CH 2103: Chemistry of Transition Elements

Dr. Somit Kumar Singh

Introduction
Three series of elements are formed by filling the 3d, 4d and 5d shells
of electrons. Together these comprise the d block elements. They are
often called transitions elements because their position in the periodic
table is between the s-block and p-block elements. Their properties are
transitional between the highly reactive metallic elements of the s-
block, which typically forms ionic compounds, and the elements of p-
block, which are largely covalent.

In the s and p- blocks, electrons are added to the penultimate shell,

expanding it from 8-18 electrons. The elements make up three
complete rows of ten elements and an incomplete fourth row. The
position of the incomplete fourth series is discussed with the f-block
elements.
 Elements
3 4 5 6 7 8 9 10 11 12 Group

21
Sc Ti V Cr Mn Fe Co Ni Cu 30
Zn First Transition Series

39
Y Zr Nb Mo Tc Ru Rh Pd Ag 48
Cd Second Transition Series

57
La 72
Hf Ta W Re Os Ir Pt Au 80
Hg Third Transition Series

89
Ac Incomplete…….Studied with f-block elements Fourth Transition Series

Z= 58-71 Lanthenide series

Z= 90-103 Actinide series

The transition elements

Those elements or ions have partially filled d or f subshells are reffered
to as transition elements or ions and inner transition elements or ions
respectively.
 Electronic configuration of d-block elements

The elements from scandium to zinc constitute the first transition

series, the electronic configuration are shown below.
Elements Electronic configuration Valance shell E.C
21
Sc 1s2 2s2 2p6 3s2 3p6 4s2 3d1 [Ar] 4s2 3d1
22
Ti 1s2 2s2 2p6 3s2 3p6 4s2 3d2 [Ar] 4s2 3d2
23
V 1s2 2s2 2p6 3s2 3p6 4s2 3d3 [Ar] 4s2 3d3
24
Cr 1s2 2s2 2p6 3s2 3p6 4s1 3d5 [Ar] 4s2 3d5
25
Mn 1s2 2s2 2p6 3s2 3p6 4s2 3d5 [Ar] 4s2 3d5
26
Fe 1s2 2s2 2p6 3s2 3p6 4s2 3d6 [Ar] 4s2 3d6
27
Co 1s2 2s2 2p6 3s2 3p6 4s2 3d7 [Ar] 4s2 3d7
28
Ni 1s2 2s2 2p6 3s2 3p6 4s2 3d8 [Ar] 4s2 3d8
29
Cu 1s2 2s2 2p6 3s2 3p6 4s1 3d10 [Ar] 4s2 3d10
30
Zn 1s2 2s2 2p6 3s2 3p6 4s2 3d10 [Ar] 4s2 3d10
• The atoms of Cr and Cu have a single electron in 4s orbital. This is
due to the additional stability gained by the atom when the d
subshell is exactly half filled or completely filled. One of the 4s
electron moves to the 3d level in the atom of chromium and copper,
3d level in the case of chromium gets exactly half filled and that in
the case of copper gets completely filled.

• Zinc having completely filled d-subshell, therefore its behavior

with other elements are different.

• The elements from Yttrium (39Y) to Cadmium (48Cd) constitute the

second transition series. The electronic configurations are given
below.
Elements Electronic configuration Valance shell E.C
39
Y 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p6 5s2 4d1 [Kr] 5s2 4d1
40
Zr 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p6 5s2 4d2 [Kr] 5s2 4d2
41
Nb 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p6 5s1 4d4 [Kr] 5s1 4d4
42
Mo 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p6 5s1 4d5 [Kr] 5s1 4d5
43
Tc 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p6 5s2 4d5 [Kr] 5s2 4d5
44
Ru 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p6 5s1 4d7 [Kr] 5s1 4d7
45
Rh 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p6 5s1 4d8 [Kr] 5s1 4d8
46
Pd 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p6 5s0 4d10 [Kr] 5s0 4d10
47
Ag 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p6 5s1 4d10 [Kr] 5s1 4d10
48
Cd 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p6 5s2 4d10 [Kr] 5s2 4d10
• The electronic configuration of Mo (5s1 4d5) and Ag (5s1 4d10) can be
easily understood on the basis of higher stability exactly half filled
and completely filled subshell.
•
• Anomalous electronic configuration of Nb (5s1 4d4), Ru (5s1 4d7), Rh
(5s1 4d8) and Pd (5s0 4d10) can be explained by nuclear-electrons and
electrons-electrons interections.

