f14 electron configuration. Practically, by definition
which is in accordance with IUPAC rule, a transition element is an
element which has an incomplete d-subshell in either neutral atom
or in chemically significant(or common ) oxidation state. According to
this definition zinc, cadmium and mercury are excluded from the list of
transition elements as they neither have partly filled d-subshell in their
neutral atoms or ions nor do they show the usual properties of transition
elements to an appreciable extent. However in order to rationalize the
classification of elements, they are studied along with other d-block
elements.
Why are they called transition elements?.They are referred to as
transition elements because they exhibit gradual transition between highly
reactive(electropositive) s-block elements/metals and less
reactive(electronegative) p –block elements/metals . Thus their properties
are found to be between those of the s-block and p- block elements. These
elements are located in the middle of the periodic table and are members of
the groups 3 to 12 in the modern periodic table.
1.1. CLASSFICATION OF TRANSITION ELEMENTS
There are four series of d-block elements. Each series comprise ten elements
as shown below.

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1. Elements of the first transition series or 3d-Transition series. These are
the elements from scandium (Sc, Z= 21) to zinc(Zn , Z= 30)- they are
referred to as 3d –series or first row transition elements.
2. Elements of the second Transition Series or 4d-Transition series. This
series consists of the elements from yttrium(Y,Z=39) to cadmium (Cd ,
Z=48).They are referred to as the 4d transition series or the second
rowtransition elements.
3. Elements of the third Transition series or the 5d-Transition series.
These include elements lanthanum(La, Z= 57) and hafnium(Hf, Z= 72)
to mercury and are referred to as the 5dTransition series or third row
transition elements.
4. Elements of the fourth Transition Series or the 6d transition series.
These include the elements actinium(Ac, Z= 89) and
rutherfordium(Rf,Z=104) to copernicium(Cn, Z = 112). All these
elements are radioactive and do not occur in nature. They are
artificially synthesized in the laboratory.

The f –block elements comprise two series of inner transition elements

which appear, firstly after lanthanum and secondly after actinium in
the periodic table. The elements from cerium to lutetium are known as
lanthanides and because of its chemical similarity to these elements,
lanthanum is included in them. Scandium and yttrium also show strong
chemical similarities to the lanthanides, so the chemistry of these
elements is also often considered in conjunction with that of the
lanthanides series. The general electronic configuration of these
elements is [Xe]4f1-14 5d 0-1 6s2. The second series of f-block elements
from thorium to lawrencium is known as the actinide series and as
usual actinium is considered together with actinides. They have the
general electronic configuration [Rn]5f1-14, 6d 0-1, 7s2
NB: The elements after uranium (U, Z = 92) are manmade in the
laboratory and are known as transuranic elements

Position in the Periodic Table

d-block

Group → 3 4 5 6 7 8 9 10 11 12

Series ↓

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 3d Sc Ti V Cr Mn Fe Co Ni Cu Zn
4d Y Zr Nb Mo Tc Ru Rh Pd Ag Cd
5d La Hf Ta W Re Os Ir Pt Au Hg
6d Ac Rf Db Sg Bh Hs Mt

f - block

4f La Ce Pr Nd Pm S Eu Gd Tb Dy Ho Er Tm Lu
m
5f Ac Th Pa U Np Pu Am Cm Bk Cf Es Fm Md Lr

 The primary distinction between transition metals and inner transition

metals is that transition metal atoms have their valence electrons in
the outermost d orbital, whereas inner transition metal atoms have
them in the inner penultimate f orbital.[ antipenultimate ]

In this course, we shall also study the comparative chemistry of both d and f
–block elements.

1.2. Transition Series of d Block Elements

The d block position in the periodic table consists of elements in the group of
3 to 12 in which the orbitals are progressively filled in each of the four long
periods.In this block, the d orbitals are filled progressively. In the d transition
elements, the last electron usually enters the penultimate d orbitals i.e. (n-1)
d orbitals and that is why they are called d-block elements in the modern
periodic table. The general valence shell configurations of every transition
element is (n-1) d1–10.ns0, 1, 2.

All the d-block elements are classified into four series which are called 3d,
4d, 5d and 6d series corresponding to the filled outer shells of 3d, 4d, 5d,
and 6d orbitals. Present in the center of the periodic table, the ‘d’ block
elements lie in the middle of the s block elements on the left, and the non-
metals of the p block, to its right.

The following are the transition series of the d block elements:

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  First transition series or the 3d series: Those elements which
have an atomic number from 21 to 30 are usually included in this
series. Included in this series are ten elements which are Sc, Ti, V, Cr,
Mn, Fe, Co, Ni, Cu, and Zn. They always correspond to the filling of the
3d subshell.
 Second transition series or the 4d series: Included in this series
are the elements which have an atomic number from 39 to 48 and are
Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, and Cd. All of these elements have a
corresponding filling of the 4 subshell.
 Third transition series or the 5d series: Included in this series are
elements that have an atomic number from 72 to 80 and 57.
 Fourth transition series or the 6d series: Elements which have an
atomic number from 104 to 112 and 89 form the elements in this
group.

1.3. CHARACTERISTIC PROPERTIES OF d-BLOCK ELEMENTS

The transition elements have a number of properties in common which can

be related to the presence of of partly filled d orbitals
i. They are all metals and almost all are hard, strong, have high melting ,
boiling points, are malleable, lustrous, ductile and conduct heat and
electricity effectively.
ii. They form alloys with one another and with other elements
iii. Many of them are electropositive enough to dissolve in mineral acids
iv. They exhibit variable oxidation state
v. Many of their compounds are coloured, a property mainly due to
electronic transitions involving the d-orbitals
vi. Their compounds are paramagnetic because of partially filled d
orbitals
vii. They form compounds which are good catalysts

1.3.1 Electronic configuration and exhibition of variable oxidation

states
The d-block elements have a valence shell electronic configuration of (n-1)d 1-
10
ns1-2 where (n-1) stands for inner shell whose d-orbitals may have one to
ten electrons and the s-orbitals of the outermost shell may have no electron
or one or two electrons. The filling of d-orbitals takes place after the s-orbital
of the net higher shell has already filled as has been discussed in your
previous course. This is because ns orbitals have lower energy than the (n-
1)d orbitals. But during ionization of the elements (oxidation) the electrons
are removed or lost from the ns level followed by the expulsion from the (n-
1)d subshell which is a deviation from the expected behavior Why? because

CHEM 419: CHEMISTRY OF TRANSITION METALS ELEMENTS JANUARY-APRIL 2025 NOTES

(n-1)d subshell becomes of the lower energy than the ns subshell once the
filling of electrons commences in the (n-1)d subshell
• Most of the d-block elements show several oxidation states(variable
oxidation states in their compounds due to the availability of d-
electrons in the valence shell which comprises of the two subshells viz
(n-1)d and ns whose orbitals are quite close together in energy and
hence electrons can be used from both the subshells for bonding. The
variability in the oxidation state increases towards the middle of the
series from both ends i.e left-middle-right. In other words the metal
which exhibits the greatest number of oxidation states occur in in the
middle of the series. Why is this the case?

• Reason: Maximum oxidation state exhibited by transition metals is

equal to the sum of (n-1)d and (ns) electrons.

• In a transition series, the maximum number of unpaired electrons

occur in the elements present in the middle of the series. This why the
metals in the middle of the transition series exhibits maximum number
of oxidation states , i.e Mn present in the middle of the first transition
series and whose electronic configuration is 3d 54s2 has sum of (n-1)d
and (ns ) equal to +7 and therefore exhibits maximum oxidation
states of +2,+3,+4,+5,+6 +7

• The lesser number of oxidation states on the extreme ends are either
due to too few electrons to lose or share or too many d-electrons so
that fewer orbitals are available to share electrons with others

• It has been observed that the d-block elements can form ionic bonds in
their lower oxidation states and the ionic character of the bond
decreases as well as the covalent character increases with increasing
oxidation state. As a result, with decreasing ionic character the acidic
character of the oxides and chlorides increases.

1.3.2 Tendency to Form Complexes

The cations of d-block elements are unique in their tendency to form
complexes with several different ligands such as ammonia, water, cyanide,
NO2-, halides ions etc. The complex forming tendency of these elements is
attributed to the following factors
i. They have small ionic radii and high charge density
ii. They have high effective ionic charges
iii. They have high ratio of ionic charge to ionic radius

CHEM 419: CHEMISTRY OF TRANSITION METALS ELEMENTS JANUARY-APRIL 2025 NOTES

 iv. They have vacant d-orbitals of the right energy that can
accommodate the lone pairs of electrons from the approaching ligands
to form complexes
v. They show variable oxidation states. Transition metal ions have the
tendency to acquire stable electronic configurations of the nearest
inert gas and thus form stable complexes after accepting the electrons
from the ligands to which they are coordinated

1.3.3. Magnetic Properties

Many compounds of d-block elements exhibit magnetic properties.
Qualitatively there are several kinds of magnetism. The substances which
are weakly repelled by the strong magnetic field are termed diamagnetic
while those which are weakly attracted by the strong magnetic field are
called paramagnetic.These substances lose their magnetism on removing
the magnetic field. Diamagetism is the property of the completely filled
electronic subshells and is shown by all substances to more or less extent.
Paramagnetism is produced by the presence of unpaired electrons and
because most d-block atoms and ions have unpaired electrons, they are
paramagnetic in behavior.In some transition elements e.g Fe, Co and Ni
unpaired electron spins are more pronounced and show much more
paramagnteism than the other d-block metals. Such metals are
calledferromagnetic metals and magnetic property shown by them is
known as ferromagnetism. Such metals can be permanently magnetized.
1.3.4 Formation of coloured ions/compounds
Majority of compounds of d-block elements whether ionic or covalent are
coloured in solid or solution state. This property of d-block elements is
remarkably different from those of s or p-block elements which are white or
light coloured.The colour of a substance arises from the propensity of the
substance to absorb light of certain wavelength in the region of visible
light(white light) when light interacts with the substance. The colour of the
substance is the colour of the transmitted light component and is
complimentary to the colour of the light component absorbed.
• What is visible light? .Visible light consists of electromagnetic
radiation with wavelengths ranging from about 400nm to 750nm.White
light contains all wavelengths in this visible region as illustrated below.

CHEM 419: CHEMISTRY OF TRANSITION METALS ELEMENTS JANUARY-APRIL 2025 NOTES

• What is complementary colour? The complementary colour is the
colour generated from the wavelength left over when a sample
absorbs light; i.e if green light is absorbed by a complex, it appears
red. A blue colour corresponds to the absorption of light towards red
end of the visible spectrum while a red colour corresponds with the
absorption of light at the blue end of the spectrum. The two pair of
colours are complimentary.

• Complimentary colours can be determined using artist’s colour wheel

shown below

• Artist's complementary colours appear as wedges opposite each other

on the wheel

CHEM 419: CHEMISTRY OF TRANSITION METALS ELEMENTS JANUARY-APRIL 2025 NOTES

The colour of the d-block element is associated with
i. An incomplete d-subshell in the metal ion
ii. The nature of the surrounding groups around the metal ion.

The whole act of exhibition of colour by d-block ions/compounds can be

explained as follows: In a free gaseous or isolated metal ion the five d –
orbitals are degenerate i.e of the same energy .

Since the five d-orbitals are oriented differently in space, the surrounding
groups affect the energy of some orbitals more than the others in the
compounds. This destroys the degeneracy of the five d orbitals. For example,

CHEM 419: CHEMISTRY OF TRANSITION METALS ELEMENTS JANUARY-APRIL 2025 NOTES

in the simplest case of an octahedral complex they form two groups of
orbitals of different energy as shown below.

Partial orbital energy-level diagram (showing 3d levels only) for (a) a free
transition metal ion (b) a transition-metal ion in a sphere of negative charge,
and (c) a transition –metal ion in an octahedron of six point negative
charges.
in d-block metal ions with partially filled d-subshell, it is possible to promote
electrons from one set group to another set of higher energy by fairly small
energy absorbed from the visible light.
It is significant to note that the colour of the compound depend on the
energy difference (gap) between the two groups of d-orbitals. This in turn
depends on the nature of ligands and their arrangement around the metal
ion in the compound or complex.
1.3.5. Formation of Interstistial and non-stoichiometric Compounds
The d-block elements form interstitial compounds with small non-metals
atoms such as H,C,N,B,Si etc due to the ability of metal lattice to
accommodate these non-metal atoms between the metal atoms without
distortion of the structure. One other striking properties of these metals is
the formation of non-stoichiometric compounds which often exhibit
semiconductivity, fluorescence and behave as heterogenous catalysts. This
non-stoichiometric behavior is due to the defects in the solid structures
1.3.6. Catalytic Activity
 Many transition metals and their complexes are used as catalysts
which influence the rate of chemical reaction. The rate of chemical
reaction increases by the decrease in the activation energy of the

CHEM 419: CHEMISTRY OF TRANSITION METALS ELEMENTS JANUARY-APRIL 2025 NOTES

 reactants. This decrease is caused by the catalyst which probably alter
the path of the reaction.

 A number of d-block elements and their compounds are used to

catalyze various reactions of industrial importance eg vanadium (v)
oxide used in the manufacture of sulphuric acid

 The catalytic activity of d-block elements and their compounds is

associated with the presence of vacant orbitals, their ability to
adopt variable oxidation state and their capability of forming
interstitial compounds. These properties enable transition
elements to form bonds between reactants and atoms on the
surface of the catalsty

 It significant to understood that the mechanism of catalysis is based

on the fact that at solid surface of the catalyst, bonds would be
formed between the molecule of the reactants and atoms of the
catalyst thereby increasing the concentration of the reactants at the
surface . With an increase in the concentration of the reactants on the
surface, of the catalyst, the rate of reaction increases .This weakens
the bonds of the reactant molecules due to lowering of the activation
energy

 Thus the ability of d-elements to form complexes enable them to

provide a suitable large surface area with free vacancies on which
suitable reactants bond on the surface of the catalysts to form
intermediate compounds which are unstable and a new path with
lower activation energy for the reaction is thus provided . These
intermediates decompose yielding products and regenerating the
original substance

1.3.7.Metallic Character and alloy Formation

All d-block elements are metals, which are good conductors of heat and
electricity, are malleable and ductile. All except mercury which exists as
liquid at room temperature are lustrous solids which have high melting point
and high boiling points. These metals form alloys with each other due to
almost similar sizes of the atoms and with main group elements . Thus atoms
of one metal can easily take up positions in the crystal lattice of the other.
The alloys are usually harder and have higher melting points than the parent
metals, and are more resistant to corrosion than their constituents.

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1.3.8. Periodic Properties and their variation along the series
The atomic radii, atomic volumes, ionic radii, melting point and boiling
points, ionization energies and reactivity, standard electrode potential and
reducing properties etc are very important periodic properties of the d-block
elements which vary and have a definite trend, in general along each series:
1.3.9. Atomic Radii, Atomic volumes and ionic radii
• The atomic radii generally decrease, with a few exceptions , on
moving from left to right in each series of transition elements due to
increased nuclear charge at each step and constant value of angular
momentum quantum number as well as the principal quantum
number.

• The d elements have low atomic volumes as compared to those of the

neighbouring s and p block elements. This is due to the fact that in
these elements (n-1)d-subshells are being filled and the increased
nuclear charge pulls the electron cloud inwards.

• The ionic radii of the d-block elements follow the same trend as the
atomic radii i.e the radii of the ions having the same charge decrease
with increasing atomic numbers

1.3.10.Melting Points and Boiling Points

The M.P and B.P of these elements are generally high showing that they are
held by very strong forces. The M.P and B.P have the highest values in the
middle of the series because perhaps these elements have the maximum
number of unpaired d-electrons available for bonding
1.3.11.Ionization Enthalpy and reactivity
The ionization energy values of the d-block elements are fairly high and lie in
between those of the s- and p- block elements i.e they are less
electropositive than the s-block elements and more electropositive than the
p-block elements. Hence these elements do not form ionic compounds as
readily as s-block elements and form covalent compounds as well. Because
of the existence of covalent bonding, they have high heats of sublimation, i.e
large amounts of energy is required to convert them from solid to vapour
state. The metals ions do not get hydrated easily. Due to these parameters,
the metal ions have a small tendency to react.
1.3.12. Standard Electrode Potentials and the reducing Properties.

CHEM 419: CHEMISTRY OF TRANSITION METALS ELEMENTS JANUARY-APRIL 2025 NOTES

 • Standard reduction potential is a measure of the tendency of chemical
species to be reduced at standard conditions while standard oxidation
potential is a measure of the tendency of chemical species to be
oxidized at standard conditions

• The standard reduction potential values of these elements are

generally lower (negative) than that of standard hydrogen electrode
(taken as zero). Thus they evolve H 2 gas from acids though most of
them do that at low rate. These metals though are poor reducing
agents which are contrary to the expected behavior because of high
heats of vaporization, high ionization energies and low heats of
hydration.

2.0. PROPERTIES OF THE FIRST ROW TRANSITION SERIES

These elements are much more important than those of the second and third
transition series. Their chemistry is best considered separately from that of
the second and third row for several reasons which includes the following.
i. The chemistry of the first member of a triad is distinct from that of the
two heavier metals . e.g Zr and Hf have similar chemistries bit that of
Ti differs
ii. Electronic spectra and magnetic properties of many complexes of the
first row metals can often be rationalized using crystal field or
molecular orbital theories but effects of spin-orbit coupling are more
important for the heavier metals of second and third rows.
iii. Complexes of the heavier metal ions(second and third-row series)
show a wide range of coordination numbers than those of the first row
congeners.
iv. The trends of the oxidation states are not consistent for all members
of a triad. For example: although the maximum oxidation state of Cr,
Mo and W is +6, its stability is greater for Mo and W than for Cr
v. Metal - metal bonding is more important for the heavier metals than
for those in the first row.

2.1. Electronic configuration of first Transition series

• The general valence shell electronic configuration of these elements is
3dn4sm where n=1-10 and m =2. Thus the 3d- subshell has one to ten
electrons from Sc to Zn and 4s subshell, in general has two electrons
i.e 4s2 except in Cr and Cu which have only one 4s electron i.e 4s 1. The
exceptional valence shell configuration of Cr and Cu is attributed to the

CHEM 419: CHEMISTRY OF TRANSITION METALS ELEMENTS JANUARY-APRIL 2025 NOTES

 exchange energy effect and the extra stability resulting to half-filled
and completely filled subshell. The shifting of an electron from one
subshell to another of similar or slightly higher energy in order to
achieve the half-filled or completely filled subshell results to loss in
exchange energy – an effect known as exchange energy effect which
leads to maximum stability.

• Cr(Z=24) 3d44s2(expected but unstable)3d54s1(actual, more stable)

• Cu(Z=29) 3d94s2(expected but less stable ) 3d 104s1 (actual more stable

)

• As shown there is exchange of electrons from 4s to 3d subshell thereby

increasing the stability of the valence shell configuration in Cr and Cu
atoms.

• Thus among the 3d elements, only chromium and copper exhibit

irregularities/anomalous electronic configuration

2.1 Oxidation States

The first transition series show variable oxidation states in their compounds/
ionic forms. The cause of showing different oxidation states is that these
elements have several 3d electrons which are close to 4s – electrons in
energy. All these electrons can be lost one at a time. From Ti to Mn the
highest oxidation state is commensurate with the loss of all the 3d and 4s
electrons. The stability of the highest oxidation state decreases from Ti(IV) to
Mn(VII) and ater Mn the highest oxidation states are rarely encountered
These The minimum oxidation state shown by these elements is +2 except
Cr and Cu which show +1 oxidation state as well. The number of oxidation
states shown by these metals increases from Sc to Mn and then decreases
till Zn which shows +2 oxidation state only. As a result, among these
elements Cr and Mn show the maximum number of oxidation states from +1
to +6 and +2 to +7 respectively. From Sc to Mn , the highest oxidation state
shown by any element is equal to the group number but the later elements
do not follow this trend as shown below.