• Just like Zn, Cd also having completely filled d-subshell and hence
shows different properties than other elements.

• The third transition series starts from Lanthanum ( 57La), Hofnium

(72Hf) to Mercury (80Hg). The electronic configurations are given
below.
 Elements Electronic configuration Valance shell E.C
57
La 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p6 5s2 4d10 5p6 6s2 4f0 5d1 [Xe] 6s2 4f0 5d1
72
Hf 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p6 5s2 4d10 5p6 6s2 4f14 5d2 [Xe] 6s2 4f14 5d2
73
Ta 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p6 5s2 4d10 5p6 6s2 4f14 5d3 [Xe] 6s2 4f14 5d3
74
W 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p6 5s2 4d10 5p6 6s2 4f14 5d4 [Xe] 6s2 4f14 5d4
75
Re 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p6 5s2 4d10 5p6 6s2 4f14 5d5 [Xe] 6s2 4f14 5d5
76
Os 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p6 5s2 4d10 5p6 6s2 4f14 5d6 [Xe] 6s2 4f14 5d6
77
Ir 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p6 5s2 4d10 5p6 6s2 4f14 5d7 [Xe] 6s2 4f14 5d7
78
Pt 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p6 5s2 4d10 5p6 6s0 4f14 5d10 [Xe] 6s0 4f14 5d10
79
Au 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p6 5s2 4d10 5p6 6s1 4f14 5d10 [Xe] 6s1 4f14 5d10
80
Hg 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p6 5s2 4d10 5p6 6s2 4f14 5d10 [Xe] 6s2 4f14 5d10

The first element lanthanum and last element mercury shows

anomalous properties than that of other elements.
 General Characteristics of d-block elements

Metallic Character
• All the transition elements are metals. This is to be expected since
the number of electrons in the outermost shell is very small being
only 1 or 2 which can be readily lost.
• They are good conductor of heat and electricity.
• They are also malleable and ductile and form alloys with several
other metals.
• Covalent and metallic bonding both exists amongst the atoms of the
transition elements. The overlapping of unfilled d-orbitals of metal
atoms causes covalent bonding and the valance s-electrons causes
metallic bonding. Copper, silver and gold are particularly
outstanding in their thermal and electrical conductivity.
 General Characteristics of d-block elements

Molar volumes and densities

Molar volumes of transition elements are much lower than those of s
and p block elements of the neighbouring groups. As the inner
orbitals get filled, the increased nuclear charge pulls the electrons
inward. The molar volume therefore decreases. As a result of
decrease in molar volume, there are corresponding increases in
density.
Accordingly, the densities of the transition elements are quite high.
Most of these elements have densities greater than 5g/cm 3.
Scandium, titanium and yttrium, with densities 3.01, 4.51, 4.47 g/cm 3
respectively are the only exceptions. The densities of second and
third transition series are quite high. The two elements with the
highest densities are osmium 22.57 g/cm3 and irridium 22.61 g/cm3.
First Molar Density Second Molar Density Third Molar Density
T.S. volume T.S. volume T.S. volume

Sc 15.03 3.01 Y 19.8 4.47 La 22.5 6.17

Ti 10.6 4.51 Zr 14.1 6.49 Hf 13.6 13.1
V 8.35 6.1 Nb 10.8 8.4 Ta 10.9 16.6
Cr 7.23 7.19 Mo 9.4 10.21 W 9.53 19.3
Mn 7.39 7.43 Tc …. 11.50 Re 8.85 21.0
Fe 7.10 7.86 Ru 8.3 12.20 Os 8.43 22.6
Co 6.7 8.9 Rh 8.3 12.4 Ir 8.54 22.5
Ni 6.6 8.9 Pd 8.9 12.0 Pt 9.1 21.4
Cu 7.1 8.96 Ag 10.4 10.51 Au 10.22 19.3
Zn 9.2 7.14 Cd 13.1 8.65 Hg 14.82 13.6
Atomic and Ionic radii

The covalent radii of the elements decrease from left to right across a
row in the transition series until near the end when the size increases
slightly. On passing from left to right, extra protons are placed in the
nucleus and extra orbital electrons are added. The orbital electrons are
shield the nuclear charges incompletely (d-electrons shield less
efficiently than p-electrons, which in turn shield less effectively than s-
electrons). Because of this poor screening by d-electrons, the nuclear
charge attracts all of the electrons more strongly; hence contraction in
size occurs.
Atoms of the transition elements are smaller than those of the group 1
and group 2 elements in the same horizontal period. This is partially
because of the usual contraction and partially because of the orbital
electrons is added to the penultimate d-shell rather than to the outer
shell of the atom.
The transition elements are divided into vertical groups of the three
(triads) or sometimes four elements, which have similar electronic
structure. The elements in the first group of d-block (group-3) shows
the expected increase in size Sc→Y→La. However, in the subsequent
groups (4-12), there is an increase in radius of 0.1 to 0.2 Å between the
first and second member, but no increase in size occur between second
and third elements.

This trends shows both in the covalent radii and in the ionic radii. This
is only because of the incorporation of 14 lanthanide elements in
between lanthanum and Hofnium, in which the antepenultimate 4f-
shell of electrons is filled.
The elements of second and third row of transition series having almost equal
covalent and ionic radii due to lanthanide contraction, which possesses similar lattice
energy, solvation energies and ionization energies. Thus the differences in properties
between the first row and second row elements are much greater than the differences
between the second row and third row elements.
K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn
1.57 1.74 1.44 1.32 1.22 1.174 1.17 1.17 1.16 1.15 1.17 1.25
Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd
2.16 1.91 1.62 1.45 1.34 1.29 ….. 1.24 1.25 1.28 1.34 1.41
Cs Ba La * Hf Ta W Re Os Ir Pt Au Hg
2.35 1.98 1.69 1.44 1.34 1.30 1.28 1.26 1.26 1.29 1.34 1.44

Covalent radii of transition elements (* 14 lanthanide elements)

Ca++ 1.00 Sc3+ 0.745 Ti4+ 0.605 V3+ 0.64

Sr++ 1.18 Y3+ 0.9 Zr4+ 0.72 Nb3+ 0.72

Ba++ 1.35 La3+ 1.032 * Hf4+ 0.71 Ta3+ 0.72

The effect of lanthanide contraction on ionic radii (* 14 elements)

Melting and boiling point
Melting and boiling point of transition elements are generally very
high. The melting point of most of the elements except (Cd and Hg) is
above 900oC. This seems to be very high temperature when compared
with M.P. of s-block elements.

Zn, Cd and Hg have relatively low MP such as 419.5oC, 320.9oC and

−38.4oC respectively. These elements, like the other d-block elements
are moderately volatile. Exceptional behavior of these elements are
only due to completely filled d-orbital, therefore, atoms in these
elements lack covalent bonding which is only responsible for higher
MP and BP. Three transition elements melt above 3000oC (Ta=3000oC,
W=3410oC and Re=3180oC).
Ionization Energies
The ionization energy of an element gives an idea of the ease with
which an electron can be removed from its isolated gaseous atom in its
ground state. The ionization energies of first transition series are given
below.
Elements Ionization energies
First Second Third
Sc 632.6 1245.1 2450.6
Ti 659 1320.5 2721
V 650 1376.1 2873.6
Cr 652.3 1635.1 2994.9
Mn 716.3 1513.3 3258.1
Fe 762.3 1564 2963.9
Co 758.1 1647 3237.6
Ni 736 1756 3400
Cu 744.7 1961.9 3560.6
Zn 906.7 1736.3 3838.8
• Since the atoms are small in size, their ionization energies are fairly
high. The values in most cases lie in between those of s and p-block
elements. This indicates that transition elements are less
electropositive than the elements of group I and group II (s-block).
Unlike the alkali and alkaline earth metals, the transition elements
do form covalent compounds under certain conditions. Generally,
the compounds in which a higher valancy is exercised are covalent
compounds.
• The ionization energy along a period is generally expected to
increase with increase in the atomic number. In case of transition
elements, the addition of increasing number of d-electrons increases
the screening effect and hence shields the outer s-electrons from
inward pull of positive nucleus. The increase in nuclear charges
cancelled by increase in shielding as we move from left to right in a
transition series, therefore very less increase in ionization energies.
• In the first transition series, the values for the first four elements
(Sc, Ti, V, Cr) differ only slightly from one another, similarly the
values for Fe, Co, NI and Cu are fairly close to each other. The
value for Zn is appreciable higher due to the additional stability
conferred on the atom on account of complete filling of the 3d
subshell.
• The second ionization energies are seen to increase, more or less
regularly with increase in atomic number. The values for Cr and Cu
however are notably higher than those of their neighbours because
singly charged Cr and Cu has outer electronic configuration 3d5 and
3d10 respectivelly and removal of electrons from exactly half filled
3d5 or full filled 3d10 are quite difficult due to its extra stability.
Reactivity of metals
Many of the metals are sufficiently electropositive to react with
mineral acids. The atoms of transition elements are rather small and
therefore ionization energies are fairly high. Due to existence of
covalent bonding, they have high heat of sublimation, i.e., they require
a large amount of energy to change them from solid to vapour state.