Element Sc Ti V Cr Mn Fe Co Ni Cu Zn
Group 3 4 5 6 7 8 9 10 11 12
number
Lowest +2 +2 +2 +1 +2 +2 +2 +2 +1 +2
oxidation +2
state
Highest +3 +3 +3 +3 +3 +3 +2 +2
Oxidatio +4 +4 +4 +4 +4 +4 +4
CHEM 419:
n state CHEMISTRY OF TRANSITION
+5 +5 +5 METALS ELEMENTS JANUARY-APRIL 2025 NOTES
+6 +6 +6
+7
It has been observed that the lower (+2, +3) oxidation states generally
dominate the chemistry of the first transition series. For an element the
relative stability of the various oxidation states can be explained on the basis
of the stability of d0, d5 and d10. Ti4+ ion (3d04s0) is more stable than
Ti3+(3d14s0) because of the presence of 3d 0 subshell. Similarly Mn2+(3d54s0)
ion is more stable than Mn3+(3d44s0)ion since Mn2+ ion has 3d5 subshell
The relative difficulty in obtaining compounds containing Ni(III) and Cu(III) is
due in large part to the relatively high values of the third ionization energy
Because of the stability of the filled 3d orbital, copper is the only element in
this series which affords compounds containing Cu+ unsupported by π-
acceptor ligands
It has also been observed that the first transition series elements form ionic
oxides and chlorides in the lower oxidation states which are basic in nature.
As the oxidation state of the elements increase, covalent character and
acidic nature of these compounds also increases eg MnO(Mn has +2
oxidation state) is basic, and Mn2O3 (Mn has+3 oxidation state) and
MnO2( Mn has +4 oxidation state) are amphoteric and Mn 2O7(Mn has +7
oxidation state) is acidic. Similarly CrO( Cr has +2 oxidation state) is basic,
Cr2O3( Cr has +3 oxidation state) is amphoteric and CrO 3(has +6 oxidation
state) is acidic. Also VCl2( has +2 oxidation state) is basic and VOCl 3( V has
+5 oxidation sate) is acidic.
The following points need to be noted.
i. The elements which give the greatest number of oxidation states occur
in or near the middle of the series. manganese, for example exhibits all
the oxidation states from +2 to +7.
ii. 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 orbital available in which to share electrons with
others)for higher valence(Cu,Zn). Thus ,e arly in the series scandium(II) is
virtually unknown while Sc(III) and its compounds are known. Ti(IV) is more
stable than Ti(III) or Ti(II). At the other end , the only oxidation state of zinc is
+2(no d electrons involved).
iii. The maximum oxidation states of reasonable stability correspond in

value to the sum of the s and d electrons upto manganese. Thus we

have (Ti(IV)O2, V(V)O2+, Cr(VI)O42-, Mn(VII)O4-) followed by a rather abrupt
decrease in stability of higher oxidation states, so that the typical species to
follow are Fe(II), Fe(III), Co(II), Co(III), Ni(II), Cu(II), Zn(II) which are stable

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iv. The variability of oxidation states , a characteristic of transition
elements , arises out of incomplete filling of d orbitals in such a way
that their oxidation states differ from each other by unity e.g V(II),
V(III), V(IV), V(V). This is in contrast with the variability of oxidation
states of non-transition elements where oxidation states normally
differ by a unit of two.
v. An interesting feature in the variability of oxidation states of the d-
block elements is noticed among the groups(groups 4 through 10).
Although in the p -block elements the lower oxidation states are
favoured by the heavier members (due to inert pair effect), the
opposite is true in the groups of d-block. for example, in group 6,
Mo(VI) and W(VI) are found to be more stable than Cr(VI). Thus Cr(VI)
in the form of dichromate in acidic medium is a strong oxidising agent,
whereas MoO3 and WO3 are not
.Low oxidation states are stabilized and found when a complex has
ligands capable of π -acceptor character in addition to the sigma
bonding. For example in Ni(CO)4 and Fe(CO)5, where the oxidation
state of nickel and iron is zero

Stabilization of Oxidation States

• (i). Stabilization of High Oxidation States

 High oxidation states of transition elements are exhibited and

becomes stable when the metals are in combination with fluoride
ions or oxide ions.These ligands are small, highly
electronegative and hence most difficultly to oxidize to
anions .They are called hard bases and are known to stabilize
metals in high

oxidation states (hard acids).

 For example, fluorine is often said to bring out the maximum oxidation
of any element. Thus when vanadium reacts with the halogens it
gives a fluoride VF5, a chloride VCl4 and a bromide VBr3.

 In other words vanadium (V) is too strong oxidizing agent to exist

in combination with chloride or bromide ions they become
oxidized to the free halogens.

 With oxide ions we get stabilization of the highest oxidation state of V,

Cr and Mn in the vanadate VO43-, chromate CrO42- and permanganate
MnO4- ions.
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 The high oxidation states of iron and cobalt (that is greater than +3)
and of nickel and copper (that is greater than +2) almost invariably
occur in compounds containing oxygen or fluorine

• (ii).Stabilization of Low Oxidation states

 The ligands that favour low oxidation states are those that are capable
of forming both sigma and π bonds. For these ligands to coordinate
to the metal ion, they must possess lone pair electrons and vacant
orbitals of π symmetry.

 The lone pair electrons from the ligand are donated along the sigma
bond leading to accumulation of negative charge on the metal.The
accumulated negative charge is then delocalized back on to the ligand
empty π orbitals. Such ligands are called π acceptor ligands

 These ligands have empty π* molecular orbitals as shown below for

molecular orbital energy level diagram for CO as an example

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 In this case CO ligand can function as a σ donor using an electron pair
in its highest occupied molecular orbital σ2p (HOMO).
 At the same time, CO has empty π* orbitals of suitable orientation to
accept electron density from the metal.
 These interactions are shown below

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 Since the ligands are accepting the electron density in the π * orbital
they are sometimes called π acid ligands or π acceptor ligands.
 Typical examples of π acid ligands are CO, N2, NO, PR3,
RNC,bipyridines and phen
 Thus in the formation of σ bond the ligand acts as an electron pair
donor (i.e Lewis base) while the metal acts as an electron pair acceptor
(Lewis acid).
 Similarly, in the formation of π bond the metal acts as an electron pair
donor (i.e Lewis base) while the ligand acts as an electron pair
acceptor(Lewis acid).
 Note that the formation of π-bond removes the electron density from
the metal to the ligand and prevents the accumulation of excess
negative charge on the metal.
 Since the π bond is formed by the donation of a pair of electrons from
the metal to the ligand (M → CO).This process is called back donation
or backbonding
 For binary metal carbonyls such as Cr(CO)6 and Fe(CO)5,the metal is
in zero oxidation states
 The bonding in these carbonyls consists of an M-CO σ bond formed by
donation of the lone pair of electrons on carbon and an M-CO π bond

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 formed from the electron density from metal d orbitals into the vacant
antibonding molecular orbitals ( π antibonding) on the carbon
monoxide. Formation of these two bonds are shown below

2.2 Tendency to form Complexes

• The elements of the first transition series fulfill all the conditions of
forming complexes and are thus most suitable for this purpose. As a
result, cations of these elements have strong tendency to form
complexes with certain molecules eg CO, NO,NH 3 etc or several ions ef
F-, Cl-, CN-. These molecules are called ligands and have one or more
lone pairs of electrons on their donor atoms which they donate to the
metal ion/atom during the process of complex formation via M---L
coordinate covalent bonds . Why does this happen?. This happens
because the metal ions are electron deficient in most of their oxidation
states or even their atoms and therefore are electron acceptors
(Lewis acids) .Small size and high charge density of the metal ions
facilitate the formation of the complexes which also depends on the
basicity of the ligands. The complex formation tendency increases as
the positive oxidation state of the metal ion increases.

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2.3. Magnetic Behaviour
Among the transition metals compounds, paramagnetism is common though
some metals in the elemental form such as Fe, Ni and Co also show
ferromagnetism
Origin of paramagnetism: Electrons being charged particles act as tiny
magnets by themselves and determine the magnetic properties of the
substance in two ways
i. Spin motion or the spinning of the electron on its axis
produces spin magnetic moment and
ii. Orbital motion or the movement of the electron round the
nucleus produces orbital magnetic moment

The resultant of the above two moments gives the total moment produced
by an electron. The observed magnetic moment of the compounds is the
sum of the moments of all the electrons present in them. If the two
electrons with opposite spins are paired in the same orbital, the magnetic
moment produced by one electron is cancelled by that cased by the other
electron because both the electrons will have equal but opposite moments
thereby giving zero resultant magnetic moment. Such substances which
have paired electrons will not show paramagnetism rather they are
diamagnetic.
But if there are unpaired electrons in the ions/atoms of the substance it has
the moment produced by all the unpaired electrons.The resultant or total
moment in them is sufficiently high to overcome the magnetic moment
induced by an approaching magnetic field. Hence such substances instead of
experiencing repulsion are attracted in a magnetic field and are called
paramagnetic substances.
The magnetic moment of a single electron is given by the expression
µs(BM) = g√ S (S+1)
where S = resultant spin quantum number and g= gyromagnetic ratio(called
g factor)

The quantity g√ S ( S +1 ) is the value of the spin angular momentum of the

electron and thus g is the ratio of the magnetic moment to the angular
momentum. For a free electron g value is nearly 2(i.e 2.00023)
OR when orbital contribution is taken into account
μS+L = √ {g2S(S+1)+ L(L+1)} BM

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Where L is the quantum number of an atom which defines the orbital
contribution to the magnetic moment. Thus looking at the above equation
the magnetic moment is as a contribution of two quantities, the total
spin quantum number S and the total orbital angular momentum
quantum number L.
In the first row-transition metal complexes, the unpaired electrons are in the
outer shell of the metal ions and in such cases the spin component is much
more significant than the orbital contribution because the orbital motion of
these electrons is said to be quenched or suppressed. Therefore, the later
can be neglected in comparison to the former. In such cases the total
magnetic moment is therefore considered entirely due to the spin of the
unpaired electrons and µs is given by
µs = 2√ S (S+1) = √ 4 S (S +1) BM
Now S= nxs where n is the number of the unpaired electrons and s = is the
spin quantum number of one electron which has a value of 1/2
S = nx1/2=n/2
Putting this value of S in the above expression
µs = √ 4 n/2(n /2+1) = √ 2 n(n+2/2)BM or µs = √ n(n+ 2)BM
µs is also expressed µeff effective magnetic moment which is dependent only
on the number of unpaired electrons and their spins. Hence this formula of
magnetic moment is also called spin only formula
Thus the permanent magnetic moment of 3d- transition elements or
compounds gives important information about the number of u.p.e present
in them and it varies with n. The calculated magnetic moment s
corresponding to 1,2,3,4 and 5 u.p.e will be using the spin only formula 1.73,
2.83, 3.87, 4.90 and 5.92 BM respectively
What is the importance of the number of u.p.e evaluated from the
magnetic moment?
For a complex this number gives a valuable information regarding the
structure of the complexes or molecules [provided we have the idea of
strength of the ligands (spectrochemical series)] and the type of orbitals
that are occupied by the electrons as well as those available for hybridization
For example, consider the structure of [MnBr 4]2- complex ion in which Mn is
in +2 oxidation state and its coordination number is 4
In this complex ion, Mn2+ ion is linked with four Br - ions as ligands which
exert weak field on the metal ion orbitals. As a result the five unpaired d-

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orbitals remain unaffected and one s and 3p empty orbitals of the metal
ion(only four hybrid orbitals are needed to hybridize before bond formation
producing sp3 hybrid orbitals thus giving a tetrahedral structure to the
complex ion. The calculated magnetic moment of this complex is nearly
5.92BM which indicates the presence of five u.p.e. If that is the situation, the
tetrahedral structure of the complex ion is confirmed involving only s and p
orbitals
Similarly for the complexes with coordination number six, i.e six ligands are
attached to the central metal ion we can predict whether the complex is
outer or inner orbital complex from the knowledge of weak and strong field
ligands e.g [Co(H2O)6]2+ is an outer orbital complex and [Co(NH 3)6]2+ is an
inner orbital complex having central metal ion Co 2+involving sp3d2 and d2sp3
hybridization respectively.
2.4.Formation Of Coloured Compounds
The cause of exhibition of colour by the ions/compounds/ complexes of the d-
block elements is due to the presence of unpaired electrons in them. For
example [Co(H2O)6]2+ is pink Cu+(d10) is colourless ion and its salts are
colourless but Cu2+(d9) ion and its compounds are coloured, CuSO 4.5H2O is
blue which is actually represented as [Cu(H 2O)4]SO4.H2O and [Cu(NH3)4] is
dark blue(almost violet. Similarly [Ni(NO2)]4- is red and [Ni(NH3)6]2+ is blue.
Among other compounds VO2+ is pale yellow, CrO42- is strongly yellow, MnO4-
is purple in colour and [Ti(H2O)6] is green in colour
The colour of the complex ion depends on the nature of the ligands and type
of the complex formed. The metal ion with completely empty or completely
filled d-orbitals as well as their compounds are colourless viz Sc 3+(3d0),
Ti4+(3d0), Cu+(3d10) and Zn2+(3d10).
Reason: The colour of complexes is due to the presence of incomplete (n-
1)d orbitals . Under the influence of approaching ions or molecules towards
central metal ion, the d-orbitals of central metal split into different energy
levels . This phenomenon is called crystal field splitting . eg when six ions or
molecules approach the metal ion(octahedral field), the d orbitals split into
two sets; one set of d-orbitals of higher energy(d x2-y2, dz2) and the other set
consisting of d-orbitals (dxy, dxz aand dyz) of lower energy. The electrons are
easily promoted from one to another energy level in the same d-sub shell.
These are called d-d transitions . The amount of energy required to excite
some of the of some of the electrons to a higher energy states within the
same d-sub shell corresponds to energy of certain colours of visible light.
Therefore, when white light falls on the compounds, some part of its energy
corresponding to certain colours is absorbed and the electron gets raised

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from lower energy and excess colour is trannsimited. The observed colour is
complementary of colour absorbed e.g Ti3+(d1) is purple.
2.5.. Catalytic Activity
Elements of the first transition series 3d and their compounds are known for
their catalytic activity and have been used in many industrial processes. This
activity is ascribed to their ability to adopt multiple oxidation states and to
form complexes. Thus their availability in a variety of oxidation states makes
them capable of forming intermediate products with various reactants and
their tendency to form interstitial compounds which can absorb and activate
the reacting species facilitate their application as catalysts. For example
finely divided nickel is used in the hydrogenation reactions, MnO 2 catalyses
the decomposition of H2O2. TiCl4 is used as a catalyst for polymerization of
ethane in the manufacture of polyethene . V 2O5 is employed in the catalytic
oxidation of SO2 to SO3 in the contact process of manufacture of sulphuric
acid. Finely divided Fe is used in the manufacture of NH 3 by Haber process,
nickel is used in catalytic hydrogenation while Cu acts as a catalyst in the
manufacture of (CH3)2SiCl2 during the synthesis of silicones. Cu/V is used in
the large scale production of Nylon-66. Fe(III) ions catalyzes the reaction
between iodide and peroxodisulphate ions. These are some of the known
examples where 3d elements are used as catalysts.
Reason: Transition metals show catalytic property because of their ability to
adopt multiple oxidation states. Catalysts at a solid surface involve the
formation of bond between reactant molecules and atoms of the surface of
the catalyst. This has the effect of increasing the concentration of the
reactants at the catalyst surface and also weakening of the bonds in the
reacting molecules and the activation energy is lowered.
The catalytic property of transition metals is due to their tendency to form
reaction intermediates with suitable reactants. These intermediates
decompose yielding products and regenerating the original substance. The
transition metals form reaction intermediates due to the presence of vacant
orbitals and tendency to form variable oxidation state
2.6. Formation of Interstitial and non stoichiometric Compounds
• Def: Interstitial compounds are those which are formed when small
atoms like H,C N B etc are trapped inside the crystal lattices of
metals. They are usually non stoichiometric i.e The formulas quoted do
not correspond to any normal oxidation state of the metal. They are
neither typically ionic nor covalent.

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• It has been found that elements of the 3d transition series are capable
of forming interstitial compounds examples being Ti2C, V2C, ScN, TiN,
Mn4N, Fe3H, Fe4N, TiC, VH0.56 and TiH1.7

• The small atoms enter into the void sites between the packed atoms of
crystalline transition metals to form bonds.Infact,the existence of
vacant (n-1)d orbitals in transition elements and their ability to make
bonds with trapped small atoms is the main cause for the formation of
interstitial compound .

• These compounds have the properties of alloys- being hard and good
conductors. For example steel and cast iron becomes hard by forming
interstitial compound with carbon.

• The 3d elements also form non-stoichimetric compounds. For example,

titanium forms TiOx(x = 1.988-2.00) Vanadium forms VOx (x= 0.79-
1.29). Manganese forms MnxO(x= 0.848-1.00) iron form FexO( x=
0.833-0.957). These compounds have variable composition and are
formed due to the variability of oxidation states and solid defects.

• Sometimes the interstitial and non-stoichiometric compounds are the

same.

• Why do these compounds form?

• This can be understood in the light of imperfections of solids when they

are formed.

• Solids are basically of two Shapes. One is an amorphous solid which

has no specific shape or structure. Another is a crystalline structure or
crystals which have a specific organized structure of their particles.

• Crystals have a structure made up of a regular arrangement of their

atoms (or particles). When such an arrangement of atoms is
represented in a three-dimensional structure, it forms what is called
a crystal lattice .

• Thus a crystalline solid has a very special

• Structure that gives it the unique properties of a solid. This structure

is made up of repeating units which we call a unit cell

• Defects in a Solid

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• When we talk about crystalline solids, we say they have a definite
structure. They have long term arrangement of their molecules

• This means that they have repeated arrangement of a unit cell to form
a space lattice structure. So the arrangement of molecules, in the long
run, will remain the same.

• However, these crystals are not perfect. They have defects or

imperfections in their arrangement of constituent particles. These
defects are a deviation from their uniform arrangement of particles

Types of Defects
• There are various kinds of defects. Among them stoichiometric
defects, interstitial defects and non-stoichiometric defects

• Stoichiometric Defects

• Stoichiometric compounds are those which maintain their

stoichiometry. That means they maintain their ratios of cations and
anions as indicated by their chemical formula.

• The defects in the solid do not affect this ratio. They are of various
kinds, such as vacancy Defect.

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• Here the lattice site is simply vacant, which means there is a missing
particle. In a perfect crystal, there would not be this vacancy. This
defect will lead to a reduced density of the solid. Some surrounding
particle may move to fill in the gap, but the vacancy will only shift in
the opposite direction Also the solid structure of the crystal
Interstitial Defect

• There is an unoccupied space at the very center of the cube structure

of the solid. When the eight spheres of a unit cell meet at the center
they leave a little space, the interstitial site. Sometimes another
particle will occupy this space. This is what we call an interstitial
defect.

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•

• Non-Stoichiometric Defects

• These defects will change the ratio of ions in the solid. The number of
cations and anions will not reflect as stated in their chemical formula.
This imperfection is generally found in a large number of inorganic
compounds. There are mainly two types of non-stoichiometry defects.

• (i). Metal excess defect and (ii).Metal deficiency defect

• will ensure that the particles surrounding the vacant spot do not
collapse.

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 • Metal Deficiency Defects

• In such compounds, there is less metal than its ideal stoichiometric

proportions. Sometimes a positive ion is missing from the lattice site,
but the neutrality of the solid will remain same as a neighbouring ion
will take up two charges. The metal deficiency defect is normally found
in Transition Elements, that have the ability to Metal Excess Defects

• Here there is a surplus of metal ions in the space lattice. This can
happen in one of two ways;

• a).Anionic Vacancy: Sometimes an anion may be missing from its

usual position in the unit cell. This empty space will be occupied by
an electron to maintain the electric neutrality of the solid. This space
that the electron invades, is known as the F-center. This F-center
electron is what gives the compound a color, One common example is
NaCl and the yellow color it obtains on being heated.

• b)Extra Cations: On being heated many compounds result in having

extra cations. These cations fit into the interstitial sites. To balance the
neutrality an equal number of electrons do the same. But the ultimate
result is the excess of metal in the solid. An example of this is when
Zinc Oxide is heated and it losses oxygen have multiple valences.

• Characteristics of interstitial compounds.

• The chemical properties of interstitial compounds are similar to those

of the parent transition metals

• They are hard and lustrous- their borides and carbides extremely hard
approaching that of diamond

• They exhibit electrical and thermal conductivity

• They have melting points higher than pure metals , due to stronger
metal—nonmetal bonds as compared to metal –metal bonds in pure
metals

• They have low densities when compared to parent metals

• They are chemically inert

2.7. Metallic Character and Alloy Formation

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• Definition. An alloy is a blend of metals prepared by mixing the
components. They may be homogenous solid solutions in which atoms
of one metal are distributed randomly among the atoms of the other.
Such alloys are formed by atoms with metallic radii that are within
about 15% of each other.

• Because transition metals have similar atomic radii and other

characteristics they readily form alloys .

• The alloys formed are hard and have high melting points and more
resistant to corrosion than the individual metals.

• Reasons:

• The metals of the first transition series are hard, malleable and ductile.
They exhibit face centered cube(fcc), body centered cubic(bcc) or
hexagonal close packed(hcp) shown below type of lattice structure
and therefore metal atoms are held strongly together.

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 • These metals with these lattices therefore are good conductors of heat
and electricity. Copper and metals of the iron triad [ iron, cobalt and
nickel]are softer than other metals.

• Common alloys

• The best known and common alloys are ferrous alloysOther metals
such as chromium, vanadium, tungsten, molybdenum and manganese
are used in the formation of a variety of steel such stainless steel (Fe-
Cr-Ni-Mn), alnico steel (Fe-Ni-Co-Al).

• Others are nichrome (Ni-Cr) monel metal(Cu-Ni) german silver(Cu-Ni-

Zn)

• Some alloys of transition metals and non transition metals such as

brass(Cu-Zn) and bronze(Cu - Zn) are also common and of
considerable industrial importance

2.8. Periodic Properties and Their Variation along the series

2.8.1. Atomic radii, Atomic Volumes and Ionic radii
The atomic radii of 3d elements generally decrease along the series up to
nickel then increase slightly for copperfor the but pronouncedly lowfor zinc.
The zinc has exceptional value only lower than those for the first two
elements and higher than those of others. This is shown in table below.

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Metal Sc Ti V Cr Mn Fe Co Ni Cu Zn
atoms
Atomic 144 122 118 118 117 117 116 115 117 125
radii(pm
)
• Why does this happen?

 The decrease in atomic radii is due to increased attraction between

the outer electrons and the increased nuclear charge along the period.

 The close values of the atomic radii from chromium to copper are due
to the existence of increased screening effect of 3d-electrons which
are added in each step and which shield the 4s-electrons from the
inward pull though the nuclear charge increases continuously in the
series from one element to the other.

 The screening effect in Zn (3d 10) is maximum and hence has

exceptional high value of atomic radius .

 The atomic volumes of the elements are comparatively low because of

the filling of 3d-orbitals instead of 4s which is the subshell of the last
shell. This causes increased nuclear pull acting on the outer electrons.

 Atomic volumes decrease up to copper and increase thereafter for Zn

 The densities of these elements are very high.

Metal Sc Ti V Cr Mn Fe Co Ni Cu Zn
atoms
Atomic 15.0 11.0 8.3 7.2 7.3 7.1 6.7 6.6 7.1 9.2
volume(cm 3

)
•

• Ionic Radii.

• The ionic radii of the first row transition elements follow the same
trend as their atomic radii.

• Thus the radii of the ions with the same charge generally go on
decreasing as we move across the series except only for the last
element.