The metal ions due to large size and low charge density do not get
hydrated easily. Thus on account of their high heat of sublimation,
high ionization energies and low heat of hydration of their ions, the
transition elements have small tendency to react. They have rather a
tendency to remain unreactive or noble. This tendency is very well
pronounced in Pt and Au.
Oxidation States

The outer electronic configuration of scandium (Sc) is 4s2 3d1. It

exhibits an oxidation of +2 in those compounds in which it uses both
of its 4s electrons. It can also exhibit an oxidation state of +3 when it
uses its two 4s electrons as well as one d electron in chemical bonding.

The outer electronic configuration of titanium (Ti) is 4s2 3d2. It shows

an oxidation state equal to +2 when it uses both 4s electrons, equal to
+3 when the both 4s electrons and one 3d electron used and +4 when
both 4s electrons and two 3d electrons are used in chemical bonding.

Similarly, vanadium (V), with electronic configuration 4s2 3d3, shows

oxidation states equal to +2, +3, +4, +5, depending upon whether it
uses the two 4s electrons only or also in addition to that, it uses one,
two or three of its d-electrons as well.
Chromium (Cr), the next element with outer electronic configuration
4s1 3d5, has only one 4s electron. Accordingly, it can have an oxidation
state of +1 when it uses only this electron in chemical bonding. In
addition, it may have oxidation state equal to +2, +3, +4, +5 and +6
when it uses one, two, three, four and five 3d electrons as well.
Similarly manganese (Mn), having the outer electronic configuration
4s2 3d5, may have oxidation state from 2 to 7.

It is clear from the above discussion that the first five elements of the
first transition series up to Mn in which the 3d sub shell is no more
than half filled, the minimum oxidation state is given by the number of
electrons in the outer s-subshell and the maximum oxidation state is
given by the sum of the outer s and d electrons.
In the next elements, viz., iron (4s2 3d6), cobalt (4s2 3d7), nickel (4s2 3d8), copper (4s1 3d10),
and zinc (4s2 3d10), in which the number of 3d electrons is more than five, the minimum
oxidation state is still equal to the number of outer s-electrons. The maximum oxidation state,
however, is not related at all with the electronic configuration. In fact, the maximum
oxidation state of iron, which has outer electronic configuration as 4s2 3d6 is largely confined
to +2 or +3. The +4, +5, +6 oxidation states are known but are rare and +8 oxidation state is
unknown. The +8 oxidation state, however is important in the chemistry of the other members
of the iron family, namely, ruthenium and osmium.
Oxidation states of the elements of the first transition series
Elements Outer electronic configuration Oxidation states
Sc 4s2 3d1 +2, +3
Ti 4s2 3d2 +2, +3, +4
V 4s2 3d3 +2, +3, +4, +5
Cr 4s2 3d5 +1, +2, +3, +4, +5, +6
Mn 4s2 3d5 +2, +3, +4, +5, +6, +7
Fe 4s2 3d6 +2, +3, +4, +5, +6
Co 4s2 3d7 +2, +3, +4
Ni 4s2 3d8 +2, +3, +4
Cu 4s2 3d10 +1, +2, +3
Zn 4s2 3d10 +2
Standard electrode potentials
The standard electrode potential (oxidation) of a transition element is
generally higher than that of the standard hydrogen electrode (taken as
zero). For instance, the standard oxidation potentials of the elements
of the first transition series, excepting copper, are appreciably higher
than that of the standard hydrogen electrode which is taken as zero. It
is expected, therefore these metals, except copper would evolve
hydrogen gas when reacted with acid solution.
M + 2H+(aq) → M2+(aq) + H2(g)
However in actual practice, the rate of which most of these metal
reacts with acids is very low. Some of the metals, in fact, get protected
from the attack of acids by a thin impervious layer of an inert oxide.
Chromium for instance, inspite of its high electrode potential, is so
unreactive that it can be used as protective non oxidizing metal. The
reason is that it gets coated with a non-reactive oxide, Cr 2O3.
Elements Electrode Reactions Standard electrode potentials (oxidation)
volts
Sc Sc → Sc3+ + 3e− 2.10
Ti Ti → Ti2+ + 2e− 1.60
V V → V2+ + 2e− 1.2
Cr Cr → Cr3+ + 3e− 0.74
Mn Mn → Mn2+ + 2e− 1.18
Fe Fe → Fe2+ + 2e− 0.44
Co Co → Co2+ + 2e− 0.28
Ni Ni → Ni2+ + 2e− 0.25
Cu Cu → Cu2+ + 2e− −0.34
Zn Zn → Zn2+ + 2e− 0.76