• Radii for the bivalent and trivalent ions are shown below

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Bivalent Sc2+ Ti2+ V2+ Cr2+ Mn2+ Fe2+ Co2+ Ni2+ Cu2+ Zn2+
ions
Ionic 95 90 88 84 80 76 74 72 72 74
radii(pm
)
Trivalen Sc3+ Ti3+ V3+ Cr3+ Mn3+ Fe3+ Co3+ Ni3+ - -
t ions
Ionic 81 76 74 69 66 64 63 62
radii(pm
)

2.8.2. Melting and Boiling Points

The MP and the BP of these elements are generally high and have irregular
trend as shown below
Element Sc Ti V Cr Mn Fe Co Ni Cu Zn
s
MP oC 154 167 190 187 124 153 149 145 108 42
0 0 0 5 5 5 5 3 3 0

As is evident from the table, the highest MP is for V(1900 oC) and Zn has the
lowest MP420oC). Among other elements Mn and Cu have lower MP as
compared to other memmbers. The BP are very high >> 2200 oC except for
Zn(906oC) as expected.
• Reasons:

 Generally transition metals crystallize with hcp, ccp or bcc lattices.

They are held together by strong metallic bonds with significant
covalent character

 The high melting and boiling point is due to strong metallic bonds
between the atoms of these elements.

 To melt the metal, metallic bonds should be broken. This requires

significant amount of energy.

 The metallic bond is formed due to interaction of electrons in

the outermost orbitals i.e u.p.e. Therefore the strength of the
bonding depends on the number of the unpaired electrons in the
outermost orbital . Greater the number of the unpaired electrons,

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 stronger is the metallic bonding and consequently , higher the M.P
and the BP

 Therefore in a given period of transition elements, the number of u.p.e

in the (n-1)d orbital increases upto d 5 configuration. This results in the
increase in the strength of metallic bonds and the M.P and B.P.

 Thus the metallic strength increase up to the middle till d 5

configuration and then decreases as a result of unavailability of
unpaired d-electrons(from Fe onwards).

 Pairing of electrons results in decrease in the number of u.p.e from d 6

to d9 configuration.

 This decreases the strength of the metallic bonds and results in

progressive decrease in the M.P and BP

 Note: The dip in Mn is due to the fact that Mn has stable electronic
configuration (3d54s2). As a result 3d electrons are more tightly held
by Mn atomic nucleus and this reduces delocalization of electrons
resulting in weaker metallic bonding.

2.8.3.Ionization Enthalpies and Reactivity

 Def: Ionization enthalpy is defined as the amount of energy
required to remove the outermost electron completely from a
gaseous atom in its ground state

 The ionization enthalpies of d-block elements are higher than those of

s-block elements and lower than the ionization enthalpies of p-block
elements. This is due to the trends in atomic radii and nuclear charge

• As we have said, the atomic radii of transition elements are lower than
the atomic radii of the s block elements and higher than the atomic
radii of the p-block elements.

• We have also said that the nuclear charge of transition elements are
higher than the nuclear charges of the s-block elements and lower
than the nuclear charges of p-block elements

• Due to an increase in nuclear charge which accompanies the filling of

the inner d orbitals, there is an increase in ionization enthalpy along
the series of transition elements from left to right.

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 • However the first IE values for 3d elements show irregular trend as
shown in the figure and table below

Elemen Sc Ti V Cr Mn Fe Co Ni Cu Zn
t
Atomic 21 22 23 24 25 26 27 28 29 30
numbe
r
IE(∆ iHo) 631 656 650 653 717 762 758 736 745 906
M+
IE(∆ iHo) 123 130 141 159 150 156 164 175 195 1734
M2+ 5 9 4 2 9 1 4 2 8
IE(∆ iHo) 239 265 283 299 326 296 324 340 355 3829
M3+ 3 7 3 0 0 2 3 2 6

 The appreciably higher values of 1 st IE for Zn is attributed to the

additional stability associated with completely filled 3d-subshell
(3d104s2).

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 The2nd and 3rd IE values generally show the increasing trend from Sc to
Zn.

 The variation or the irregularity occurring in the value of IE across the

series are mainly due to the changes in atomic radii because of the
screening effect of extra electrons added to 3d-subshell which is
exerted on the nuclear charge.

 Because of high IEs,the elements of the first transition series show

less reactivity compared with those of s block elements

 Reason:

 The increase in IE is due to the effect of increasing nuclear charge

which would tend to attract outer electrons with greater force.
Consequently, IE is expected to increase smoothly. But the addition of
electrons take place in last but one (3d-subshell and this increases the
screening effect and causes slight irregularities in IEs

 With the increase in electrons in d-sub shell the outer electrons are
shielded more and more. Thus the effect of increased nuclear charge is
opposed by additional screening effect of the nucleus and the IE
increases but slowly.

 The irregular trend in the first IE of first transition series elements is

due to the fact that removal of one electron alters the relative energies
of 4s and 3d orbitals

 Therefore there is reorganization energy with gains in exchange

energy due to increase in the number of electrons in d n configuration
and from transference of s-electrons into d-orbital

 Some exceptions observed in IE are:

 Cr and Cu have high second IE. This is attributed to their half filled (d 5)
and completely filled (d10) electronic configuration.

 The value of second IE for zinc is low because ionization involves

removal of an electron 4s1 resulting in stable 3d10 configuration

 The trend in third IE shows high value for Mn 2+ and Zn2+ because of
stable 3d5 and 3d10 electronic configuration

 Note :

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 i)Although the first IE, in general increases, across the period, the
magnitude of the increase in the second and third IE for the successive
elements in general is much higher.
ii).The irregular trend in the first IE of the 3d metals , though of little
chemical significance , can be accounted for by considering that the removal
of one electron alters the relative energies of 4s and 3d orbitals. So the
dipositive ions have dn configurations with no 4s electrons. There is thus a
reorganization energy accompanying ionization with some gains in exchange
energy as the number of electrons increases and from the transference of s
electrons into d orbitals
iii). There is the generally expected increasing trend in the values of IE as the
effective nuclear charge increases. However the value for Cr is lower
because of the absence in any change in the d configuration and the value
of Zn is higher because it represents an ionization from the 4s level.
 The lowest common oxidation state of these elements is +2. To form
the M2+ ions from the gaseous atoms, the sum of the 1st, 2nd IEs and
the enthalpy of atomization for each element is required. The dominant
term is the 2nd IE which shows unusually high values for Cr and Cu
where the d5 and d10 configuration of M+ ions are disrupted, with
considerable loss of exchange energy.

 The value for Zn is correspondingly low as the ionization consists of

removal of an electron which allows the production of the stable d 10
configuration.

 The trend in the third IE is not complicated by the 4s orbital factor and
shows the greater difficulty of removing an electron from the d 5(Mn2+)
and d10(Zn2+) ions besides the general increasing trend of the third

 In general the third IE are quite high and there is a marked break
between the values for Mn2+ and Fe2+

The high values for Cu, Ni and Zn indicate why it is difficult to obtain
oxidation state higher than two for these elements

CHEM 419 Notes Part 2

Thermodynamic stabilities of Transition metal compounds
• The thermodynamic stability of transition metal compounds can be predicted on the basis of their
IE value. Smaller the IE of the metal, more stable is its compounds in that particular oxidation state

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• In other words, when the sum of the IEs required to attain a particular oxidation state of transition
metal ions is small, the thermodynamic stability of the compounds of the metal in that oxidation
state is high.
Example: Consider the two reactions shown below.
• Ni Ni2+ + 2e IE = 2.29 x 103 kJ/mol
• Pt Pt2+ + 2e IE = 2.66 x 103 kJ/mol
• From the values of IEs, Compounds containing Ni(II) are thermodynamically more stable than Pt(II)
compounds. This is because less amount of energy is required for the ionization of Ni to Ni2+ than
the energy required for the ionization of Pt to Pt2+
• Ni Ni4+ + 4e IE = 11.29 x 103 kJ/mol
• Pt Pt4+ + 4e IE = 9.36 x 103kJ/mol
• Pt(IV) compounds are relatively more stable than Ni(IV) compounds.
• For this reason, K2PtCl6 does exist and is a well known compound of Pt(IV) but the corresponding
compound of Ni(IV) is not known
• However, in solution, the stability of the compounds or oxidation states depends upon electrode
potentials rather than IEs
• Electrode potential values depend upon factors such as enthalpy of sublimation, atomization , the
IE and the hydration enthalpy
• Thus in addition to ionization enthalpy, , ∆ Hsub, and ∆ Hhyd, explain the stability of a particular
oxidation state in aqueous solution.
• This is illustrated as follows.
• M(s) M(g). ∆ Hsub
M(g) M+(g) + e I.E
M+(g) + nH2O M+(aq) Hhyd
• The total energy , for the process M(s) M+(aq) + e
• involving sublimation, ionization and hydration simultaneously will be the sum of the three types of
enthalpies
∆T H = ∆ Hsub + I.E + ∆ Hhyd
• Smaller the value of total energy change for a particular oxidation state in aqueous solution,
greater will be the stability of the oxidation state.
• Thus ∆T H is the total enthalpy change when solid metal M is brought in aqueous medium in the
form of monovalent ion M+(aq)

CHEM 419: CHEMISTRY OF TRANSITION METALS ELEMENTS JANUARY-APRIL 2025 NOTES

• Smaller the value of total energy change for a particular oxidation state in aqueous solution,
greater will be the stability of the oxidation state.
• Similarly, the lower the electrode potential i.e more negative the standard reduction potential of the
electrode, more stable is the oxidation state of the transition metal in aqueous solution.
• More negative values of Eo for Mn2+ /Mn and Zn2+
• /Zn are due to the stability of half filled (3d5)in Mn2+ and completely filled (3d10)configuration in Zn2+
ELECTROCHEMICAL PROPERTIES IN AQUEOUS MEDIA.
(i) Reduction- Oxidation reactions
• Redox reactions involve two half reactions – a reduced half reaction and an oxidized half reaction
which always occur together
• There are different definitions and phenomena given for oxidation and reduction reactions
(ii) Oxidation number
• In case of ionic reactions, redox changes can be explained in terms of electron transfer. However,
in case of covalent compounds, the redox reactions can be explained on the basis of oxidation
number. The oxidation number is a measure of the extent of oxidation of an element in its
compound. This is the charge which appears on a species when the other atoms are removed from
the compound.
(iii). Oxidation (De-electronation): This is a process in which electrons are lost and results in the
increase in oxidation number of an element.
(iv).Oxidizing agent(OA). This is a chemical species which accepts electrons(electron acceptor)
or a species whose oxidation number of the atoms or ions decreases. We talk of strong and weak
oxidizing agents. A strong oxidizing agent is a chemical species that is itself easily reduced. Such
species are marked by large positive reduction potentials.
Example

CHEM 419: CHEMISTRY OF TRANSITION METALS ELEMENTS JANUARY-APRIL 2025 NOTES

  Fluorine molecules are extremely eager to accept electrons to become fluoride ions while
manganese (+7) is eager to accept 3 electrons to become Mn4+
(v). Reduction (Electronation): This is a process in which electrons are gained and results in the
decrease in the oxidation number of the element
(vi).Reducing agent(R.A)
 Reducing agent is a species that donate electrons (electron donor) or is a species whose oxidation
number increases.
 A very strong reducing agent is very easily oxidized, so its corresponding reduction potential is
large and negative.
 Good examples are alkali and alkaline earth metals

• These terms can be understood by considering the following example

• Here oxidation of Fe and reduction of Cr takes place

• Oxidizing agent is Cr2O72- and reducing agent is Fe2+
• Thus a reduction – oxidation (redox) reaction is a chemical reaction which comprises transfer of
electrons between two species viz oxidizing agent and reducing agent.
• From the above definitions a strong oxidizing agent can also be defined as a chemical species that
is itself easily reduced. Such species are marked by large positive reduction potential

CHEM 419: CHEMISTRY OF TRANSITION METALS ELEMENTS JANUARY-APRIL 2025 NOTES

• A strong reducing agent is chemical species that is easily oxidized, so its corresponding reduction
potential is large and negative
Electrochemical cell
• If a strip of zinc metal is immersed in an aqueous solution of copper sulphate , dark coloured solid
deposits on the surface of the zinc and the blue colour of characteristic of Cu2+ slowly disappear
from the solution. The dark coloured deposit is finely divided copper metal and the solution
contains zinc ions
• The reaction can be written as
• Zn(s) + Cu2+(aq) Zn2+(aq) + Cu(s)
• This is a redox reaction in which Zn is oxidized to Zn2+ ions and Cu2+ is reduced to Cu.
• The redox reaction can be separated into half reactions, one representing reduction and the other
representing oxidation
• Oxidation half reaction Zn(s) Zn2+ (aq) + 2e
• Reduction half reaction : Cu2+ + 2e Cu(s)
• As you recall Cu2+ is the oxidizing agent because it is gaining electrons from Zn and causes
oxidation of Zn to Zn2+

• The above is an example of a galvanic cell known as Daniel cell. Electrons flow from Zn electrode
to Cu electrode through a wire.
• The electrode at which oxidation takes place is called an anode . The electrode where reduction
takes place is the cathode.
• Anode(oxidation)half reaction

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• Zn(s) Zn2+(aq) + 2e
• Cathode(reduction)half reaction
• Cu2+ + 2e Cu(s)
• Overall reaction Zn(s) + Cu2+(aq) Zn2++ Cu
Standard Electrode Potentials.
• The standard potential of any galvanic cell is the sum of the standard half-cell potential for
oxidation at the anode and reduction at the cathode
• Eo cell = Eoox + Eo red
• Consider for example , a cell in which zinc metal is oxidized to Zn2+ ions at the anode and H+ ion s
are reduced to H2 gas at the cathode
• Anode oxidation Zn(s) Zn2+aq + 2e
• Cathode reduction 2H+aq + 2e H2(g)
• Overall cell reaction
• Zn(s) + 2H+ Zn2+ (aq) + H2(g)
• The standard potential for this cell is 0.76V at 250C and is a measure of the combined driving
forces of the oxidation and reduction half reactions
• Eo cell = Eoox + Eored or Eo Zn Zn2+aq + EoH+ H2(g) = 0.76V
• It is not possible to measure the potential of a single electrode. We can only measure the potential
difference by placing a voltmeter between two electrodes
• However we can develop a set of standard half cell potentials by choosing an arbitrary standard
half cell as a reference point, assigning it an arbitrary potential and expressing all other potentials
relative to the reference half cell. This reference half cell is called standard hydrogen
electrode(SHE). It consists of a platinum electrode with H2 gas and aqueous H+ ions at standard
state conditions [1atmH2(g) 1MH+ aq , 250c]
• The half cell reaction for this electrode is given by

 The potential Eo being defined as 0.00V under standard conditions [25OC, 1atm, and Unity
activity]
 In a cell consisting of SHE and a metal electrode, M, dipped in an aqueous solution containing Mn+
the standard potential of the electrode is the same as the measured potential of the cell since the
SHE potential is defined as 0.00V under standard conditions
Types of Electrode potential
(i)Oxidation Electrode potential

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 Oxidation potential of an electrode is for the oxidation reaction taking place at the anode. Thus the
oxidation electrode potential is the potential of an electrode at which oxidation takes place and
hence it is a measure of the tendency of the electrode in a half cell to get oxidized or lose
electrons

(ii).Reduction Electrode Potential

• Reduction potential for an electrode is for the reduction reaction taking place at the cathode. Thus
reduction electrode potential is the potential of the electrode at which reduction takes place and
hence it is a measure of the tendency of the electrode in a half cell to get reduced or to gain
electrons

Determination of standard reduction/oxidation potentials

• Standard reduction or oxidation potentials can be determined using SHE universally recognized as
having reduction and oxidation potentials of zero.
• When the standard reduction and oxidation potential of chemical species are measured, it is
actually the difference in the potential from hydrogen electrode that is measured
• By using a galvanic cell in which one side is a SHE, and the other side is half-cell of the unknown
chemical species, the potential difference from hydrogen can be determined using a voltmeter.
Standard reduction and oxidation potentials can both be determined in this fashion.
• When the standard reduction potential is determined, the unknown chemical species is being
reduced while hydrogen is being oxidized, and when the standard oxidation potential is
determined, the unknown chemical species is being oxidized while hydrogen is being reduced.
• Relation between oxidation potential and reduction potential
The oxidation potential and reduction potential are related as shown below.
• (Eox)electrode = - (Ered)electrode
• -(Eox)electrode = (Ered)electrode
Similarly for standard electrode potential
• (Eoox)electrode = - (Eored)electrode
• -(Eoox)electrode = (Eored)electrode
Important convention
• By convention the value of an electrode potential is expressed as reduction electrode potential.
Thus if we say that the value of standard electrode potential of zinc electrode is -0.76 V for
example , this means that the given value is the value of the standard reduction electrode potential
of zinc electrode i.e E0Zn2+/Zn = -0.76V

CHEM 419: CHEMISTRY OF TRANSITION METALS ELEMENTS JANUARY-APRIL 2025 NOTES

• The values of standard reduction potentials of many electrodes have been determined at 25oC and
arranged as follows (see various text books for a list of reduction potentials)
Oxidizing and reducing properties of substances in aqueous solution.
The following should be noted:
• (i).The substance which has a positive value of the reduction potential (Eored)has the tendency to
gain electrons to undergo reduction and hence is capable of acting as an oxidizing agent in
aqueous solution.
• (ii)The substance which has a negative (Eo red)value of reduction potential has the tendency to lose
electrons to undergo oxidation and hence is is capable of acting as a reducing agent in aqueous
solution
• (iii) Higher the value of the reduction potential (Eored)higher the tendency of the substance to accept
electrons to undergo reduction in aqueous solution and hence higher the oxidizing power of the
substance.
• (iv).Higher the E0 reduction potential, lower the tendency of a substance to lose electrons to
undergo oxidation in aqueous solution and hence lower the reducing power of the substance
• (v).Since the reduction potential values increases down the electrochemical series i.e - to zero to
positive, the oxidizing power of the oxidizing agent also increases.
• (vi).Since reduction potential value increases down the electrochemical series, the reducing power
of the reducing agents decreases in that order.
NOTE:If the metal electrode is positively charged with respect to the hydrogen electrode, then the
electrode potential is positive, as in the half reaction

• Where E= +0.34V.
• If the metal electrode becomes negatively charged ( it loses electrons more readily than
hydrogen), the electrode potential is negative with respect to hydrogen electrode as in the reaction
shown below
Mn2+ + 2e Mn
Where E = -1.18V
These electrode potentials reflect the electrostatics of what is happening at the metal electrode
• For the purpose of discovering whether a particular redox reaction will occur, it is more useful to
develop a thermodynamic convention involving potential Eo defined in the relationship
∆ G=−nF ∆ E o
• ∆ G is the change in Gibb’s free energy, n is the number of moles of electrons involved in the
reaction and F is the Faraday’s Constant

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• If ∆ E o is positive , the value of ∆ G will be negative and a reaction is thermodynamically feasible
i.e ∆ G <0. We say the reaction is spontaneous
• For a nonspontaneous reaction ∆ G> ¿ 0 and ∆ E o < 0 .
• The sign of E o for a half reaction or an overall reaction depends on the direction in which the
reaction is written and by convention half reactions are reported as reduction processes
• Note
• The standard reduction potentials of the elements of 3d-series except copper are lower than that of
hydrogen electrode. These elements evolve H2 from acids though at very low rate
M + H+ M2+ + 1/2H2
• These metals are easily oxidized to their ions and hence are reducing agents though poor due to
the formation of a thin impervious layer of an inert oxide
• Note that copper does not react with acids. It has the tendency to get reduced. sometimes the
metals are protected from the attack of acids by a thin impervious layer of an inert oxide.
Disproportionation reactions.
• These are the redox reactions in which the oxidation number of a species can increase and
decrease simultaneously.
• Some transition metal species in the same oxidation state can undergo chemical change in such a
way that some species get oxidized and some others get reduced at the same time .
• Example1
• Consider the following reaction in which Cu+ is oxidized to Cu2+ and reduced to Cu0 at the same
time. The question is is this reaction feasible?
• 2Cu+ 2Cu2+ + Cu0
For oxidation
• Cu+ Cu2+ + e Eo Cu+/Cu2+ = -0.16V
For reduction
• Cu+ + e Cuo Eo Cu+/Cuo = + 0.52V
• Overall reaction
• 2Cu+ 2Cu2+ + Cu0 Eo = +0.36V
• Eo is positive and therefore from the equation ∆ G=−nF ∆ E o , this reaction is
thermodynamically feasible because ∆ G< 0

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 •

• Consider also the reaction below

•
• Here , Mn which is in +6 oxidation state
• undergoes disproportionation into +7 and +4 oxidation states
Trend in M2+/M standard electrode potential
• The table below shows the thermochemical parameters and data related to the transformation of
the solid metal atoms to M2+ ions in solution and their standard electrode potentials.

Element(M) ∆a H(M) ∆i H1 ∆i H2 . ∆hyH(M2+) E/V

Ti 469 661 1310 -1866 -1.63

V 515 648 1370 -1895 -1.18

Cr 398 653 1590 -1925 -0.90

Mn 279 716 1510 -1862 -1.18

Fe 418 762 1560 -1998 -0.44

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Co 427 757 1640 -2079 -0.28

Ni 431 736 1750 -2121 -0.25

Cu 339 745 1960 -2121 0.34

Zn 130 908 1730 -2059 -076

observations

 There is no regular trend in the Eo(M2+/M) values.This is because their (IE1 +IE2)
and sublimation enthalpies do not show any regular trend.
 The general trend towards less negative Eo values along the series is due to the general increase
in the sum of first and second IE
 The unique behaviour of Cu having a positive Eo, accounts for its inability to liberate H2 from acids.
Only oxidizing acids (nitric acid and hot Conc sulphuric acid react with copper, the acids being
reduced.
 The reason for positive Eo value for copper is that the sum of enthalpies of sublimation and
ionization is not balanced by the hydration enthalpy Thus The high energy to transform Cu(s) to
Cu2+(aq) is not balanced by its hydration enthalpy.
 It is interesting to note that the value of Eo for Mn , Ni and Zn are more negative than expected from
the trend. This is due to the greater stability of the half filled d subshell in Mn2+ and the completely
filled d10 configuration in Zn2+ The exceptional behavior of Ni towards Eo from the regular trend is
due to its high negative enthalpy of hydration

Trend in M3+/M2+ standard electrode potential

 Except nicjel,copper and zinc, all other elements of the first transition series show +3 oxidation
states to form M3+ in aqueous solution.

 Element(M  ∆aH(M)  ∆i  H2  H(M2+)  E/V  E/V

) H1 M2+/M M3+/M2+

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  Ti  469  661  1310  -1866  -1.63  -0.37

 V  515  648  1370  -1895  -1.18  -0.26

 Cr  398  653  1590  -1925  -0.90  -0.41

 Mn  279  716  1510  -1862  -1.18  +1.57

 Fe  418  762  1560  -1998  -0.44  +0.77

 Co  427  757  1640  -2079  -0.28  +1.97

 Ni  431  736  1750  -2121  -0.25  -

 Cu  339  745  1960  -2121  0.34  -

 Zn  130  908  1730  -2059  -076  -

The following needs to be noted

 A very low value for Eo (Sc/Sc3+) reflects stability of the Sc3+ which has a noble gas configuration
 The comparatively high value of Eo for (Mn2+/Mn3+) shows that Mn2+(d5) is particularly stable
 The comparatively low value Eo for (Fe3+/Fe2+), is on account of extra stability for Fe3+
(d5)configuration i.e low 3rd IE of Fe
 The highest value for Zn is on account of very high stability of Zn2+. With the stable d10
configuration. It is difficult to remove an electron from it to change it to into Zn3+
 The comparatively low value for V is on account of the stability of V2+(half filled t2g level)

Chemical Reactivity and Eo values

 Transition metals vary widely in their chemical reactivity. Many of them are sufficiently
electropositive to dissolve in mineral acids, although a few are noble-that is they are not affected by
single acids.
 The metals of the first series with exception of copper are relatively more reactive and are oxidized
by 1M H+, though the actual rates at which these metals react with oxidizing agents like hydrogen
ions is sometimes slow. e.g titanium and vanadium , in practice are passive to dilute none
oxidizing acids at room temperature

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 The less negative E values for M2+/M indicate a decreasing tendency to form divalent cations
across the series. This general trend towards less negative Eᶿ values is related to the increase in
the sum of the first and second IE.
 It is interesting to note that the Eᶿ for Mn, Ni and Zn are more negative than expected from the
general trend showing greater stability for Mn2+ (half filled d - subshell (d5)} and Zn2+ completely
filled d-subshell (d10).
 Whereas the stabilities of half filled d - subshell (d5) in Mn2+ and completely filled d-subshell (d10) in
zinc are related to their Eo values, for nickel, Eᶿ value is related to the highest negative enthalpy of
hydration
 Examination of the Eᶿ values for the redox couple M3+ / M2+ shows that Mn3+ and Co3+ ions are the
strongest oxidizing agents in aqueous solutions. The ions Ti2+, V2+ and Cr2+ are strong reducing
agents and will liberate hydrogen from a dilute acid
 Example 1
 For the first row transition metals, the Eᶿ values are
 Metal V Cr Mn Fe Co Ni Cu
 Eo(M2+ /M) -1.18 -0.91 -1.18 -0.44 -0.28 -0.25 +0.34
 (i).Explain the irregularity in the above values.
 (ii) Examining the reduction potentials for redox couple (M2+ /M) given above list the elements in
the increasing order of their reducing power
 Explanation:
 The Eo values are not regular and can be explained from the irregular variation of ionization
enthalpies (∆ i H1 + ∆ i H2) and also the sublimation enthalpies which are relatively much less for
manganese and vanadium.
 (ii) Answer
 By convention, the above standard electrode potentials are written as reduction potentials for the
following reaction
 M2+. + 2e → M
 Arrangement of the metals in the increasing order of reducing power is guided by the following
principle
 The substance which has a negative (-ve) value of Eored has a greater tendency to lose electrons
to undergo oxidation and hence it is capable of acting as a reducing agent in aqueous solution.
 Higher the value of Eored ( less negative) lower the tendency of the substance to lose electrons to
undergo oxidation in aqueous solution and hence the lower the reducing power of the
substance.
 In contrast, lower the value of Eo red (more negative Eo red ) higher the tendency of the substance to
lose electrons to undergo oxidation in aqueous solution and hence the higher the reducing power
of the substance.
 Similarly, the substance which has a positive (+ve) value of Eo red has a tendency to gain electron to
undergo reduction and hence it is capable of acting as an oxidizing agent in aqueous solution.

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 Higher the value of Eored ( less negative the Eo red value) higher the tendency of the substance to
accept electrons to undergo reduction in aqueous solution and hence the higher the oxidizing
power of the substance.
 In contrast, lower the value of Eo red (more negative Eo red ) lower the tendency of the substance to
gain electrons to undergo reduction in aqueous solution and hence the lower the oxidizing power
of the substance
 From this argument, the above electrode reactions can be arranged in increasing reducing power
i.e decreasing Eo red as follows
 Cu2+/Cu E0 = + 34V < Ni2+/Ni E0 = -0.25V <Co2+//Co E0 = -0.28V<Fe2+/Fe E0 = -0.44V < Cr2+/Cr E0
= -0.91V < V2+ /V = Mn2+/Mn E0 = -1.18V
 Thus Mn and V have the highest reducing power[undergo oxidation] in the series and readily
undergoes the reaction
 Mn → Mn2+ +2e Eo Ox = +1.18V
 V → V2+ +2e Eo Ox = +1.18V
 Note the reversal of the sign of reduction potentials but the magnitude remain the same
 Example 2.
 For M2+/M and M3+/M2+ couples the E0 for some metals are as follows:
 M2+/M E0 M3+/M2+ E0
 Cr2+/Cr -0.9V Cr3+/Cr2+ -0.4V
 Mn2+/Mn -1.2V Mn3+/Mn2+ +1.5V
 Fe2+/Fe -0.4V Fe3+/Fe2+ -0.4V
 Use the above data to comment on
 (i).The stability of Fe3+ in acid solution as compared to that of Cr3+ or Mn3+
 ii. The ease with which Fe can be oxidized as compared to a similar process for either Cr or Mn

CHEM 419: CHEMISTRY OF TRANSITION METALS ELEMENTS JANUARY-APRIL 2025 NOTES

Solution

(i) The relative stability of the Cr3+ , Fe3+, and Mn3+

 The higher the reduction potential for a species, greater the tendency for
its reduction to take place, i.e more spontaneous the reaction and greater
the stability of the species formed .

M3+ + e M2+

 Reduction potential (Eo) for the three (M3+/ M2+ ) species can be represented
as follows
Cr3+/ Cr2+ Fe3+/ Fe2+ Mn3+/ Mn2+

- 0.4V +0.8V +1.5V

Increasing reduction potential

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
 From the values of the reduction potentials, Mn2+ has greater stability in acid
medium than Fe2+ which in turn has greater stability than Cr2+.
 This means that Mn3+ is reduced more readily to more stable Mn2+ (reaction
more spontaneous and accompanied by positive Gibb’s free energy) than Fe3+
( reaction is less spontaneous and accompanied by less positive Gibb’s free
energy compared to Mn3+) but less than Cr3+( reaction nonspontaneous and
accompanied by positive Gibbs free energy)
Thus relative stability of these ions is
Mn3+, < Fe3+, < Cr3


(ii). The ease with which Fe can be oxidized as compared to a similar process for
either Cr or Mn

 The lower the reduction potential of species, greater the tendency of the
species to be oxidized.
 Reduction potential (Eo) for the three M2+/ M can be represented as follows

Mn2+/ Mn Cr2+/ Cr Fe2+/ Fe

- 1.2V - 0.9V - 0.4V

Decreasing reduction potential greater tendency for oxidation

 From the above observation, Mn is oxidized more readily to Mn2+ and Fe is

oxidized least readily among the given metals Mn, Cr and Fe.
The oxidation potentials for the given pairs will be +1.2V, +0.9V, and 0.4V.
Thus the order of their getting oxidized will be in the order Mn > Cr > Fe.

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 
Or an alternative explanation may be as follows
 Eo for Cr3+/ Cr2+ is - 0.4 V i.e negative, this means Cr3+ in solution cannot be
easily reduced to Cr2+ i.e Cr3+ is stable. As Mn3+/ Mn2+ is 1.5V i.e positive
means, Mn3+ can easily be reduced to Mn2+ ions in comparison to Fe3+ions.
 Thus relative stability of these ions is

Mn3+, < Fe3+, < Cr3+.Type equation here.

 THE BINARY COMPOUNDS OF THE FIRST TRANSITION SERIES ELEMENTS

 Binary compounds are formed by combination of two different elements or ions eg, oxides,
suphides, halides etc.
 Oxides
 The elements of 3d-transition series react with oxygen at high temperature to give oxides. The
binary oxides formed by these elements are given in the table below.

Group 4 Group Group Group Group Group9 Group

5 6 7 8 10 Group 11

TiO (b) VO (b) CrO(b) MnO(b) FeO(b) CoO(b,) NiO (b) Cu2O (b)

Ti2O3(b) V2O3(b) Cr2O3(amp) Mn2O3(b) Fe2O3(am) Co2O3* Ni2O3* CuO(amp)

Mn3O4** Fe3O4**

V2O4(w.b) CrO2(a) MnO2(amp) CoO2* NiO2*

TiO2(amp)
VO2+
TiO2+

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 V2O5(amp)
VO2+,

CrO3(a)

Mn2O7(a)

• Key: b = basic, w.b weak basic a = acidic, w.a = weak acidic amp = amphoteric * compound has
not been prepared in pure state, ** denotes mixed valent compound
• All the elements except scandium form MO oxides which are ionic.
• These oxides are less basic and less soluble in water when compared to similar oxides for s block
elements.
• The highest oxidation state in the oxides coincides with the group number and is attained in
Sc2O3( Sc = group 3) to Mn2O7 ( Mn = group 7).
• Beyond group 7, no oxides are formed where the metal has greater oxidation state than +7. For
instance there is no higher oxides of iron above Fe2O3 that are known.
• Besides the oxides the oxocations exist where the oxygen stabilizes V(V) as VO2+, V(IV) as VO2+
and Ti(IV) as TiO2+.
• As the oxidation number of a metal increases the ionic character of the oxide decreases.
• Thus oxides in lower oxidation states are ionic and basic, in the intermediate oxidation states their
nature is amphoteric and in higher oxidation states, ionic nature decreases and covalent nature
increases thereby increasing the acidic character of the oxides.
• For instance Mn2O7 exists as a covalent green oil while CrO3 and V2O5 have low melting points. In
these higher oxides, the acidic character predominates.
• This has an implication that the acidity of the a salt depends on its covalent nature which in
turn is based on the oxidation state of the element.
• Thus the oxidation state is directly proportional to covalent nature and proportional to acidic nature
of its oxides. Accordingly the oxides may be classified as basic, amphoteric and acidic oxides

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 • Basic Oxides are those which are formed by the metals in the lower oxidation states. These are
ionic in nature, soluble in nonoxidising acids eg HCl. For example TiO, CrO, MnO, FeO, Cu2O
CoO, NiO
• Amphoteric oxides are the oxides containing the metals in the high/intermediate oxidation states.
These oxides are also soluble in nonoxidising acids eg HCl Examples TiO2, VO2, Cr2O3, Mn3O4,
MnO2, CuO ZnO
• Acidic oxides are of weak acidic nature and are formed by elements in higher oxidation states.
These are soluble in bases. For example V2O5, CrO3, MnO3, Mn2O7 etc.
• NB:Combination with oxygen stabilizes the very high oxidation states of 3d metals. The highest
oxidation state towards oxygen is reached with manganese
• It is important to note that the highest oxidation state is generally shown among halides
and oxides of first row transition series. Why is this? This is because fluorine and oxygen are
hard bases . They are small in size and highly electronegative. They can therefore oxidize metals
to the highest oxidation state and are known to stabilize the ions in those states.
• It is important to note that the highest oxidation state is generally shown among halides
and oxides of first row transition series. Why is this? This is because fluorine and oxygen are
hard bases . They are small in size and highly electronegative. They can therefore oxidize metals
to the highest oxidation state and are known to stabilize the ions in those states.
• Reducing and oxidizing nature of oxides .
 The electron exchange property determines the redox nature of the oxides.
 The oxides containing the metal in lower oxidation state acts as electron donor and hence are
reductant (reducing agent).
 As atomic number increases, the reducing property in the lower oxidation state also increases e.g
TiO < VO < CrO. This is presumably due to increase in shielding effect
• If the metal in the oxide is in higher oxidation state, the oxide is electron acceptor or oxidizing agent
eg CrO3, Mn2O7
• Halides: Fluorides

The binary fluorides, together with some mixed oxide fluorides of 3d metals are shown below

Group 4 Group5 Group6 Group7 Group8 Group9 Group10 Group11

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 VF2 CrF2 MnF2 FeF2 CoF2 NiF2 CuF2

TiF3 VF3 CrF3 MnF3 FeF3 CoF3 NiF63- CuF63-

TiF4 VF4 CrF4 MnF4* CoF62- NiF62-

VF5 CrF5 MnO3F*

CrF6*

* Denotes a compound which is thermally unstable at or below room temperature.

• Transition metals react with halogens at high temperature as they have high activation energies to
form halides. High temperature is required to start the reaction but heat of reaction is sufficient to
continue the reaction.
• The above table shows that the highest oxidation states are brought out in combination with the
fluorides. As we move across the period, the highest oxidation state shown in a binary fluoride
reaches a maximum and then falls off quite sharply. Thus in the 3d series, the highest oxidation
state is reached with chromium although in a very unstable compound.
• Thereafter manganese forms unstable MnF4 and iron and cobalt their trifluorides as the highest
oxidation in combination with fluorine
The +7 oxidation state for Mn is not represented in simple halides but MnO3F is known and beyond Mn no
metal has a trihalide except FeX3 and CoF
Chlorides
The binary chlorides and some mixed oxide chlorides are shown below
Group 4 Group5 Group6 Group7 Group8 Group9 Group10 Group 11

TiCl2 VCl2 CrCl2 MnCl2 FeCl2 CoCl2 NiCl2 CuCl

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 TiCl3 VCl3 CrCl3 MnCl3* FeCl3 CuCl2

TiCl4 VCl4 CrCl4* MnCl62-*

VOCl3 CrOCl3

CrO2Cl2*

MnO3Cl

• For some low oxidation states, the binary chloride is known but the fluoride is not. Conversely for
some high oxidation states, the fluoride, but not the chloride, can be made. The highest oxidation
state in a binary chloride is +4 in the first series(with vanadium and chromium). As observed , the
highest oxidation state tends to increase as the atomic number increases .
• Note that much less is known about the bromides and iodides and we shall not consider
them further

2.0 CHEMISTRY OF THE ELEMENTS OF THE SECOND TRANSITION (4d) SERIES

As we said previously the elements of first transition series are more important than their heavier
congeners hence their chemistry is best of the studied separately
Why is this?
Reasons:
(i).The chemistry of the first member of a triad is distinct from that of the two heavier metals . e.g Zr and Hf
have similar chemistries but that of Ti differs
(ii).Electronic spectra and magnetic properties of many complexes of the first row metals can often be
rationalized using crystal field or molecular orbital theories but effects of spin-orbit coupling are more
important for the heavier metals of second and third rows therefore the properties are not easy to interpret
(iii)Complexes of the heavier metal ions show a wider range of coordination numbers than those of the first
row congeners. Generally CN of the elements of the second and third transition series are greater than that
of the first series because the ionic radii are larger. Thus tetrahedral coordination is considerably less
frequent although observed in species such as [WO4]2-, [ReO4]- and OsO4 square planar are known for
Rh(I),Pd(II), Pt(II) and Au(III) which are stabilized by CFSE. Octahedral complexes are common and the
occurrence of CN 7,8 9 and 10 are fairly common.
(iv)The trends of the oxidation states are not consistent for all members of a triad. For example: although
the maximum oxidation state of Cr, Mo and W is +6, The stability of the +6 oxidation state is greater for Mo
and W than for Cr. Thus the heavier congeners show pronounced tendency toward higher oxidation states

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(v).Metal - metal bonding is more important for the heavier metals than for those in the first row
The chemistry of the so-called heavy transition metals (those of the 4d and 5d periods) is often overlooked
in the study of the transition metals.In this study, we will describe some patterns and trends of these
elements without going into details on specific elements.
The main differences between the second and third series of transition elements on one hand and those of
the first series of transition elements on the other hand will be discussed with respect to
• (i). Atomic and ionic radii

• (ii) Oxidation state

• (iii). Magnetic properties

• (iv). formation of metal-metal bond

• (v) Ligand-donor atoms preference and

• coordination number

2.3.1: Electronic configuration and variable oxidation states

In yttrium 4d-subshell begins filling, its valence shell configuration being 4d15s2. The filling of 4d-subshell
continues as we move along the series towards the last element Cd which has 4d105s2 valence shell
configuration. There are observed pronounced irregularities in the valence shell configuration of these
elements which have the general valence shell configuration 4d1-10 5s1-2 except for the last three elements
viz Pd, Ag and Cd which have completely fiiled 4d-subshell (4d10) all have incomplete d-subshells.
Y,Zr, Tc and Cd have two electrons in 5s-subshell(5s2) but incomplete d- subshell but Nb, Mo, Ru, Rh and
Ag have only one electron i.e 5s1 in the last shell and Pd does not have any5s-electron(5so). The
anomalous valence shell configuration of Pd-4d105s0 is due to the shifting of both 5s-electrons to 4d-
subshell sothat it has completely filled state 4d10 and become stable though no satisfactory explanation is
available for this shifting.
For the elements which have partly filled 4d-subshell, but still have one electron in 5s –subshell(5s1), the
anomalous behavior has not been explained with effective reasoning, only it is said that for these elements
the nuclear-electron and electron-electron interactions play a significant role for this behavior.
In Mo(4d5) and Ag(4d10), one electron is said to have shifted from 5s to 4d subshell to make the atoms of
these elements extra stable due to exchange energy effect as has been given earlier for Cr and Cu
elements of 3d-transtion series.
Like the elements of first transition series(3d), the elements of this series also exists in various oxidation
states in their compounds. This is because of the availability of several electrons in 4d and 5s subshells
whose energies are fairly close to each other. Hence under different experimental conditions different
number of electrons can be used from both the subshells for bonding
It has been observed that that for second transition series the higher oxidation states become more stable.
This can be illustrated by taking Fe and its next higher analogue, Ru. Fe shows +2 and +3 stable oxidation

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states and +4 and +6 unstable states but Ru has +2, +3, +4 and +6 as stable oxidation states while +5, +7
and +8 are unstable states for this element.
The first element Y(+3) and the last element Cd(+2) exhibit only one oxidation state(though scandium in 3d
transition series has also been assigned a very uncommon oxidation state of +2) because of the stable
valence shell configuration of the ions viz Y3+ [Kr]4d05s0 and Cd2+ [Kr]4d105s0. All the other elements
show a variety of oxidation states, both stable and unstable, the variability being the maximum towards the
middle of the series as with 1st Row elements.
Ru lying almost in the middle of the series, exhibits maximum number of oxidation states (i.e +7) among all
the elements of the series, including the unstable ones, ranging from +2 to +8 .Up to Ru, the the next
higher member of Fe group, the highest oxidation state is equal to the group number eg Sc +3 and Zr +4
Nb: +5 Mo +6 Tc +7 and Ru +8 but the later members of the series don’t follow this trend. The lowest
oxidation state is +1 only for Ag, the next congener of Cu. For Ru, Pd and Cd, the loweststate is +2 and +3
is the lowest state for the other members of the series as shown below
Element Y Zr Nb Mo Tc Ru Rh Pd Ag Cd
Group 3 4 5 6 7 8 9 10 11 12
number
Lowest +3 +3 +3 +3 +4 +2 +3 +2 +1 +2
oxidation
state
Highest +3 +4 +5 +6 +7 +8 +6 +6 +3 +2
oxidation
state

Thus the electronic structure of the atoms of the second row transition elements does not follow the pattern
of the elements of the first transition series and also among the 4d series elements, the higher oxidation
state become more stable.
2.3.2 Complex formation tendency
The availability of various oxidation states facilities the complex formation tendency. The complex formation
tendency is found in the elements of second transition series also though it is less pronounced. These
metals a re weakly electropositive and do not form stable complexes with wide range of ligands as is found
incase of first transition series elements. These elements form stable complexes with P, S and heavier
halogens as donor atoms in the ligands in contrary to the elements in the 3d series. They also form pi
complexes with CO as ligands. The 4d series show the common as well as the unusual coordination
numbers in their complexes which may be 4,6 and even more than six Examples.
Yttrium forms complexes readily wit NCS, acac, EDTA etc viz [Y(NCS)6]3+, [Y(acac)3.H2O]
[Y(EDTA)]. Its complexes with CN 8 are also known
Zirconium usually gives halo complexes of the type [ZrX6]2- and [ZrX7] (X= halide ions), [Zr(acac)4],
[Zr(C2O4)4]4- , [Zr(bipy)3] and also [Zr2F13]5- and [ZrCl4]3(POCl3)2
Niobium form clusters eg [Nb6X12]n+ where n = 2, 3 or 4, [Nb6X15] and [Nb6X16] etc

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Molybdenum forms a variety of complexes having Mo in different oxidation states and coordination
numbers eg [Mo2Cl8]4-, [Mo2Cl9]3-, [MoCl6]2-, [Mo(CO)5]2-, [Mo(CO)6], [Mo(CN)8]4-, [MoS2CNMe2]
Ruthenium forms variety of complexes both with normal and π ligands such as N2, CO etc For example
[Ru(NH3)5N2], [Ru(NH3)6]3+ [Ru(CO)5] [ Ru3(CO)12]. The first complex further gives polynuclear complex
[(H3N)5RuN2Ru(NH3)5]4+ + H2O (N2 is a weak π ligand
Technetium also forms many complexes though not as many as are formed by managanese and rhenium
for example [Tc(CO)4]3-, [Tc2(CO)10] [ Tc(CO)5], Tc (CN)7]4-, [Tc(NCS)6]- [ TcH9]-
The complexes of Rh, Pd and cd are as follows
[Rh(CO)4], [Rh4(CO)12], [Rh6(CO)16] [Pd(NH3)2Cl2], [Pd(NH3)4]2+, [Cd(CN)4]2- [Cd(NH3)4]2+ and [Pd(NH3)6]2+
2.3.3 Magnetic Properties
The elements of the second row transition metals exhibit paramagnetism due, obviously to the presence of
u.p.e in elemental or ionic forms. It has been observed that the magnetic moment a measure of magnetism
in the substances, increases with the number of upe. The relationship is called spin only formula bcos only
spin contribution towards the total magnetic moment is considered and orbital is regarded as quenched.
However if the orbital contribution is also considered inits full capacity to the total magnetic moment of the
substance can be calculated by the formula
µeff= √ {4 S (S+1)+L(L+1)}
Where S is the resultant spin angular momentum and L is the resultant orbital angular momentum.
In the ions/compounds/complexes of the second transition series elements, the spin only formula is used to
calculate the number of u.p.e from µeff
2.3.4 Formation Of Coloured Compounds
The elements of the second transition series also form coloured ions/compounds /complexes whether in
solid orin solution state, due to usual reasons as we have seen for the first row elements as well as for
general d-block elements. The cations having vacant or completely filled d-orbitals are colourless 4d0 and
4d10. Cations with partly filled d – orbitals are coloured.i. e 4d1-4d9. In addition to the presence of upe in d-
subshells or incomplete d-subshell, the nature of atoms (in compounds) or ligands(in the complexes)
attached to the central metal ion determines the coulour of the compounds as a whole.
As explained earlier, the colour in the substances is developed due to the movement of electrons from one
d-orbital to another under the influence of of visible light falling on the substance. The colour is intense if
the transition is allowed but becomes dull if the transition is forbidden. If inplace of interorbital transition,
interatomic transitions take place, intense colours are produced bcos such transitions are not affected by
the selection rules thereby allowing free transitions of electrons.