Standard electrode potentials (oxidation) of the elements of the first

transition series
Reducing properties
All the elements, except copper have standard oxidation potentials
higher than that of standard hydrogen electrode (taken as zero).
Hence, these metals, excepting copper, are oxidized easily to their ions
in aqueous solutions.
M → M2+(aq) + 2e−
They should, therefore, be good reducing agents. However, they are
not as good reducing agents as the metals of group I, II and III. The
reducing capacity of a metal depends on its tendency to change in to
aquatic ions. On account of their high heats of vaporization and high
ionization energies and low heats of hydration of their ions, the
transition metals do not get converted in to aquatic ions as easily as
the metals of group I, II and III and therefore, are not as good reducing
agents as the metals of group I, II and III, although some of the later
(eg. Al) have smaller oxidation potentials.
Copper has a negative oxidation potential. This means that copper is
not able to displace H+ ions from acid solutions. The reaction simply
does not occur.
Cu + 2H+(aq) → Cu++ + 2e−
The tendency of copper to change in to cupric ion is extremely small.
Hence, copper is a particularly poor reductant.
Cu → Cu++(aq) + 2e−
Colour: Most of the compounds of transition metals are coloured in
the solid or in solution states this is unlike the compounds of s and p
block which are usualy colourless or in any case not strongly coloured.

Colour of a substance arises invariably from the property of the

substance to absorb light of certain wave lengths in the region of
visible light (λ= 3800 – 7600 Å). If a substance absorbs wavelength
corresponding to red light, the transmitted light will consist of wave
lengths corresponding to other colours of blue in particular. The
substance will therefore appear blue. The transmitted light has
complementary colour of that of the absorbed light. Hydrated copper
(II) ion, for example, absorbs radiations corresponding to red light. The
ions, therefore, transmits radiations of wavelengths corresponding to
blue colours which is complementary to red colour. Anhydrous cobalt
(II) compounds also absorbs red light and therefore blue. The hydrated
cobalt (II) compounds, however, absorb radiations of wave lengths
corresponding to blue colour and therefore appear red.
Energies of d orbitals of metal ions in their complexes are split into
two sets of energy level because of crystal field effects. The colour of
transition metal ions arises from the excitations of electrons from the d
orbitals of lower energy to the d orbitals of higher energy. Light
radiations corresponding to such small amounts of energy which are
required for the above mentioned d-d electron excitations, are
available in the visible range. It is for this reason that transition metal
ions have the property to absorb certain radiations from the visible
region and exhibit complementary colours.

The transition metal ions which have completely filled d orbitals are
colourless. There are no vacant d orbitals to permit the above type of
excitation of electrons. Thus Zn2+ (3d10), Cd2+ (4d10), Hg2+ (5d10) ions
are colourless. Colours and outer electronic configuration of important
ions of the elements of the first transition series are given below.
Ion Outer electronic configuration No. of unpaired electrons Colour
Sc3+ 3d0 0 Colourless
Ti3+ 3d1 1 Purple
Ti4+ 3d0 0 Colourless
V3+ 3d2 2 Green
Cr3+ 3d3 3 Violet
Mn2+ 3d5 5 Light pink
Mn3+ 3d4 4 Violet
Fe2+ 3d6 4 Green
Fe3+ 3d5 5 Yellow
Co3+ 3d7 3 Pink
Ni2+ 3d8 2 Green
Cu2+ 3d9 1 Blue
Cu+ 3d10 0 Colourless
Zn2+ 3d10 0 Colourless
The ions of s and p block elements are colourless because the
excitation of electrons from the lower s or p orbital to the higher s, p
or d orbital can only be carried out by the absorption of a very high
amount of energy which is associated only with the radiation in the
ultraviolet region therefore no absorption of light from the visible
region. As a result, the s and p block elements are colourless.
Magnetic properties
Matter, in general, is associated with magnetic properties. Majority of
substances are either paramagnetic or diamagnetic. A paramagnetic
substance is one which is attracted in to a magnetic field and a
diamagnetic substance is one which is replaced by a magnetic field.
The diamagnetic behavior is due to the fact that small magnetic
moments are induced in to a substance when a magnetic field is brought
in the vicinity of the substance. The magnetic moments induced,
however, are in opposite direction to the induced field. This causes
repulsion of the substances by the magnetic field.