2.3.5 Catalytic Activity

Like the elements of the first transition series (3-d) those of second transition series also show catalytic
activity, some of them being very important and useful as catalysts in a variety of reactions of industrial
importance.This is because these are capable of forming intermediate products with the reactants or have

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active centres on their surface in the activated state which can activate the reactants for the desired
reaction
Examples
i. Pd is used in the hydrogenation of phenol to cyclohexanol
ii. Pd/Pt catalyses the hydrogenation of unsaturated hydrocarbons
iii. Mo is used as a promoter in the manufacture of ammonia by Haber process
iv. Pt/Rh is used as a catalyst in the oxidation of NH3 to NO in the manufacture of HNO3

2.3.6 Formation of Interstitial and non stoichiometric Compounds

The metals of the second series in general form interstitial compounds with small non –metallic elements
such as H, N, C etc. The lattice of these metals is capable of accomodaing these small atoms with no
change in the lattice structure. Examples are PdH0.6, ZrH1.98 ZrC NbC,MoC Mo2C, ZrN, NbN, Mo2N etc.
These compounds have conductivity properties and are hard behaving as alloys.
These elements also form non-stoichimetric compounds which often exhibit semiconductivity, flouresec ne
and have centres of colour. Above examples of PdH and ZrH2 also furnish the examples of non-
stoichimetrry. Apparently the molecular formulal of these compounds does not correspond to M:H ratio of
1:1 and 1:2. Actually, the M: H ratio in these compounds is 1:0.6 and 1: 1.98 respectively.
2.3.7 Metallic Character and Alloy Formation
All the metals of the second transition series are metals which are hard, some of them malleable and
ductile(e.g Ag), fairly good conductors of heat and electricity. They crystallize in one of the following lattice
structures, body centered cubic(bcc), face centred cubic(fCC) or hexagonalclose packing (hcp)
The elements of this series also form alloys though to the lesser extent than the elements of the first
transition for reasons given earlier . These alloys are harder and have higher melting points than parent
metals . They are also corrosion resistant/proof. These metals are less important than those of the first and
third transition series
2.3.8 Periodic Properties and Their Variation along the series
(i). Atomic radii, Atomic Volumes and ionic radii
The atomic radii of 4d elements though not known with certainty, decrease from Y to Rh , the next cogner
of Co and increase thereafter up to the last element , Cd. The values are very close from Mo to Pd
because of the increased screening effect of the 4d electrons which more or less counter balance the
nuclear pull exerted on the 5s electrons. Then the screening effect becomes more and more pronounced
thereby decreasing the attractive force between the nucleus and the outer electrons. As a result the atomic
radii of Ag and Cd are increased .Cd has the second highes atomic radius which is only lower than that for
Y.This is shown in table below
Metal Y Zr Nb Mo Tc Ru Rh Pd Ag Cd
atoms
Atomic 162 145 134 130 127 125 125 128 134 148
radii(pm)

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The atomic volumes of the elements which are dependent on atomic radii show the same trend in their
variation. The atomic volumes are shown below
Metal atoms Y Zr Nb Mo Tc Ru Rh Pd Ag Cd
Atomic 19.8 14.0 10.8 9.4 - 8.3 8.3 8.9 10.3 13.0
volume(cm ) 3

For Tc its value has been calculated but its not known with certainity. The values decrease from the first
element Y upto Rh and then increase due to the obvious reason, i.e increase atomic raii value
The ionic radii of these elements follow the same trend as the atomic radii. These elements form ions of
variety of oxidation states but only those ions may be considered which bear the same charge as the radii
of the ions with the same charge generally go on decreasing as we move across the series except only for
the last element. For various ions, the ionic radii are shown below.
Bivalent Y3+ Zr4+ Nb3+ Mo4+ Tc4+ Ru3+ Rh3+ Pd2+ Ag+ Cd2+
ions
Ionic 104 86 70 79 - 81 80 80 123 97
radii(pm)

As shown above , ionic radii values are showing an irregular trend particularly for the later elements
(ii). Melting and Boiling Points
The MP and the BP of these elements are generally very high and almost similar to those of the elements
of the first transition series except for a few elements which have very high values eg Nb to Ru have
irregular trend as shown below
Elements Y Zr Nb Mo Tc Ru Rh Pd Ag Cd
MP oC 1490 1860 2415 2620 2200 2450 1970 1550 960 321

The highest MP is for Mo followed by Ru and other elements have comparable values of MP. Cd has the
lowest value. These element have very high BP greater than 22000C except for Cd (7650C)
(iii) Ionization Energies and Reactivity
The first IE values for 4d elements generally increase from the first element to the last one with a marked
drop in the value for Ag.
Element Y Zr Nb Mo Tc Ru Rh Pd Ag Cd
s
1st IE 636 669 664 694 698 724 745 803 732 866

These high values of 1st IE may be correlated with the values of atomic radii which generally decrease
along the series and the screening effect increases, therefore accordingly have higher values. For Ag low
value is attributed to slightly higher atomic radii and availability of of single 5s electrons. Appreciably higher
values of IE for Cd is due to the stability associated with the filled 4d and 5s subshell 4d105s2
(iv). Standard Electrode potentials and Reducing Properties

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As is well known that the standard electrode potential(reduction) is related with the reducing properties of
the elements, in general. Metals with negative values of standard electrode potentials as compared to the
standard hydrogen potential for which E0 is zero acts as reducing agents. Such metals can displae
hydrogen gas from dilute acids. For metals with –ve E0 values but not reacting with acids, some other
factors also play an important role such as formation of a protective coating on the metal surface and
making it unreactive. Strong reducing properties of metals make them displace other metal ions from their
solutions. Though standard electrode potentials values are only available for a few elements of this series,
these are given below
Cd2+ + 2e Cd, E0 = -0.40V ( can evolve H2 from dilute acids)
Ag+ + e Ag, E0 = + 0.80 (does not react with dilute acids
From the above it can be concluded that Cd2+ ions can give up the electrons and act as reducing agents
while Ag+ ions do not give the electrons, rather take up electrons easily. Hence act as oxidizing agents
when react with reducing ions eg
Zn + 2Ag+ Zn2+ + 2Ag
SPECTRAL PROPERTIES AND STEREOCHEMISTRY OF THE ELEMENTS OF THE SECOND
TRANSITION SERIES.
The electronic spectra of the complexes of the second and third series are less important than those of the
first transition series. However, it is important to remind ourselves about this phenomena.
Electromagnetic radiation of white light such as sunlight consists of a continuous spectrum of wavelengths
corresponding to different colours. If such light falls on a compound, the light -matter interaction results in
the absorption of either all the radiation giving black colour to the compound or that of one radiation of a
particular colour. In the latter case, the light of different colour is transmitted or reflected which is the
complimentary colour of the absorbed colour and is the colour of the compound. If the compound does not
absorb in the visible region, it appears white
The transition metal ions/complexes show a variety of colours depending on the nature of the metals and
ligands. The colour of the compound arises due to the transition of electrons from the ground state(lowest
energy) to the excited state(higher energy). When a photon having energy equal to the difference between
two states i.e ground aand excited states, strikes a compound or the ion, electronic transition (here
promotion) takes place. In the complexes of the transition metals, this transition occurs from t2g to eg levels
in octahedral field and from e to t2 level in tetrahedral ligand environment.
The energy difference between the two states involved in electronic transitions is given by the following
∆E = E2- E1 = hυ = hc/ λ
Where ∆E = energy, h = Planck's constant = c = velocity of light, λ wavelengthof light absorbed, υ
frequency of light absorbed
E2 Excited state

hυ (light absorption)

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 E1 Ground state

The colour of the compound/complex exhibited due to the above transition is called the colour due to d-d
transition. Greater ∆E, the more energy is required to cause d-d transition .For 4d-series elements,
increasing value in an octahedral field is Mo3+< Rh3+< Ru3+< Pd4+
The other type of electronic transitions which are responsible for the colour of the ions particularly of the 2nd
transition series are the charge transfer process. from the metal to ligands or ligands to metal. However,
the electronic spectra of the complexes of the second and third series are less important than those of the
first transition series because in the former case the d-d and CT bands cannot be separated but this is
possible in the later case.In the compounds of the heavier elements of the 4d series, because of the larger
magnitude of crystal field splitting energy, the d-d bands are found in the lower wavelengths and hence
overlap with the CTbands.
The charge transfer process is similar to the internal redox process because electron transfer takes place
during the process from metal to ligand or ligand to metal within a complex compound. Thus it is possible to
classify and rank the metal ions according to their oxidizing power of the metal ion thus Rh4+> Ru4+>
Pd2+>Rh3+ Greater the oxidizing power of the metal ion and also greater the reducing power of the metal ion
lower the energy at which the CT bands appear. In the compounds of the heavier elements of the 4d
series, because of the larger magnitude of crystal field splitting energy, the d-d bands are found in the lower
wavelengths and hence overlap with the CT bands.
CT transactions are Larporte and spin allowed unlike d-d transitions i.e ∆l = ±1 and ∆s = 0 because in
these transitions there occurs a transition of electrons between the orbitals of different atoms viz metal and
ligands . This gives rise to more intense or strong absorptions. When these transitions occur in visible
region, the compound shows intense colour. CT Transitions are of 4 types
i. Ligand to metal transition

ii. Metal to ligand transitions

iii. Intervalence or metal to metal transition

iv. Intraligand charge transfer

Among the oxo ions of 4d series elements, the decreasing order of energy of ligands to metal charge
transfer is as follows: NbO43-> MoO42->TcO4-
But the energy of charge transfers increases for the similar ions of 5d-series elements. For the above ions
>The energy difference between 2p-orbitals of oxide ion and 4d-orbitals of the metal ions is very large lying
in UV region and hence these ions are colourless. An example of metal to metal intervalence charge
transfer is the complex Ru-Complex shown below.

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Or [(NH3)5Ru(II) – pyz-Ru(NH3)]5+where the bridging ligand is pyrazine group. In this complex electronic
occurs from Ru(II) to Ru(III) through pyrazine bringing ligand and gives intense colour e.g the compounds
wwith The compounds with M-M bonds also give intense colour eg [Mo2Cl8]4+ is red in colour. Also the metal
carbonyls with M-Mbonds are often intensely coloured (polycarbonyls)
COMPARATIVE STUDY OF THE ELEMENTS OF THE SECOND TRANSITION SERIES AND THOSE OF
THE FIRST.TRANSITION SERIES.
(a). Oxidation States
The elements of both the transition series exhibit variable oxidation states. Some of them are common and
the others uncommon or unfamiliar oxidation states. For the first transition series generally the lower
oxidation states (+2, +3) are most stable while the higher oxidation states are less stable. That’s why their
compounds in the higher oxidation states are less stable and more reactive e.g Cr2O72- (Cr in +6 oxidation
state) and MnO4- (Mn in +7 oxidation state) are strong oxidizing agent and in their reactions get reduced to
Cr3+ and Mn2+ which are stable respectively. Generally, we can say the lower oxidation states +2 and +3
dominaate the chemistry of the 1st transition series e.g Co2+ is quite stable in aqueous medium as well as
Co3+ in [Co(NH3)6]3+ is highly stable. On the other hand Rh3+ion, the next heavy congener of Co is hardly
known. Similarly, no such ammonia complex of Rh3+ is known as is formed by Co3+ ion with NH3
For the elements of second transition series, lower (+2 and +3) oxidation states are of relatively little
importance but the higher oxidation states (eg +5, +6 and +7) are stable and important. For example, in
manganese group, Mn2+ ion is stable while Tc2+ ion is unstable. Tc3+ occurs in some π complexes and
clusters only. In group six, Cr3+ forms a large number of compounds and complexes, while Mo3+ forms only
a few. Cr6+ ions are less stable as discussed above, but Mo6+ ions are highly stable. [MoO4]2- is not easily
reduced. In group 7 again [MnO4]- is unstable but [TcO4]- is stable and very weak oxidizing agent. Similarly,
FeO4, CrCl6 and NiF6 are not known, while RuO4, MoCl6 etc are quite stable. The highest oxidation state for
3d-series elements is +7(in MnO4- but for 4d series members it is +8 (in RuO4)
(b). Ionic Radii
In terms of the ionic radii, it has been observed that the radii of 3d series elements are smaller than those
of the 4d series elements. The comparative table of ionic radii of the elements of the two series is given
below
Ions Sc3+ Ti4+ Cr4+ Zn2+
Radii (pm) 81 75 68 74

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Ions Y3+ Zr4+ Mo4+ Cd2+
Radii (pm) 104 86 79 97
This is due to the changes in the value of n from 3 to 4
(c). Magnetic Behaviour
It has been observed that the magnetic properties of 3d series could be easily be interpreted and the
magnetic moment of their ions / atoms or compiunds can be frepresented by the spin only formular which
give the idea of the number of unpaired electrons in them. From this the geometry of the complexes of
these elements could be explained.
But the magnetic behavior of the second transition elements is more complex and difficult to use the spin
only formula to get the number of u.p.e or the magnetic moment because the orbital contribution could not
be ignored outrightly for the compounds/complexes of these elements
This is bcos 4d –orbtals are too much spread out in space and as a result the interelectronic repulsions in
these are much less as compared to first transition series orbitals. A given set of ligands produces very
large crystal field splitting energy in 4d orbitals than in 3d orbitals. Therefore, heavier elements of this
series will tend to give low spin or inner orbital complexes as compared to those of first series which form
mainly high spin (outer) orbital complexes.
3.0. CHEMISTRY OF THE ELEMENTS OF THIRD TRANSITION SERIES
Introduction
The third transition series contains 10 elements and starts from Lanthanum (La, Z = 57), the element of
group 3 with 5d16s2 valence shell configuration. The next element of the series is hafnium (Hf, Z= 72) the
element of group 4 with 5d26s2 configuration in the valence shell. In between these two d block elements,
there are a series of 14 elements from (from Z= 58 – Z=71) which are called lanthanides because they
succeed La and are closely related to it. These 14 elements are also known as elements of 4f series. Thus
5d series elements La precedes and Hf succeeds the lanthanides. After Hf the filling of the 5d subshell
continues in tantalum (Ta, Z = 73), tungsten (W, Z= 74), rhenium (Re, Z = 75), osmium (Os Z = 76), iridium
(Ir, Z = 77), platinum (Pt, Z = 78), gold (Au, Z = 79) and mercury (Hg, Z = 80), the element of Group 12, with
5d106s2 valence shell configuration.

All the elements of this series have 2 electrons in 6s subshell and 5d subshell is being progressively filled
with 1 to 10 electrons, except Au which has one electron (6s1) due to the shifting of one s- electron to (n-1)d
to completely fill it(exchange energy effect). Because the last or the differentiating electron in the atom of
these elements enters the 5d subshell, the third transition series of elements is also known as the 5d
transition series.
These elements are much more important than those of the second transition series. These elements lie
between barium (Ba, Z = 56), the elements of group 2, and thallium (Tl, Z = 81), the element of group 13,
so the gradual transition of the properties occurs in the period. The elements also exhibit all the
characteristic properties of the d-block elements as happens for those of the first transition and second
transition series.

GENERAL CHARACTERISTICS OF THIRD TRANSITION (5d) SERIES ELEMENTS

3.3.1 Electronic Configuration and Variable Oxidation States

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The elements of this series show a regular trend in the electronic configuration of the valence shell like
those of first series. The general valence shell electronic configuration of these elements is 5d 1-106s1-2. The
last two elements viz gold and mercury have completely filled 5d-subshell i.e 5d 10 whereas all other
elements have 1 to 8 electrons i.e 5d1-8 and in the d –subshell of penultimate shell. As has been given in
the introduction, only Au has 6s1 configuration and all other elements have 6s 2 configuration in the last
shell. In Au exchange energy effect plays an important role to cause the shifting of one 6s electron to 5d
subshell so that it has a stable 5d10 configuration as was the case with Cu and Ag
Like the elements of the first transition series, the elements of this series exist in various oxidation states in
their compounds. i.e the variation of the oxidation states is equally pronounced in the elements of all three
series i.e 3d,4d and 5d. This is due to the availability of several electrons in 5d and 6s subshells whose
energies are fairly close to each other series and under different conditions different numbers of electrons
can be used from both subshells for chemical bonding

Unlike the elements of the first transition series and like the elements of the second series, the higher
oxidation states become more stable and pronounced. The minimum oxidation state varies from +1 to +3
for these elements. In general, La and Hf have +3, elements in the middle have +2 and the last two
elements Au and Hg have +1 minimum oxidation state. Elements up to the middle from the left, have the
highest oxidation state as the group number of the elements but this analogy does not apply to the latter
elements as happens for the second transition series.

Elements La Hf Ta W Re Os Ir Pt Au Hg
Group 3 4 5 6 7 8 9 10 11 12
Number
Lowest +3 +3 +4 +2 +3 +2 +2 +2 +1 +1
oxid sate
Highest +3 +4 +5 +6 +7 +8 +6 +4 +3 +2
oxid state

From the above table, it is clear that the lowest oxidation state is +1 for both Au and Hg and the highest is
+8 for Os

3.3.2. Complex formation Tendency

Most of the elements of this series also have the complex formation tendency though to a lesser extent
because of the weak electropositive nature and non-availability of wide range of ligands. Still some of them
form the complexes with halide, cyanide, NH 3, H2O and π ligands (such as CO). The examples of
complexes are given below.
Hafnium gives complexes of the type [HfCl4.2POCl3],[HfF6], [Hf(acac)4][Hf(C2O4)4] etc.
Ta forms complexes of the type [Ta(CO) 6], [TaCl6], [TaF6] [Ta(S2C6H4)3] and also gives clusters of [Ta 6X12]2+
with halides
Tungsten , like its 3d and 4d analogues chromium and molybdenum forms a large number of complexes eg
[W(CO)6]2-, [W2(CO)10]2-, [W2Cl9]3- [W(CN)8]4- [WF6]-
Rhenium gives various complexes with halides, pyridine and CO in different oxidation states eg [Re2(CO)10],
[ReCl2(Py)2], [Re2Cl8]2- [ReF8]2-,
The complexes of Ir, Pt and Au in different oxidation states with various ligands are given below
[Ir4(CO)12] [IrCl3(H2O)3] [IrCl4(H2O)2] [Ir (C2O4)3]2-

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Pt gives various complexes in two coordination numbers which are related with the oxidation states +2, CN
4 and oxidation state +4 CN 6. For example, [PtCl 4]2- [[Pt(NH3)2Cl2], [PtCl6]2-[Pt(NH3)4Cl2], etc. Similarly, gold
forms complexes such as K[Au(CN)2] (oxidation state +1, coordination number 2), K[AuCl4],( oxidation state
+3,coordination number 4) [AuI2(diars)2]+ (oxidation state +4, coordination number 6) etc

The complex formation in the lower oxidation states by these elements provides an excellent tool for
stabilization of these oxidation states which are otherwise unstable.

3.3.3. Magnetic Properties

As discussed earlier chemical substances may be diamagnetic, paramagnetic or ferromagnetic.
Diamagnetism is inherent in every substance irrespective of the presence or absence of the
paramagnetism and ferromagnetism. s and p block elements always give diamagnetic compounds, the
compounds or the ions of ferrous metals viz iron, cobalt and nickel have ferromagnetism and there is
attraction between these substances and the magnetic fields.Ferromagnetic ions are permanently
magnetized even after their removal from the applied magnetic field. Most of the d block elements either in
the elemental or ionic form (in the compounds/complexes) are paramagnetic and this is due to the
presence of of upe in them. The property of paramagnetism, in particular is expressed in terms of magnetic
moments, expressed by the term µ which has the units of Bohr Magneton, BM. This is related to the
number of unpaired electrons n by the following expression
µs = √ n(n+ 2)BM
Based on this expression the magnetic moments of various substances can be calculated and compared
with those obtained experimentally. It is clear that the substance containing the metal ion with the highest
number of upe will have the maximum magnetic moment
The above formula of µs has been arrived at by taking into consideration only the spin motion off the
electrons assuming that in the compounds /complexes of d- block elements, the orbital motion is quenched
(or suppressed). If the orbital motion of the electrons is also considered and taken into acco. unt, the
formula for µs given by
µeff= √ {4 S (S+1)+L(L+1)}
3.3.4 Formation Of coloured ions/compounds
The anology given for 1st TS and the 2nd TS to exhibit colour also applies to 3 rd TS. In solid state or in
solution, the compounds or complexes are coloured although a few such compiunds are known. The
elements of 5d transition series which have upe only can exhibit colour due to usual reasons as has been
discussed for 3d, 4d TS. The attached aatoms in compounds or ligands in complexes are also responsible
for the type of colour of the compounds because this affect transition of electron within the subshell or
between the subshells. The selection rules for electronic transitions also play an important role in
determining the intensity of the colour of the ions/compounds/complexes. If any of the selection rfule says a
particular transition is not allowed, it occurs due to the breakdown of the selection rule and the intensity of
the colour is low-dull.But if the transition is allowed the intensity of the colour is high-fast. This is why some
compounds are dull coloured but some have very intense colour
3.3.5. Catalytic Activity
The elements of the third TS and their compounds also show the catalytic activity, some of them being very
important and useful catalysts in a variety of reactions used in the industry.
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Examples
1. Pt/PtO is used as Radians catalyst in the oxidation reactions
2. Platinum gauge catalyses the oxidation of NH 3 to NO at high temperature and the process is used
in the manufacture of nitric acid by Ostwalds process.
3. Mixture of Pt and Pd is used as a catalyst in the hydrogenation of unsaturated hydrocarbons
4. Platinised asbestos catalses the reaction between SO 2 and O2 in the manufacture of H2SO4 by
contact process
5. Pt black is used to prepare formaldehyde from methyl alcohol
6. Red hot finely divided Pt is used in the preparation of hydrogen halides from hydrogen and
halogens
7. Finely divided Pt is widely used in many hydrogenation and dehydrogenation reactions
8. Large quantities of platinum are also used in petroleum industry, synthetic fiber industry and glass
industry

3.3.6. Formation of Interstitial and Non-Stoichiometric Compounds

The elements of Third TS also form interstitial compounds with small non-metallic elements such as
hydrogen, carbon and nitrogen. During the formation of these compounds there is no change in
the.lattice structure of the metal because the non-metallic atoms just fit in the voids of the metal lattice
e.g Ta0.78, HfC, TaC WC,W2C, HgN, TaN, W2N.
Many of these compounds are non-stoichimetric type like Ta 0.78. Such compounds are semiconductors
and have semiconductivity properties and centres of colours. The non-stoichiometry is perhaps due to
the defects in the solid structure of Transition elements. The apparent molecular formula shows whole
number ration but actgually its not so
3.3.7.Metallic Character and Alloy Formation
All the elements of this series are metals, most of them being hard. Some of them are malleable and
ductile(eg Au, Pt etc). All the elements of the series are solids exept mercury which among all the d-
elements exist as a liquid at ordinary temperature. They are good conductors of heat and electricity.
These elements also crystalise in one of the close lattice structures as has been given for 3d and 4d
series elements. Apart from Mercury all the elements of this series have high melting points. In all the
three series, it has been found that the metals of the groups 8.9,10 and 11 are softer and more ductile
which can be explained in the light of their crystal structure.
These metals crystalize to form face centered cubic(fcc) lattice type close packed crystal lattice with
large number of planes where deformation can occur, while others crystallize with hexagonal close
packed(hcp) or body centred cubic(bcc) lattice type structure. The hardness of the d-block elements
indicates the presence of covalent bonding. The number of covalent bonds gives the measure of
overall bond-strength and the hardness of the metal. Beccause the unpaired d electrons can take also
take part in the covalent bond formation and their number increases from Group 3to 6 {(n-1)d 5ns1}.
Hence the metallic lattice becomes stronger and then strength decreases progressively.
These metals also form alloys but only a few alloys have been prepared and used because of the rare
nature of these elements. Na-Hg alloys have been used as reducing agents called almalgams. Pt-Ir
alloys have been used to prepare coins, standard weights etc. Pt-Ru and Pt-Cu alloys are also

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important materials. The metals like Pt, Au and Hg are very important the first two Pt&Au aare used in
jewelry. Au is also used as coinage metal and in preparing ornamental vessels.
3.3.8 Periodic Properties and their variation along the Series
i. Atomic Radii, Atomic Volumes and Ionic Radii
The values of atomic radii for these elements have been found to decrease from La to Os, the element
in the middle and then have increasing tendencty up to the element the last Hg. The values are very
close from W to Pt because perhaps of the increased screening effect of the 5d electrons which
neutralizes the nuclear pull extered on the 6s-electrons. Then the screening effect becomes more
effective in the later elements that too are still more prounced in the last element Hg which has atomic
radius only less than that of La and more than that of any element of the series. This trend is shown
below.
Elements La Hf Ta W Re Os Ir Pt Au Hg
Atomic 169 144 134 130 128 126 127 130 136 150
radius
(pm)

The atomic volumes of the elements also have the similar trend as is found for the atomic radii. The
values first decrease in the series up to the middle and then till the last elements. Atomic Volumes of
the se elements are shown below.
Elements La Hf Ta W Re Os Ir Pt Au Hg
Atomic 22.50 13.60 10.90 9.52 8.85 8.44 8.54 9.10 10.22 14.80
volumes
(cm3)

The ionic radii follow almost the same trend as the atomic radii for most of the elements. Ionic radii of
the elements have been found in different oxidation states and the trend along the series can only be
established for the ions having the same oxidation state. Some values are given below
Elements La Hf Ta W Re Os Ir Pt Au Hg
Ionic 117 85 70 80 72 77 82 77 85 106
radius
(pm)

It has been observed that the ionic radii of the cations of different elements in the same oxidation state
generally decrease with the increasing nuclear charge or the atomic number. The ionic radii of the
elements of the third transition series are almost the same as those of the corresponding cations
derived from the elements of the second transition series. The similarity in their ionic radii is due to the
presence of the fourteen lanthanides between La and Hf.
(ii). Melting and Boiling Points
The MP and BP of these elements are very high except for mercury, a liquid in physical state with very
low MP or freezing point (-38.4 0C. Thee values for these elements are given below

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 Elements La Hf Ta W Re Os Ir Pt Au Hg
MP 0C 920 2222 2996 3410 3180 2700 2454 1769 1063 -38.4

From the list it is very clear that Hf, Ta, W Re, Os and Ir have very high MP in comparison to La, Pt, Au
and mercury. The BP of these elements are above 30000C leaving aside Hg which has low BP of
3570C

(iii) Ionization Energies and Reactivity

The first IE values of these elements increase gradually as we move from left to right in the series from
La to Hg. These values are given below.
Elements La Hf Ta W Re Os Ir Pt Au Hg
1st IE 538 684 761 770 760 840 880 870 890 1008
kJ/Mole

If compared with the 1st IEs of the elements of the second series, it can be observed that Y has higher
value than La(both elements are in Group3) due to its smaller size. From Hf to Hg, These elements have
higher values of first IE than those of the elements of the second TS. This is attributed to the increased
nuclear charge in the elements of this series though the atomic sizes of the elements viz the 4d and 5d
series do not vary much. Thus higher nuclear charge causes strong inward pull on the outer electrons
which are therefore strongly held with the nuclei and their removal becomes difficult. This ultimately results
in the higher values of the first IEs for the theses elements . Hg has exceptionally high value of 1 st IE
because more energy is required to remove an electron from the stable 5d 106s2 configuration of this
element
Due to high IEs and other factors discussed in section 1.3 above these elements show low reactivity such
that some of these elements viz Ir, Pt, Au etc are known as noble metals due to their passive nature
towards the chemical reactions with other elements and reagents.
Standard Electrode Potentials and Reducing Properties
These two terms, the standard electrode potential(reduction) and the reducing properties of the elements
are intimately related with each other.For 3d- and 4d- transition series elements examples have been
given earlier and it has been stated that metals with negative E 0 values of standard electrode potentials as
compared to standard hydrogen electrode for which E0 value is taken as zero act as reducing agents.
Such metals can displace hydrogen gas from dilute acids as well as other metals from their solutions.
However, there are other metals particularly some d-block elements which have positive Standard
reduction electrode potential with the tendency to get reduced by H 2 or the metals with negatgive standard
electrode potentials values. Cu & Ag are such metals belonging to 3d and 4d transition series.
Among the 5d transition elements such as Pt, Au and Hg provide excellent examples of such metals as
shown below.

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Au++ e Au Eo = + 1.68V
Au3+ +3e Au Eo = + 1.42V
Pt2++ 2e Pt Eo = +1.20V
Hg2+ + 2e Hg Eo = + 0.85V

The above metals may thus act as oxidizing agents and have a tendency to take up the electrons. They
hardly provide electrons for reduction

COMPARATIVE STUDY OF THE ELEMENTS OF THE THIRD TRANSITION SERIES AND THE FIRST
TRANSITION SERIES.

i. Oxidation States
The elements of both transition series exhibit variable oxidation states including both common and
uncommon oxidation states.
The lower oxidation states are most stable and their chemistry is more pronounced for the elements of first
transition (3d) series while their higher oxidation states are less stable. This fact can be exemplified by
taking the strong oxidizing nature of the dichromate (Cr2O72-, oxidation state of chromium = +6) and
permanganate (MnO4-, oxidation state of Mn = +7) ions. These ions under suitable conditions take part in
redox reactions and get reduced to Cr(III) and Mn(II) states which are stable.

Lower oxidation states are of relatively little importance for most of the elements of the third TS. For
example the Ir2+ ion (5d) is hardly known but the 3d analogue Co 2+ is quite stable in aqueous media.
Similarly Ir3+ ion does not form complexes with NH 3 molecules while [Co(NH3)6]3+ is highly stable in
aqueous medium. In Manganese group(Group 7) Mn2+ is stable, Re2+ ion (5d) is unstable and occurs only in
some complexes with π - ligands and metal clusters . Similarly Cr 3+ (3d) form a large number of complexes
and other normal compounds, W3+ ion (5d) forms only a few complexes.

The higher oxidation state is generally more stable for the elements of the third series than for the element
of the first TS. For example OsO4, WCl6, PtF6 etc are quite stable while FeO4, CrCl6, NiF6 etc are not known.
Also WO42- ion is highly stable and is not reduced easily whereas CrO 42- is strong oxidizing agent and is
readily reduced to +3 states. Similarly, MnO4- is a strong oxidizing agent but ReO4- is stable and very weak
oxidizing agent. The highest oxidation state for 5d TS is +8 in OsO 4 while that for the 3d TS element is +7
in MnO4- ions

ii. Ionic Radii

The ionic radii of 3d series elements are smaller than those of the 5d-series elements but there is only a
small difference between the radii of the ions of 4d and 5d-series elements, Thus 3d<4d<5d.. This
comparison shown below.

Ions Sc3+ Ti4+ Cr4+ Zn2+

Radii(pm) 81 75 68 74

Ions La3+ Hf4+ W4+ Hg2+

Radii(pm) 81 75 68 74
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Note (i). The change in the values after lanthanides is small because of the lanthanide contraction.
(ii). The second and the third members of each group of transition elements have very similar atomic
radii due to lanthanide contraction which arises due to poor shielding effect of 4f electrons

(iii) Magnetic Behaviour

As seen before, the magnetic moments or magnetic behavior of ions/atoms or compounds of elements of
the third TS is more complex and difficult to explain by using spin only formula. Thus the calculated
magnetic moment can’t predict the number of upe. This is because the 5d orbitals are too much
diffused or spread out in space and hence the inter electronic repulsions in these are much less in
comparison to 3d orbitals. Hence a given set of ligands produces very large Crystal field splitting
energies in 5d orbitals than in 3d orbitals. The heavier elements of this series will therefore give low spin
complexes as compared to those of 3d series which generally form high spin complexes. However, the
magnetic moments of the ions/atoms or compounds of the first transition series can be represented by the
spin only formula. Thus the calculated magnetic moment gives the number of upe in them as well as the of
geometry of the complexes of these metals can be predicted which is not the case with 5d series `

3.5 SPECTRAL PROPERTIES OF THIRD TRANSITION SERIES ELEMENTS

Most of the complexes of TS are highly coloured because the metal ions are capable of absorbing radiant
energy in the visible region of the electromagnetic spectrum causing d-d transitions. (see earlier notes on
1st and 2nd TS for details of the reasons for absorption of light}
It has been observed that d-d transitions (electronic )spectra) of the third row TS are less important than
those of the 3d series because more energy is required to cause d-d transitions due to greater value of ∆,
the crystal field splitting energy. In Octahedral ligand field, the increasing ∆o is as follows Ir 3+< Re4+<Pt4+
etc

The other type of electronic transition which is encountered in the complexes of the 3 rd TS and responsible
for their intense colours are the charge transfer spectra) in which electronic transition occurs from metal to
ligand or ligand to metal preferably the latter. Sometimes the M-M transition is also observed is in some
polynuclear complexes. In the compounds/complexes of the heavier elements of the 5d series, because of
the larger magnitude of ∆o, the d-d bands are found at lower wavelengths or higher frequency and hence
overlap with the charge transfer bands. Charge transfer reflects the internal redox tendencies of both the
central metal atom/ion and ligands. Thus it is possible to classify and rank metal ions according to the
oxidizing power Os4+> Re4+ = Os3+ , Pt4+> Pt2+.= Ir3+
Greater the oxidizing power of the metal ion and also greater the reducing power of the ligand, lower the
energy at which the CT (L M) bands appear. The compounds with M-M bonds also give intense colours

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eg(Re2Cl8]2- is royal blue. The metal carbonyls of these elements with M-M bonds are often intensely
coloured
Because the d-d transitions are spin forbidden and Larporte forbidden, the breakdown of the selection rules
gives light colours to the complexes, but CT transitions give rise to strong absorptions and when these
transitions occur in visible regions, the complex/compound shows intense colour. This is because CT
transitions are both spin and Larporte allowed.

COMPARATIVE STUDY OF THE ELEMENTS OF THE FIRST AND SECOND &THIRD TRANSITION
SERIES.
The main differences between the second and third series of transition elements on one hand and those of the first
series of transition elements on the other hand may be discussed with respect to

• (i). Atomic and ionic radii

• (ii) Oxidation state

• (iii). Magnetic properties

• (iv). formation of metal-metal bond

• (v) Ligand-donor atoms preference and stereochemistry

(i). Atomic/ ionic radii

Atomic and ionic radii of first row transition elements gradually decrease from left to right because of the
increase in nuclear charge. The atomic and ionic radii of 2nd and 3rd row transition elements are almost
identical because of lanthanide contraction. However note that there is normal increase in atomic and ionic
radii between the 2nd and the 3rd row transition elements as one goes down the group.
(ii). Oxidation state
Heavier transition metals of the second and third rows exhibit higher oxidation states as the most stable
states. Higher oxidation states in first row transition elements are unstable and are strongly oxidizing .
Mo6+ and W6+ are stable while Cr6+ is unstable and strongly oxidizing.

(iii). Formation of metal-metal bonds

The second and third row transition elements favour formation of metal –metal bonds when compared to
first row transition elements This is because of the large d orbitals which allow good metal-metal overlap.
Furthermore, the 4d and 5d orbitals are more diffuse relative to the nucleus than the 3d orbitals which make
them overlap maximumly during the metal-metal bond formation
The second and third row transition elements favour formation of metal –metal bonds when compared to
first row transition elements This is because of the large d orbitals which allow good metal-metal overlap.
Furthermore, the 4d and 5d orbitals are more diffuse relative to the nucleus than the 3d orbitals which make
them overlap maximumly during the metal-metal bond formation

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(iv). Magnetic properties
The second and third row transition metals tend to give low spin complexes because of the greater splitting
of the d orbitals by the ligands therefore, ions with an even number of electrons are usually diamagnetic√ .
Even where there is an odd number of electrons, there is only one u.p.e. This tendency to form low spin
complexes complicates interpretation of magnetic moments that are usually possible for the first row
paramagnetic species
Furthermore 2nd and 3rd row transition metals paramagnetic complexes usually have magnetic moments
which differ considerably from spin-only values because of spin –orbit coupling. This once again
complicates interpretation of their magnetic moments.
(v). Ligand –donor atom preference and stereochemistry
Since 2nd and 3rd row transition metals have stable high oxidation states, they act as hard acids and prefer
hard bases such as oxygen and fluoride ions during the formation of complexes. 1st row transition elements
form complexes with many common ligands with common donor atoms.
The elements of second and third transition elements are larger than the elements of the first transition
series and they show higher coordination number
For the early members of 2nd and 3rd row transition metals, higher coordination numbers of 7 and 8 are
more common than in the first row elements
CHEMISTRY OF THE SCANDIUM GROUP AND THE LANTHANIDE ELEMENTS
f Block Elements in Modern Periodic Table
The ‘f’ – block elements are also collectively known as inner transition metals or rare earth. They occur
in period 6 and 7 in the periodic table. There are two distinct series of these metals:
(i). The lanthanides constitute distinct series of 14 elements in the periodic table that follow lanthanum. i.e
elements from cerium(Z = 58) to letitium(Z=71).They are so called because these elements succeed
lanthanum(La, Z=57).
(ii).The actinides constitute the other series of 14 elements following actinium i.e elements from
thorium(Z= 90) to Lawrencium (Z = 103).They are so called because these elements succeed actinium(Ac,
Z=89)
The General electronic configuration of f – block elements is (n–2) f1–14(n–1) d0–1ns2. In the case of
Lanthanides, the electronic configuration is [Xe]4f1–145d0–16s2 while in the case of Actinides it is [Rn]5f1–146d0–
7s
1 2

In these elements, the last electron (differentiating electron) usually enters the penultimate i.e. (n – 2) f of
the orbital.
In lanthanides, the differentiating electron enters the 4f orbital. In the case of actinides, the differentiating
electron enters the 5f orbitals.
Why are they called rare earth elements ?
They are called rare because they were once difficult to extract economically, so it was rare to have a pure
sample i.e due to similar chemical properties, it is difficult to separate any one lanthanide from the others.

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However, newer separation methods, such as ion exchange resins similar to those found in home water
softeners, make the separation of these elements easier and more economical.Most ores that contain
these elements have low concentrations of all the rare earth elements mixed together
However, newer separation methods, such as ion exchange resins similar to those found in home water
softeners, make the separation of these elements easier and more economical.
The scandium Group of elements
This group comprises of scandium, yttrium, lanthanum and actinium. They have the outer electronic
configuration (n-1)d1ns2 and are formally part of the d-block elements of the periodic table. However as the
chemistry of these elements is entirely that of +3 oxidation state, which involves the loss of the d electron
and the s electrons, this group is best regarded as forming a transitional region between the s elements
and the main d block elements. Following lanthanum, the third member of the scandium Group, the 4f shell
fills for the next fourteen elements.
Although La and Ac are strictly group 3 metals , the chemical similarity of La to the elements Ce-Lu and of
Ac to Th- Lr means that La is commonly classified with the lanthanides and Ac with actinides..The symbol
Ln is often used to refer generally to the elements La-Lu
Lanthanides share many similar characteristics. These characteristics include the following:
 Similarity in physical properties throughout the series
 Adoption mainly of the +3 oxidation state. Usually found in crystalline compounds)

They can also have an oxidation state of +2 or +4, though some lanthanides are most stable in the
+3 oxidation state.
 The general behavior of the lanthanides are that of +3 oxidation state and are very similar to that of
the scandium group and as such is convenient to include these elements here. Thus all these
elements said to be the members of Group 3 i.e Sc- group and have been allotted one single
position in the periodic table

 In analogy with various series of d-block elements, lanthanide elements are called first inner
transition series elements. All the 14 elements of the series resemble closely in their electronic
configuration and chemical properties with one another as well as with lanthanum which may be
called a prototype of lanthanide elements.

 Adoption of coordination numbers greater than 6 (usually 8-9) in compounds

 Tendency to decreasing coordination number across the series

 A preference for more electronegative elements (such as O or F) binding

 Very small crystal-field effects

 Little dependence on ligands

Properties which demonstrate that f block elements are different from d-block elements

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(i). f block elements have almost identical atomic and ionic sizes due to lanthanide contraction. For d block
elements, atomic/ionic radii decrease gradually from left to right of the periodic table
(ii).f – block elements form limited number of complexes because their common oxidation state is +3. d
block elements form wide range of complexes due to variable oxidation states
(iii).f-block elements are strongly electropositive and readily react with air, water and dilute acids . d block
elements are generally inert towards air, water and dilute acids due to their high ionization energies and low
heat of hydration
(iv).f – block elements have generally large ionic sizes and stable high oxidation states due to their high
electropositive nature. They are hard Lewis acids which readily form complexes especially with oxygen and
polydentate ligands which have oxygen donor atoms . d block elements have moderate ionic sizes and
have stable low oxidation states. They are generally soft acids which readily form complexes with most
ligands
(v)f-block elements form complexes which are ionic in nature. d - block elements form complexes which are
mostly covalent in nature.