Paramagnetism arises from the presence of unpaired electrons in atoms,

ions, complex ions or molecules. Motion of an electric charge creates a
magnetic field. Thus, the motion (spin motion and orbital motion) of
an electron, a charged particle, creates a magnetic field. Each electron
may, in fact, be regarded as a micro magnet having a certain value of
magnetic moment. The total magnetic moment of a substance is the
resultant of the magnetic moments of all the individual electrons.
The substances in which electrons in their atoms are completely paired,
the effects of individual electrons are naturally compensated these
substances, therefore, do not show paramagnetic behavior. In fact, they
show diamagnetic behavior when placed in magnetic field.

If the atoms of a substance contain one or more unpaired electrons, the

effects are not mutually compensated. The magnetic moments due to spin
and orbital motion of such electrons get aligned parallel to the direction of
external magnetic field applied. The magnetic moments due to unpaired
electrons are of sufficiently high magnitude to overcome the small
magnetic moment induced due to the paired electrons in the atoms by
external magnetic field. Such a substance, therefore, instead of
experiencing repulsion, experiences attraction in a magnetic field, i.e. it
shows paramagnetic behavior.

Paramagnetism is shown by ions and molecules containing odd number of

electrons. It is also shown by molecule containing even number of
electrons provided there is one or more unpaired electrons in their
structures (O2 molecule).
The total or effective magnetic moments (μeff) of a substance
containing an unpaired electron, is made up of two components:
a) The contribution due to the orbital motion of the electron, μorbital,
which is due to orbital quantum number L.
b) The contribution due to the spin motion of the electron, μspin, which
is due to spin quantum number S.

In transition metal ions, the unpaired electrons are generally present in

the outer orbitals. The orbital motion of such unpaired electrons is
severely disturbed by the electrons of the surrounding ligands thereby
quenching the μorbital in the transition metal compounds. Therefore, in
such cases, the μspin contribution becomes much more significant than
the μorbital contribution so that the later may be neglected in many cases.
The effective magnetic moments, μeff, in such cases may thus be given
by the expression:
μeff ≈ μspin ≈ √n(n+2)
Where n is the number of unpaired electrons.
The magnetic moment is expressed in Bohr Magneton (BM) is given
by the expression:
B.M. = eh/4πmc
Where, h is plank’s constant, e is the electronic charge, c is the
velocity of light and m is the mass of electron.

The effective magnetic of a substance thus depends mainly on the

number of unpaired electrons present in it. If there is only one
unpaired electron, the magnetic moment, evidently, will be
approximately √3 or 1.732 B.M., if there are two unpaired electrons,
the magnetic moments will be approximately √8 or 2.83 B.M., for 3,
4, 5 and 6 unpaired electrons, the values will be approximately 3.87,
4.90, 5.92 and 6.93 respectively.
 Ions Outer electronic Number of unpaired Calculated magnetic
configuration electrons moments (μspin)
Sc3+ 3d0 0 0
Ti3+ 3d1 1 1.732
Ti2+ 3d2 2 2.84
V2+ 3d3 3 3.87
Cr2+ 3d4 4 4.90
Mn2+ 3d5 5 5.92
Fe2+ 3d6 4 4.90
Co2+ 3d7 3 3.87
Ni2+ 3d8 2 2.84
Cu2+ 3d9 1 1.732
Zn2+ 3d10 0 0