Chemistry of the Lanthanides

The Lanthanides consist of the elements in the f-block of period six in the periodic table. While these metals
can be considered transition metals, they have properties that set them apart from the rest of transition
elements.
Abundance
Lanthanides (elements 57–71) are fairly abundant in the earth’s crust, despite their historic characterization
as rare earth elements. Thulium, the rarest naturally occurring lanthanide , is more common in the earth’s
crust than silver (4.5 × 10−5 % versus 0.79 × 10−5 % by mass). There are 17 rare earth elements, consisting
of the 15 lanthanides plus scandium and yttrium.
Electronic configuration
The electronic configuration of the lanthanides have been derived from the electronic spectra of the atoms
of these elements. The technique used is based on the fact that each line in an emission spectrum reveals
the energy change involved in the transition of an electron from one energy level to another. However, the
problem with this technique with respect to the Lanthanide elements is the fact that the 4f and 5d sub-shells
have very similar energy levels, which can make it hard to tell the difference between them. These spectra
have great complexity thereby inferring to some doubt about the configurations of the lanthanides.
Why are the electronic configurations of the lanthanides not known with certainty?
Reasons
(i).The Lanthanide elements have the 4f and 5d sub-shells which have very similar energies. This
makes it hard to tell the difference between these two levels. i.e electrons can easily jump from 4f
to 5d or vice versa
(ii) The outermost 6s-orbital remains filled with two electrons 6s2 for all the elements in the series.

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 (iii) Irregularities arise in electronic configurations depending on the occupancy of the f –orbitals
that would lead to f0,f7 and f14 configurations which are stable .
Another important feature of the Lanthanides is that they have similar electronic configuration and similar
ionic radii hence they have similar chemical and physical properties
Note that the elements occurring after lanthanum do not develop the subcoating 5d (except gadolinium and
lutetium, which possess the electrons 5d1) but all the elements have the subcoating 4f.
Considering lanthanides as f-electron elements, the configuration 4f1-145d0-16s2 can be ascribed to them
The expected and alternative (observed )electronic configurations of the elements are shown below. The
expected configurations have been derived by taking into account the electronic configuration of
Lanthanum and supposing that in all the lanthanide elements succeeding lanthanum, additional electrons
are filled in the 4f-subshell successfully from cerium to lutetium.
Thus the 4f-electrons are embedded in the interior of the atom while 5d and 6s electrons are exposed to
the surroundings
Electronic structures of the lanthanum and lanthanides

Element Atomic Expected Alternative

number(Z) Electronic Electronic
Configuration Configuration
Lanthanum(La) 57 [Xe]5d16s2 -
Cerium(Ce) 58 [Xe]4f15d16s2 [Xe]4f26s2
Praseodymium(Pr) 59 [Xe] 4f25d16s2 [Xe]4f36s2
Neodymium(Nd) 60 [Xe] 4f35d16s2 [Xe]4f46s2
Promethium(Pm) 61 [Xe] 4f45d16s2 [Xe]4f56s2
Samarium(Sm) 62 [Xe] 4f55d16s2 [Xe]4f66s2
Europium(Eu) 63 [Xe] 4f65d16s2 [Xe]4f76s2
Gadolinium (Gd) 64 [Xe] 4f75d16s2 [Xe]4f75d16s2
Terbium(Tb) 65 [Xe] 4f85d16s2 [Xe]4f96s2
Dysprosium(Dy) 66 [Xe] 4f95d16s2 [Xe]4f106s2
Holmium(Ho) 67 [Xe] 4f105d16s2 [Xe]4f116s2
Erbium(Er) 68 [Xe] 4f115d16s2 [Xe]4f126s2
Thulium (Tm) 69 [Xe] 4f125d16s2 [Xe]4f136s2
Ytterbium(Yb) 70 [Xe] 4f135d16s2 [Xe]4f146s2
Lutetium(Lu) 71 [Xe] 4f145d16s2 [Xe]4f145d16s2

In a nutshell It is observed that lanthanum, gadolinium and lutetium show different electronic configuration
from other lanthanides for the following reasons
(i).The 5d and the 4f- orbitals are nearly of the same energy and the distinction between the two is difficult.
(ii).Due to the closeness of 5d and 4f orbitals, some extra stability is achieved when the 4f is half filled and
completely filled so the next electron after lanthanum goes in 5d- orbital instead of 4f orbital.

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(iii).5d orbital contains one electron in 5d subshell in case of La, Gd and Lu while it is empty in case of other
lanthanides
(iv).f0, f7 and f14 configurations have extra stability due to empty, half-filled and completely filled f orbitals
respectively
(v). The electron configuration of La, Gd and Lu in +3 oxidation states are as follows La3+ : [Xe]4f0 Gd3+ :

[Xe]4f7 Lu3+ : [Xe]4f14 .The f orbitals in these ions acquire extra stability when it is half filled and
completely filled Hence Gd and Lu exhibit +3 oxidation state. La in +3 oxidation state form noble gas
configuration which is also stable. Thus these elements only exhibit +3 oxidation state
Thus it may be concluded that the general electronic configuration of lanthanide elements could be written
as [Xe](n-2)f1-14(n-1)d0,1ns2 where n is the principal quantum number i.e 6.
The three subshells viz (n-2)f, (n-1)d and ns together form the valence shell of these elements i.e 4f, 5d,
6s= valence shell.
Characteristics of f orbitals
 For an f orbital, the quantum numbers are n = 4 or 5, l = -3,-2,-1, 0, +1, +2, +3(A set of f orbitals is
seven fold degenerate)

 f- Orbitals are ungerade

 The valence shell of a lanthanides element contains 4f orbitals and that of an actinides, 5f atomic
orbitals.

 A crucial difference between the 4f and 5f orbitals is the fact that the 4f orbitals are deeply buried in
the atom and the 4f electrons are not available for covalent bonding. This makes ionization
beyond the M3+ ion energetically unfavaourable and this leads to a characteristic +3 oxidation state
across the whole row from La to Lu

Spectral Properties of Lanthanide

 Properties Associated with the Presence of f Electrons

 The electrons in the f level are too strongly bound by the nucleus to be involved in the chemistry of
the elements except under unusual conditions. In addition, f orbitals appear to be too diffused to
enter into bonding generally so that there are few effects from the presence of f electrons or
unfilled f orbitals

 However there are electronic effects which show up in the spectra and magnetic properties of the
lanthanides.

Oxidation State
 Lanthanide elements are highly electropositive and form essentially ionic compounds. It is
observed for these elements that +3(i.e formation of tripositive ions, Ln3+) is the principal or
common oxidation state exhibited by all of them. This is said to be the most stable oxidation state
of the lanthanides.

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 Some of these elements also show +2 and +4 oxidation states but except a few such ions, they
have the tendency to get converted to +3 states. For example Sm and Ce form Sm2+ and Ce4+ ions
but are easily converted to +3 states. That’s why Sm2+ is a good reducing agent while Ce4+ is a
good oxidizing agent i.e

 Sm2+ Sm3+ + e (electron provider, a reductant)

 Ce4+ + e Ce3+ (an electron acceptor an oxidant)

What does this mean?

 It means Ln2+ and Ln4+ ions are less frequent than Ln3+ ions among the lanthanides.

 +2 and +4 oxidation states are shown by the elements particularly when they lead to

(i). Noble gas electronic configuration e.g Ce4+ (4f0)

(ii). Half-filled f-orbital eg Eu2+ and Tb4+ (4f7) and
(iii) Completely filled f-orbital e.g Yb2+(4f14) in the valence shell
 Among the above +2 and +4 oxidation states, which exist only in aqueous solutions are exemplified
by Sm2+, Eu2+ , Yb2+ and Ce4+

 There are some exceptions also i.e sometimes +2 and +4 oxidation states are also shown by the
elements which are close to f0,f7 and f14 states eg the valence shell configurations of the ions given
below are 4f4, 4f2, 4f3, 4f6 and 4f8

 Ce3+( 4f1) , Ce2+(4f2), Sm2+(4f6), Pr4+(4f1), Pr3+(4f2), Dy2+(4f8), Nd4+(4f2), Tm2+(4f13). No satisfactory
explanation for these exceptions has yet been given. These oxidation states have only been
explained on the basis of thermodynamic and kinetic factors that are too arbitrarily.

 Due to the only one stable oxidation state (i.e +3), lanthanide elements resemble each other much
more than do the transition elements (or the d-block ) elements.

 It has also been observed that the higher oxidation states of the lanthanides are stabilized by
fluoride or oxide ions while the lower oxidation states are favoured by bromide or iodide ions.

 Among the lanthanides, in addition to +3 states, +2 states is shown by Nd, Sm, Eu, Tm and Yb
whereas +4 state is exhibited by Ce, Pr, Nd,Tb and Dy elements. The rest five elements show only
+3 states.

Ionic Radii and Lanthanide Contraction

 Here we consider the ionic radii of tripositive ions (i.e Ln3+) because +3 is the most stable and
common oxidation state of all the lanthanides in general.

 It has been observed that the atomic as well as the ionic radii of lanthanides decrease steadily as
we move from Ce to Lu.The ionic radii are listed below

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 From the above table it is clear that the ionic radii decrease steadily along the series amounting in
all to 18pm.This shrinking in the ionic size of the Ln3+ ions with increasing atomic number is called
lanthanide contraction. The term steadily means the values decrease regularly and with a very
small difference though the nuclear charge increases by +14 units from the first to the last element

 The atomic radii of these elements also decrease from Ce to Lu(Ce: 165pm, Lu:156pm). These
values do not decrease regularly like the ionic radii rather there are some irregularities at Eu and
Yb which have abnormally high atomic radii (Eu: 185pm, Yb:170).

 The atomic radii for the metals are actually the metallic radii which are recorded for the metal
atoms surrounded by 8 to 12 nearest neighbors.(in bulk) various metal atoms in metal crystals are
bonded together by metallic bonding. In Eu and Yb, only two 6s- electrons are generally available
for this purpose. This results in larger atomic volumes for Eu and Yb because of weaker bonding
among atoms. the larger values ultimately give rise to larger size to the atoms of the elements .

Ln3+ Ce3 Pr3+ Nd3+ Pm3 Sm3 Eu3 Gd3 Tb3 Dy3 Ho3+ Er3 Tm3 Yb3+ Lu3+
+ + + + + + + + +

Ionic
Radii 103 101 100 98 96 95 94 92 91 90 89 88 86 85
(pm)

Cause of lanthanide contraction

• As we move along the lanthanide series from Ce to Lu, addition of electrons takes place to the 4f-
orbitals one at an each step. The mutual shielding effect of one 4f-electron by another is very little,
being even smaller than that of one d-electron by another. This is due to the scattered or diffused
shape of the f orbitals. In other words the 4f electrons are not very efficient at shielding the
nuclear charge which becomes more effective along the series.

• However the nuclear charge goes on increasing by one unit at each step(i.e each next element).
Thus the attraction between the nucleus and the outermost shell electrons also goes on increasing
gradually at each step.

 The 4f-electrons are not able to shield effectively the attraction of the nucleus(i.e inward pull) for
the electrons in the outer most shell as the atomic number of the lanthanide elements increases.
This results in the increased inward pull of the outer most electrons by the nucleus, finally causing
the reduction in the atomic or ionic size of these elements. The sum of the successive reductions
gives the total lanthanide contraction It may be concluded that the lanthanide contraction among
the 4f-series elements and their ions takes place due to the poor shielding effect of 4f-electrons
and gradual increase in the nuclear charge.

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 Consequences of Lanthanide Contraction
 Lanthanide contraction plays an important role in determining the chemistry of lanthanides and
that of heavier transition elements series. Some important consequences of lanthanide contraction
are as discussed below.

(i).Basic character of lanthanide hydroxides (Ln(OH)3):

 Because the size of tripositive lanthanide ions (Ln3+)decreases regularly with increasing atomic
number(or nuclear charge), the process being called lanthanide contraction, therefore, the covalent
character between Ln3+ ion and OH- ions increases from La(OH)3 to Lu(OH)3 (Fajans’rules). As a
result of the increase in covalent character of the lanthanide hydroxides from Ce(OH)3 to
Lu(OH)3 ,the basic character of the hydroxides decreases in that order i.e La(OH)3 is the most
basic while Lu(OH)3 is the least basic.

 ii). Difficult in separation of Lanthanide elements

 The lanthanide contraction is an important factor in allowing the separation of lanthanides from one
another. due to the very small change in sizes ,all the Lanthanide elements resemble one another
in chemical and physical properties. Hence it becomes difficult to separate them

(iii). Resemblance between the atomic radii of the second and third transition series
elements
 Lanthanide contraction has a significant effect on the relative properties of the elements which
precede and succeed lanthanides.

 Normally in the same group, the atomic(or covalent) radii increase as the value of n (principal
quantum number) increases due to increased distance between the nucleus and the outermost
shell of the electrons which counterbalances the increased nuclear charge.

 This fact is evident when the values of atomic radii are compared for the elements of the first and
second transition series . On the same analogy, the atomic radii of the elements of the third
transition series should be greater than those of the second transition series. This statement is
valid only for the elements of Group 3 i.e Sc, Y and La in terms of their atomic radii, but when these
values are compared for the elements of 4d and 5d series in the next group viz group 4, 5,
6………….12, it is observed that the values are inexpertly almost equal.

 The similarity in the values of atomic radii for the elements of second and third transition series
attributed to the inclusion of 14 lanthanides between La(Z=57,

 Group 3) and Hf(Z=72, Group 4) of the third transition series which due to lanthanide contraction
cancel the increase in the values of atomic radii

 Due to similarity in the size of the elements of the two series (2nd&3rd), the elements of a particular
Group resemble each other more closely in their properties than do the elements of the 1st and
2ndtransition series.

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 The examples of the pairs of elements which show similar properties and hence are difficult to
separate are Zr-Hf, Nb-Ta, Mo-W , Ru-Os, Rh-Ir, Pd-Pt and Ag-Au

 The atomic radii of the elements of the three transition series are given below.

 Groups 3 4 5 6 7 8 9 10 11 12

Elements of 3d
series Sc Ti V Cr Mn Fe Co Ni Cu Zn
Atomic radii 144 132 122 117 117 117 116 115 117 125
(pm)
Elements of 4d Y Zr Nb Mo Tc Ru Rh Pd Ag Cd
series
Atomic radii 162 145 134 130 127 125 125 128 134 148
(pm)
Elements of 5d La –Ln Hf Ta W Re Os Ir Pt Au Hg
series
Atomic 169 144 134 130 128 126 127 130 136 150
radii(pm)

 From the above table, it is evident that due to Lanthanide contraction, the atomic and ionic radii of
the second and third transition series elements do not differ much though they are appreciably
higher than those of the first transition series .

 It is also observed that the atomic radii of the elements falling immediately after lanthanide series
are closer to those of their 4d-congeners and the effect slowly decreases along the series of 5d-
elements as we move away from it..

Also note
 (i)That properties that depend mainly on atom or ion size eg lattice energies, solvation energies,
complex stability constants are highly the same for corresponding pairs of 4d and 5d metal
compounds.

 (ii). Pairs of 4d and 5d metals often occur naturally together eg Zr and Hf, Nb and Ta) and are
difficult to separate

 Densities of the elements of the three transition series.

 The density and atomic volumes are inversely proportional to each other.

 All the transition metals have low values for their atomic volumes and hence their densities are
high.

 In a given transition series, the atomic volumes of the elements first decrease on proceeding from
left to right and generally attain a minimum value for the elements of group 8,9 10. They then start
increasing further up to group 12. Accordingly the density of the elements increases from left to
right up to the elements of Group 8,9,10 and then decreases up to group 12

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 Down the group, the densities of the elements increase regularly.

 But the striking features that has been observed on moving from the first element to the last
element in every group is that the densities of the elements belonging to second TS are only
slightly higher than those of the corresponding elements of 3d-series while the values for the
element from Hafnium to mercury(5d series) are almost double of those for the elements from Zr
to Cd respectively(4d series). This analogy does not apply to Y(Z=39) and La(Z=57).

 How can this be explained?

 Bcos of Lanthanide contraction, the atomic sizes of the elements of the third transition series after
La(Z=57) i.e from hafnium onwards become very small and as a result, the packing of atoms in
their metallic crystals becomes much compact which results in high densities. Also, there is only a
small difference in the atomic sizes of the elements of the two series viz 4d and 5d series but the
atomic masses of the elements of the 5d-series are almost double to the corresponding elements
of 4d-series. This makes the densities of 5d series elements almost double to those of the
elements of 4d-series.

 Complex Formation by Lanthanides

 The Ln have low charge density due to their large size in spite of having high charge(+3). Hence,
they do not cause much polarization of the ligands and have a weak tendency for complex
formation. This reluctance for complex formation may be attributed mainly to

 (i). Unfavorable electronic configuration on the Ln ions (ii). Larger size which leads to little
attraction for electron rich species.

 Because of the above reasons, only the high energy 5d, 6s and 6p-orbitals are available for
coordination, the 4f-orbitals are been screened and so deeply buried in the atom so that only
strong ligands (usually chelating)coordinating groups can interact. This has consequences that
only a few complexes with unidentate ligands are formed but stable complexes are formed by Ln3+
ions with chelating ligands such as oxygen containing EDTA, β-diketones , citric acid, oxalic acid,
acetyl acetone, oximes nitrogen containing ligands such as en,NCS,etc. The Ln3+ ions do not form
complexes with bonding ligands such as CO, NO, NCR etc at all. The complex forming tendency
and stability of the complexes increases with increasing atomic number. This fact is taken as a
basis to take advantage in their separation from one another.

Ce(IV) complexes are relatively common, an example of a high oxidation state ion seeking
stabilization through complexation. For instance, Nitrate ion (NO3-) which is an ambidentate ligand
can bond to a metal through more than one donor atom. i.e N and O .It bonds to Ce4+ through
oxygen donor atom . Ce4+ being a hard acid and prefers to complex with a hard base such as
oxygen. Six NO3- groups form an approximately octahedral complex of the type shown below

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  The most important class of lanthanide complexes are the anionic type . Complexation with
hydroxycarboxylic acids such as citric and tartaric acid is used in the separation procedures of
lanthanides. The EDTA complexes have achieved importance in the recent years. The coordination
number of lanthanide complexes is usually six

 The lanthanide ions show absorptions in the visible or near uv regions of the spectrum, except La3+
with no f electrons and Lu3+ with no empty f orbitals

 The colours of the lanthanide ions or atoms are due to f-f transitions and as the f orbitals lie deep
enough in the atom to be shielded from much perturbation by the environment, these transitions
appear in the visible and near uv region as sharp bands. This is in contrast to the d-d transitions
found for the transition elements which usually appear as broad bands due to the environmental
effects. A typical lanthanide ion spectrum of holium(Z= 67) is shown below Pg 160 K.M Mackay

 As these bands are so sharp they are very useful for characterizing lanthanides. The position of the
absorption s shift with the f configuration , giving rise to visible colours of different ions

Absorbance

27500 25000 22500 20000 17500

cm-1

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As these bands are so sharp they are very useful for characterizing lanthanides. The position of the
absorptions shift with the f configuration, giving rise to visible colours of different ions
Configuration Example Colour
f1 or f13 Ce(III), Y(III) Absorbs in uv region
f1 or f12 Pr(III), Tm(III) Green
f3 Nd(III) Blue -violet
f4 or f10 Pm(III), Ho(III) Pink or Yellow
f5 or f9 Sm(III), Dy(III) Cream
f6 , f7 or f8 Eu(III), Eu(II), Gd(III), Tb(III) Absorbs in the uv region
f11 Eu(III) Pink

 Note solutions of samarium(II) are red and of ytterbium(II) are green.. The much intense colours of
Ce(IV) compounds are due to charge transfer transitions between the ion and coordinated ligand

Magnetic Properties
• All the f states except f0 and f14 contain unpaired electrons and are therefore paramagnetic. These
elements differ from the d transition elements in that their magnetic moments do not obey the
simple spin-only formula

µ =√¿
• Where µ is the magnetic moment in BM

• In the f elements , the magnetic effect arising from the motion of the electron in its orbital
contributes to the paramagnetism as well as that arising from the electron’s spinning on its axis. In
transition metals the orbital contribution is usually quenched out by the interaction with the electric
field of the environment- but the f levels lie too deep in the atom for such quenching to occur.
Magnetic moment of f elements is thus given by the following formula.

• µ = √ [ 4 S ( S+1 ) + L ( L+1 ) ]

• This formula involves orbital quantum number L

• When the magnetic moments are calculated on the basis spin and orbital contributions, there is
excellent agreement between the experimental and calculated values except for Sm and EU as
shown in the table below

Ion 4fn µ Calculated µ experimental

Ce3+ 1 2.54 2.5
Nd3+ 3 3.62 3.6
Sm3+ 5 0.86 1.6
Eu3+ 6 0.00 3.4
Gd3+ 7 7.94 8.0
Dy3+ 9 10.63 10.6
Er3+ 11 9.59 9.5
Yb3+ 13 4.54 4.5

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• Occurrence and Separation of Lanthanides

• Occurrence in Nature

• Each known Lanthanide mineral contains all the members of the series. However, each mineral
contains different concentrations of the individual Lanthanides. The three main mineral sources are
the following:

• Monazite: contains mostly the lighter Lanthanides.

• Xenotime: contains mostly the heavier Lanthanides

• Euxenite: contains a fairly even distribution of the Lanthanides

• In all the ores, the atoms with a even atomic number are more abundant. This allows for more
nuclear stability, as explained in the Oddo-Harkins rule.

• The Oddo-Harkins rule simply states that the abundance of elements with an even atomic number
is greater than the abundance of elements with an odd atomic number. In order to obtain these
elements, the minerals must go through a separating process, known as separation chemistry. This
can be done with selective reduction or oxidation or by ion-exchange method.

• Extraction of Lanthanide Metals

• After conventional mineral dressing which gives minerals 90% purity, the mineral is broken down
by either acidic or alkaline attack. By making use of different solubilities of double salts: Ln2(SO4)3.
Na2SO4.xH2O for light and heavy Ln and low solubility of hydrated oxide of thorium, the lanthanide
fractions and thorium containing portions are separated in acidic media.