Calculated magnetic moments (μspin) of some of the ions of the

elements of first transition series are given above:
The actual magnetic moments may differ slightly from these values
depending upon the extent of quenching of μorbital of the electrons in the
ions. This is depends upon the type of arrangement of the anions (or
ligands) around the transition metal ions in their compounds or
complexes.
In case of iron, cobalt and nickel, the magnetic moment due to
unpaired electron spins are aligned parallel to the external magnetic
field more efficiently resulting in an exceptionally strong
reinforcement of Paramagnetism. These substances are therefore,
mush more paramagnetic than the rest of the elements and are said to
be ferromagnetic.
Catalytic properties

According to the modern theory of catalysis, a catalytic substance is

capable of forming an unstable intermediate compound which readily
decomposes yielding the product and regenerating the catalyst.
A + B + Catalyst → A.B.Catalyst → C + Catalyst
Here A and B are reactants, A.B.Catalyst is intermediate unstable
compound and C is product.

The transition elements on account of their variable valency are able to

form unstable intermediate compounds very readily. These elements
can also provide a large surface area for the reactants to be adsorbed
and thus come closer to one another for the reaction to occurs readily
on the surface of the catalyst itself.
Some important transition metals and their compounds are listed here:

TiCl3 used as a Ziegler-Natta catalyst in the production of polythene.

V2O5 converts SO2 to SO3 in the contact process for manufacturing
H2SO4.
MnO2 used as a catalyst to decompose KClO3 to give O2.
Fe promoted iron is used in the Haber-Bosch process for making NH3.
FeCl3 used in the production of CCl4 from CS2 and Cl2.
FeSO4 and H2O2 used as a Fenton’s reagent for oxidizing alcohols to
aldehydes.
PdCl2 used in Wacker process for converting ethylene in to
acetaldehyde.
Pd used for hydrogenation of phenol in to cyclohexanone.
Pt/PtO used as Adams catalyst for reduction.
Pt formerly used for SO2 → SO3 in the contact process for making
H2SO4.
Pt increasingly being used in three stage convertors for cleaning car
exhaust fumes.
Pt/Rh formerly used in the Ostwald process for making HNO3 to
oxidises NH3 to NO.
Cu is used in the direct process for manufacturing of (CH 3)2SiCl2 used
to make silicones.
Cu/V used in oxidation of cyclohexanol/cyclohexanone mixtures to
adipic acid, which is used to make nylon-6,6.
CuCl2 used in Deacon Process for making Cl2 from HCl.
Ni used as Raney nickel in numerous reduction process (eg.
Manufacturing of hexamethylene diamine, production of H2 from NH3,
reducing anthraquinone to anthraquinol in the production of H2O2). Ni
complexes used in Reppe synthesis (polymerization of alkynes to give
benzene or cyclooctatetracene).
Enzymes acts as biocatalyst, some enzymes require the presence of
metal ions as co-factors and these are called matalloenzymes. Many
metalloenzymes contain a transition metal. Some metalloenzymes are
listed below:
 Metal Enzyme/Metalloprotein Biological Function
Mo Xanthine oxidase Metabolism of purines
nitrate reductase Utilization of nitrates
Mn2+ Arginase, Phosphotransferases Urea formation, adding or removing PO 43−
Fe2+ or Aldehyde oxidase Oxidation of aldehydes
Fe3+ Catalase Decomposes H2O2
Peroxidase Decomposes H2O2
Cytochromes Electron transfer
Ferredoxin (Haemoglobin) Photosynthesis (O2 transport in animals)
Succinic Dehydrogenase Aerobic oxidation of carbohydrate
Fe & Mo Nitrogenase Fixation of dinitrogen
Co Glutamic mutase Metabolism of amino acids
Ribonucleotide reductase Biosynthesis of DNA
Cu+ & Amine oxidases Oxidation of amines
Cu2+ Ascarbate oxidase Oxidation of Ascorbic acid
Cytochrome oxidase Principal terminal oxidase
Galactose oxidase Oxidation of galactose
Lysine oxidase Elasticity of aortic walls
Dopamine hydroxylase Producing noradrenaline to generate nerve
impulses in the brain
Tyrosinase Skin pigmentation
Ceruloplasmin Utilization of iron
(Haemocyanine) (O2 transport in invertebrates)
Plastocyanine Photosynthesis
Zn2+ Alcohol dehydrogenase Metabolism of alcohol
Alkaline phosphatase Releasing PO43−
Carbonic anhydrase Regulation of pH and CO2 formation
Carboxypeptidase Digestion of protein
Non Stoichiometry:
Transition elements form non-stoichiometry compounds. These are
compounds of infinite structure and properties. For eg FeO should be
written with a bar over the formula to indicate that the ration
of Fe and O atoms are not exactly 1:1. Analysis shows that the formula
varies between Fe0.94O and Fe0.84O. Vanadium and Selenium form a
series of compounds ranging from VSe0.98 to VSe2. These are given in
the formulae.