• Procedure.Monazite is treated with hot Conc H2SO4 when thorium, lanthanum and lanthanides
dissolve as sulphates and are separated from insoluble materials (impurities). On partial
neutralization by NH4OH, thoriuom is precipitated as ThO2. Then Na2SO4 is added to the solution.
At this stage Lanthanum and light lanthanides are precipitated as sulphates leaving behind the
heavy lanthanides in solution. To the precipitate obtained above is added concentrated NaOH .
The resulting hydroxides of light lanthanides are dried in air at 100oC, to convert the hydroxides to
oxides. The oxide mixture is treated with dilute HNO3. This brings CeO2 as precipitate and other
lanthanides in solution. For the solutions obtained above for heavy and light lanthanides, individual
members are isolated by the following methods.

• Fractional Crystallization Method.

• This method is based on the difference in solubility of the salts such as nitrates, sulphates,
oxalates, bromates, perchlorates , carbonates and double salts of lanthanide nitrates with
magnesium nitrates which crystalizes well and form crystals . Since the solubility of these simple
and double salts decrease from La to Lu, the salts of Lu will crystallize first followed by those of

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 lighter members. The separation can be achieved by repeating crystallization process a number of
times. A non-aqueous solvent such as diethyl ether has been used to separate Nd(NO3)3 and
Pr(NO3)3

• Fractional Precipitation Method

• This method is also based on the difference in solubility of the precipitate formed, after addition of
the precipitant. i.e precipitating agent. If a little amount of the precipitant is added, the salt with the
lowest solubility is precipitated most readily and rapidly. For example, when NaOH is addedto the
solution of Ln(NO3)3, Lu-hydroxide being the weakest base and having the lowest solubility product
is precipitated first while La-hydroxide which is the strongest base and has the highest solubility
product is precipitated last. By dissolving the precipitate in HNO3 and re-precipitating the hydroxide
a number of times, it is possible to get the complete separation of lanthanides elements.

• Valency Change Method

• This method is based on the change of chemical properties by changing the oxidation state of the
lanthanide elements. The most important application of this method is made in the separation of
cerium and europium elements from the mixture of the lanthanides

• The mixture containg the Ln3+ ions if treated with a strong oxidizing agent such as alkaline KMnO4,
only Ce3+ ion is oxidized to Ce4+ while other Ln3+ ions remain unaffected. To this solution alkali is
added to precipitate Ce(OH)4 only, which can be filtered off from the solution

• Eu2+ can be separated almost completely from Ln3+ ions from a solution by reducing it with Zn-
amalgam and then precipitating it as EuSO4 on adding H2SO4 which is insoluble in water and
hence can be separated. The sulphates of other Ln3+ ions are soluble and remain in solution

• Complex formation method.

• This method is generally employed to separate heavier lanthanide elements from the lighter ones
by taking the advantage of stronger complexing tendency of smaller cations with complexing
agents. When EDTA is added to Ln3+ ion solution, lanthanides form strong complexes. If oxalate
ions are added to the solution containing EDTA and Ln3+ ions, no precipitate of oxalates is
obtained. However, on adding small amounts of acid, the least stable complexes of lighter
lanthanides are dissociated and precipitated as oxalates but the heavier lanthanides remain in
solution as EDTA complexes

• Solvent extraction Methods

• Solvent extraction involves extraction of a substance using a suitable solvent in a two phase
solvent system; the solute is extracted from one solvent into another, the extracting solvent being
chosen so that impurities remain in the original solvent. This method is primarily based on the
difference in the value of partition coefficient of lighter and heavier lanthanides between two
solvents eg water and tri-butylphosphate (TBP)- a phosphate ester

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•

• Heavier lanthanides are more soluble in TBP than lighter ones whereas reverse trend of solubility
is found in water and other ionic solvents. La(NO3)3 and Gd(NO3)3 have been separated by this
method because the partition coefficient of Gd-nitrate in water and TBP is different from that of La-
nitrate. Thus Gd-nitrate can be separated from La-nitrate by continuous extraction with water from
a solution of these salts in TBP in kerosene oil or by using continuous counter-current apparatus
which gives a large number of partitions automatically.

• Modern Ion-Exchange Method.

• This is the most rapid and most effective method for the isolation of individual lanthanide elements
from the mixture. An aqueous solution of the mixture of lanthanide ions (Ln3+aq) is introduced into a
column containing a synthetic cation exchange resin. A typical cation exchange resin is the
sulphonated polystyrene containing SO3H as the functional group or its Na+ salt. As the solution of
mixture containing Ln3+ ions is poured on to a resin-column, it moves through the column, and Ln3+
aq ions replace H+or Na+ions of the resin and get themselves fixed on it. Thus

• Ln3+(aq) + 3H+(resin) Ln(resin)3 + 3H+(aq)

• The H+aq ions are washed through the column. The Ln3+ aq ions are fixed at different positions on
the column. Since, Lu3+ aq is largest (Lu3+anhydrous is the smallest and is hydrated to the
maximum extent) and Ce3+ aq is the smallest , Lu3+ aq is attached to the column with minimum
firmness remaining at the bottom and Ce3+ aq ion with maximum firmness remaining at the top of
the resin column. In order to move these Ln3+ aq down the column and recover them, a solution of
anionic ligand such as citrate or 2-hydroxy butyrate is passed slowly through the column(called
elution). The anionic ligand form complexes with the lanthanides which possess lower positive
charge than the initial Ln3+ aq ions . These ions are thus displaced from the resin and moved to the
surrounding solutions as eluant-LncomplexFor example if the citrate solution(a mixture of citric
acid and ammonium citrate ) is used as the eluant, during the elution process, NH4+ ions are
attached to the resins replacing Ln3+aq ions which form Ln-citrate complexes

• Ln(resin)3 + 3NH4+ 3NH4-resin + Ln3+aq

• Ln3+aq + citrate ions Ln-citrate complex

• As the buffered citrate solution runs down the column, the metal ions get attached alternately with
the resin and citrate ions(in solution) many times and travel gradually down the column and finally
pass out of the bottom of the column as the citrate complex. The Ln3+ aq cations with the largest
size are, eluted first(heavier Ln3+aq ions) because they are held with minimum firmness and lie at
the bottom of the column

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• The lighter Ln3+ aq ions with smaller size are held at the top of the column. With maximum firmness
and are eluted last as the process is repeated several times by careful control of the
concentration of citrate buffer.

• If conditions are correct, the different elements will be separated into pure compounds as shown
below

• Y

Dy Tb Gd
Yb Tm Er Ho
Lu
Relative
Conc

Volume of eluate

• Application of rare earth elements

• The demand for rare earth element compounds has been growing mainly from their potential
applications in many fields of human life. Some of the uses of these metals are as listed

• (i).Rare earth elements find application in many advanced materials such as high performance
magnets (Nd2Fe14B and SmCo5, Sm2Co17) which revolutionized technology by miniaturization of
hard disc drives,

• (ii) Used in fluorescent materials, chemical sensors, high temperature superconductors, magnet
optical discs and rechargeable nickel-metal hybride batteries (NiMH). The alloy used for the
battery’s positive pole consists of rare earth metals and this makes up 26%of the weight of the
battery.

• (iii) Used in TVs,

• (iv)Computer hard drives, plasma and LCD screens, laptop computers, cell phones, DVD players,
cameras, electric motors and generators of hybrid cars (Nd-Fe-B magnets and La batteries).

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• (v).In cars, rare earth elements are also used in fuel injectors, airbags and seat belt sensors, anti-
lock brakes, power steering and seat adjustment motors and even in the fuel and car catalytic
converters

• (vi).Medical magnetic resonance imaging equipment, for peptide preparation as well as

microfertilizers that can increase certain crop yields by 15% etc

• (iii) Used in TVs,

• (iv)Computer hard drives, plasma and LCD screens, laptop computers, cell phones, DVD players,
cameras, electric motors and generators of hybrid cars (Nd-Fe-B magnets and La batteries).

• (v).In cars, rare earth elements are also used in fuel injectors, airbags and seat belt sensors, anti-
lock brakes, power steering and seat adjustment motors and even in the fuel and car catalytic
converters

• (vi).Medical magnetic resonance imaging equipment, for peptide preparation as well as

microfertilizers that can increase certain crop yields by 15% etc

• CHEMISTRY OF THE ACTINIDE ELEMENTS

• The group of 14 elements from thorium(Th, Z = 90) to lawrencium (Z-=103) are called actinides.
These are named so because these elements succeed the element actinium(Z=89).

• These elements are known as inner transition elements as they lie between actinium and
rutherfordium(Rf , Z=104)i.e the elements of the 4th transition series. Thus they constitute the
second inner-transition series of which actinium is the prototype

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• In these elements 5f-subshell of the antepenultimate shell(n=7) is successfully filled by the
additional or differentiating electrons, one at a time in each step, which are embedded in the
interior while 6d- and 7s-electrons are exposed to the surroundings

• In the outermost penultimate shell of these elements , the number of electrons remain almost the
same. That is why the actinide elements resemble one another very closely.

• The actinides lying beyond uranium i.e elements with Z= 93 to 103 are called transuranium
elements .

• These elements are also said to belong to group 3 and period 7 and have been allotted a position
below those of 4f series in the periodictable and thus the elements of both f-series have been
placed separately below the main body of the table toavoid unnecessary expansion of the periodic
table.

GENERAL FEATURES OF THE ACTINIDES

• (i). Occurrence

• All the actinides are radioactive.Only the first four elements viz, actinium , thorium, protactinium
and uranium occur in nature in uranium minerals. In these minerals, only thorium and uranium
occur to any useful extent. This is because the half-lives of 235U, 238U and 232Th( These isotopes are
the ones formed in the radioactive series and found in uranium and thorium minerals) are
sufficiently long to have enabled them to persist in nature.

• All the other remaining actinides i.e transuranium elements are unstable and are made artificially.
The half –lives of even the most stable of the elements following uranium are so short that any
amounts formed in the beginning would have disappeared quickly before any appreciable studies
are made. This is especially so for elements above fermium (Z=100)which exist as short lived
species some of them existing only a few seconds.

• Electronic structure (or configuration).

• The electronic configuration of actinium (Z= 89) which is followed by 14 actinides is [Rn]5f06d17s2
the last electron entering the 6d-subshell.

• In the next element, thorium the first member of the actinide series, the additional electron must
enter 5f-subshell and the filling of 5f-subshell must continue progressively till the last element
lawrencium.

• Thus 6d-subshell in all the elements must remain singly filled thereby giving the expected valence
shell configuration of [Rn] 5f 1-14 6d17s2 for these elements.

• Since the energies of 6d and 5f subshells are almost of the the same energy and the atomic
spectra of the elements are very complex, it is difficult to identify the orbital in terms of quantum
numbers as well as to write down the configuration.

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• For chemical behavior, the valence shell electronic configuration of the elements is of great
importance and the competition between 5fn6d07s2 and 5fn-16d17s2 is of interest.

• It has been observed that the electronic configuration of actinides does not follow the simple
pattern as is observed for the lanthanides. For the first four actinide, elements, viz Th, Pa, U and
Np, due to almost equal energies of 5f and 6d, the electrons may occupy the 5f or 6d subshells or
sometimes both.

• From Pu(Z=94) onwards, 6d1 electrons get shifted to 5f subshell except for Cm (Z=96) in which the
6d1 electron does not shift to 5f due to stable 5f7 and Lr( Z = 103) 5f14 configurations.

• In view of the above considerations, general valence shell electronic configuration of the actinide
elements may be written as 5f0-146d0-27s2. For individual elements the observed or actual valence
shell configuration are listed below.

• Element(Z) Valence Shell Element(Z) Valence shell Conf

Conf
Thorium( 90) [Rn]5f16d17s2 Berkelium(97) 5f96d07s2
Protactinium(91) 5f26d17s2 Californium(98) 5f106d07s2
Uranium(92) 5f36d17s2 Einstenium(99) 5f116d07s2
Neptunium(93) 5f46d17s2 Fermium(100) 5f126d07s2
Plutonium(94) 5f66d07s2 Mendelevium(101) 5f136d07s2
Americium(95) 5f76d07s2 Nobelium(102) 5f146d07s2
Curium(96) 5f76d17s2 Lawrencium(103) 5f146d17s2

• From the above valence shell configurations of the actinide elements, it is clear that thorium does
not have any f-electron though this element belongs to 5f-series actinides. For Pa,U, Np, Cm and
Lr, both the expected and observed (actual) configurations are the same. For the rest of the
actinides, 6d-subshell does not contain any d-electron.

• General Chemistry of the Actinides

• The chemistry of these elements is complicated especially in solutions. However studies of these
elements have been intensified because of the relevance in nuclear energy and in this instance the
chemistry of plutonium is better known than that of many other naturally occurring elements.

The salient features of Actinides

• The metals are all electropositive

• Actinium has only the +3 oxidation state and its chemistry resembles that shown by the
lanthanides

• Thorium and protactinium show limited resemblance to the other elements. They can perhaps best
be regarded as the heaviest elements of the Ti, Zr, Hf and V, Nb and Ta groups respectively.

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• Uranium, Np,Pu and Am are all quite similar differing only in the relative stabilities of their oxidation
states which range from +3 to +6.

• Curium is lanthanide like and corresponds to gadolinium in that at Cm, the 5f shell is half filled.. It
however differs from Gd in having +4 compounds.By comparison with the lanthanides the previous
element americium shows the +2 oxidation state like Eu and the succeeding element berkelium the
+4 oxidation state like Tb.

• The elements Cm and lawrencium are lanthanide-like . Lr like Lu has a filled f shell so that
elements 104 onwards should be analogous to Hf, Ta, W etc

• A characteristic feature of the compounds and complexes of actinides like the lanthanides , is the
occurance of high coordination numbers up to 12 as in [Th(NO3)6]2-

• The various cations of U, Np, Pu and Am have very complex solution chemistry because of
hydrolysis, polymerization, complexing and disproportionation reactions

• Oxidation States:

• The important oxidation states exhibited by actinides are compiled below in the tabular form. Some
of the oxidation states are stable but most of these oxidation states are unstable. It may be seen
from these oxidation states that the +2 state is shown by Th and Am only in the few compounds
like ThBr2, ThI2 ThS etc.

• The +3 oxidation state.This is the most common oxidation state which is exhibited by all the
actinide elements except Th and Pa.It becomes more stable as the atomic number increases. Thus
it is the preferred state for Ac, Am and all the elements following Am.

• The chemistry of +3 oxidation state is similar to that of the lanthanides. For example, the fluorides
are precipitated from dilute HNO3 solutions. Since the ionic sizes of lanthanides and actinides are
comparable, there is considerable similarity in the formation of complex ions such as citrates and
the magnitude of the formation constant.

• The +4 oxidation state is shown by the elements from Th to Bk, the +5 oxidation state by Th to Am,
the +6 state by the elements from U to Am and the +7state is exhibited by only two elements viz
Np and Pu. Np in the +7 state acts as an oxidizing agent.

• The +4 oxidation state. The +4 oxidation state is shown by the elements from Th to Bk. Indeed
this is the principal oxidation state for Th. For Pa, U, Np,Pu and Bk +4 cations are known in
solution but for Am and Cm in solution there are only complex fluoroanions. The +4 cations in acid
solutions can be precipitated by iodate, oxalate, phosphate and fluoride.

• The +5 oxidation state. This is the preferred oxidation state for Pa in which it resembles Ta. For U
to Am only a few solid compounds are known. For these elements, the dioxo ions , MO2+(aq) are of
importance as will be shown below.

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• The +6 oxidation state. The only simple compounds are the hexafluorides, MF6 of U, Np and Pu.
The only principal chemistry in this oxidation state is that of dioxo ionsMO22+ of U, Np, Pu and Am

• The +2 and +7 oxidation states. These are quite rare . The +2 oxidation state is confined to
Am(the 5f analog of Eu) while the +7 oxidation state is known only in oxoanions of Np and Pu.

• The Dioxo ions:The principal cations given by actinide elements are M3+, M4+ and oxo-cations
such as MO2+(Oxidation state of M= +5) and MO22+ (Oxidation state of M = +6). The examples of
oxo-cations are UO2+, PuO2+, and PuO22+ which are stable in acid and aqueous solutions. Most of
the M3+ ions are more or less stable in aqueous solution, Np3+ and Pu3+ ions in solution are
oxidized to Np4+ and Pu4+ by air. The latter ions are further oxidized slowly to UO22+ and PuO22+ by
air. Various oxidation states of the actinides are listed below

• Elemen Oxidation states Element Oxidation states

t

Th +2,+3,+4 Bk +3, +4
Pa +3, +4, +5 Cf +3
U +3, +4,+5, +6 Es +3
Np +3, +4,+5, +6, Fm +3
+7
Pu +3, +4,+5, +6, Md +3
+7
Am +3, +4,+5, +6, No +3
Cm +3, +4 Lr +3

• Atomic Radii and Ionic Radii

• The atomic (metallic)and ionic radii of the cations in common oxidation states (M3+ and M4+
cations ) of some of the actinide elements have been evaluated.

• The atomic radii reveals that the metallic radii first decrease from Th to Np and then increase
gradually up to Bk. For the higher actinides the values are not known.

• The values of the ionic radii for both types of ions go on decreasing as the atomic number
increases . This steady fall in the ionic radii along the actinide series is called actinide contraction
which is analogous to lanthanide contraction found in lanthanides.

• The cause of actinide contraction is the same as has been discussed for the Ln. Here also ,
increasing nuclear change and poor shielding effect of 5f-electrons play an important role.

• There is a small variation in the atomic and ionic radii of the actinide elements hence they show
similar chemical properties

• Magnetic and Spectral Properties

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• The actinide elements like Ln show paramagnetism in the elemental and ionic states. This is
because of the presence of upe.Tetravalent thorium (Th4+) and hexavalent uranium(U6+) ions are
diamagnetic due to the absence of upe. Th4+ = U6+ = Rn(Z=86) structure(diamagnetic , paired
electrons)

• Since the actinides constitute second f-series, it is natural to expect similarities with Ln (the first f
series) in their magnetic and spectroscopic properties. But there are some differences between
Lns and actinides Spin –Orbit coupling is strong (2000-4000cm-1) in the actinides than in the
lanthanides.

• The electronic spectra of actinides compounds arise from the following three types of electronic
transitions

• f-f transitions These are Larporte(orbitally) forbidden but the selection rule is relaxed partiallyby
the action of crystal field in distorting the symmetry of the metal ion . Because theactinide s show
greater field, hence the bands are more intense. These bands are narrow and more complex, are
observed in the visible and UV regions and produce the colours in aqueous solutions of simple
actinide solutions

• 5f-6d transitions. These are Larporte and spin allowed transitions and give rise to much more
intense bands which are broader. They occur at lower energies and are normally confined to the
UV region hence do not affect the colours of the ions

• Metal to ligand Charge transfer. These transitions are fully allowed and produce broad , intense
absorptions usually found in UV region, sometimes trailing in the visible region. They produce the
intense colours which are characteristic of the actinide complexes

• The spectra of actinide ions are sensitive to the crystal field effects and may change from one
compound to another. It is not possible to deduce the stereochemistry of actinide compounds due
to complexity of the spectra. Most of the actinide cations and salts are coloured due mainly to f-f
transitions. Those with f0, f7 and f14 configurations are colourless The colours of some of the
compounds in different oxidation states are given below.

• NpBr3 green, NpI3: Brown NpCl4: red-brown: NpF6: brown

• PuF3; purple, PuBr3, green, PuF4, brown, PuF6, red brown

• AmF3; pink, AmI3; yellow, AmF4; dark tan

• The coordination chemistry of actinides is more concerned with aqueous solutions . Because of the
wider range of oxidation states available in actinides, their coordination chemistry is more varied.

• Most of the actinide halides form complex compounds with alkali metal halides. For example, ThCl4
with KCl forms complexes with pyridine eg ThCl4py. Chelates are formed by the actinides with
multidentate organic reagents such as oxime, EDTA, acetyl acetone etc.

• SIMILARITIES BETWEEN LANTHANIDES AND ACTINIDES

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 • In the atoms of the elements of both series, three outermost shells are partially filled and
remaining inner shells are completely filled but the additional or differentiating electron enters (n-
2)f subshell

• The elements of both series exhibit +3 oxidation state which is prominent and predominant state.

• Like lanthanide contraction found in the lanthanide elements , there occurs contraction in size in
the actinide elements called actinide contraction. Both the contractions are due to poor shielding
effect produced by f-electron with . The elements of both series are quite reactive and are
electropositive

• v. The electronic absorption bands of the elements of both the series are sharp and appear like
lines. These bands are produced due to f-f transitions within (n-2) f subshell though such
transitions are orbital forbidden

• vi. Most of the lanthanide and actinide cations are paramagnetic .

• vii. The nitrates , perchlorates and sulphates of trivalent lanthanides and actinides elements are
soluble while the hydroxides , fluorides and carbonates of these elements are insoluble

• DIFFERENCES BETWEEN LANTHANIDES AND ACTINIDES

Lanthanides Actinides
(i). Besides +3 oxidation state, they show +2 (i). Besides +3 oxidation state, they show
and +4 oxidation states in few cases higher oxidation states of +4,+5,+6 +7
(ii).Most of the ions are colourless (ii).Most of the ions are coloured
(iii). They have less tendency towards complex (iii). They have greater tendency towards
formation complex formation
(iv) Lanthanide compounds are less basic (iv) Actinide compounds are more basic
(v).Lanthanide do not form oxocations (v) form octocations such as UO2+, PuO22+ and
UO+
(vi) Except promethium they are non- (vi) They are radioactive
radioactive
(vii) Their magnetic properties can be (vii). Their magnetic properties cannot be
explained easily explained easily as they are more complex.

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