Non-stoichiometry is shown particularly among transition metal

compounds of the group 16 elements (O, S, Se, Te). It is mostly due to
the variable valency of transition elements. For eg Cu is precipitated
from a solution containing Cu2+ by passing in H2S. The sulphide is
completely insoluble, but this is not used as a gravimetric method for
analyzing for Cu because the precipitate is the mixture of CuS and
Cu2S. Sometimes non-stoichiometry is caused by defects in the solid
structure.
Complex formation:
The transition metals are almost unique in their tendency to form
coordination complexes. The tendency of cations of transition elements
to form complexes is due to two factors. Firstly, these ions are very
small in size and, therefore, have high positive charge density. This
facilitates acceptance of lone pair electrons from other molecules.
Secondly, they have vacant orbitals and these orbitals have right type of
energy to accept lone pair of electrons. The formation and structure of
complex compounds have been discussed in details.

The transition elements have an unparalleled tendency to form

coordination compounds with Lewis bases that is with groups which
are able to donate an electron pair. These groups are called ligands. A
ligand may be a neutral molecule such as NH3 or an ion such as Cl− or
CN−. Cobalt form more complexes than any other element, and form
more compounds than any other element except carbon.
Co3+ + 6NH3 → [Co(NH3)6]3+
Fe2+ + 6CN− → [Co(CN)6]4−
Transition elements are so good at forming complexes is that they have
small, highly charged ions and have vacant low energy orbitals to
accept lone pairs of electrons donated by other groups or ligands.

Complexes where the metal is in the (+3) oxidation state are generally
more stable than those where the metal is in the (+2) state. Some metal
ions forms their most stable complexes with ligands in which the donor
atoms are N, O or F. Such metal ions include group 1 and 2 elements,
the first half of the transition elements, the lanthanides and actinides,
and the p-block elements except their heaviest member.
Occurrence, Extraction, Properties and Application of First Row
Transition Elements and their Compounds

Scandium (Sc)

Occurrence:
Scandium occurs in nature only in the combined state. It is present in
minerals such as monazite which is a complex phosphate. It is not
particularly a rare element. It is in fact, as common as arsenic and twice
as abundant as boron. However, due to low concentration of scandium
in its ores, it is difficult to obtain it in a pure state.
Extraction:
The extraction of scandium from its compound is not an easy matter.
The oxide is highly stable being more so even than alumina, hence,
even the thermite process can’t be used for its extraction. The element
is also highly electropositive and liberates hydrogen from water. The
electrolysis of aqueous solution of its compounds, therefore, can’t be
used for its preparation.

The metal can be obtained, however, by electrolysis of its fused

chloride. A small amount of NaCl is added to lower the melting point.
Zinc is used as a cathode. Scandium deposited on it form Zn-Sc alloy.
Zinc is volatilized off at low pressures. Scandium remains behind in a
reasonably pure state.
Properties:
Scandium has a silvery white lusture but gets tarnished in air due to
formation of its oxides, Sc2O3.

It has a M.P of about 1539 oC and B.P of about 2730 oC.

The entire scandium compound in +3 state are colourless and

diamagnetic because the 3d subshell in these compounds are empty.
Compounds of Scandium
Scandium forms compounds only in the +3 oxidation state. Thus, the
oxides, halides and oxohalides have the formulae Sc2O3, ScX3 and
ScOX respectively.

Scandium Oxide, Sc2O­3:

It is formed readily by heating the salts like scandium carbonate and
scandium nitrate.

It can also be obtained by interections of scandium with water.

2Sc + 3H2O → Sc2O3 (Weak base) + 3H2

Scandium halides:
All Scandium halides are soluble in water with the exception of ScF 3.
When fluoride ions are added to the solution of a Sc(III) compounds,
the precipitate of ScF3 is formed first which, in the presence of excess
fluoride ions, redissolves to give the complex ion [ScF6]3−. Scandium
halides are best prepared by heating the element in a current of
halogens.

Scandium hydride:
Scandium forms a hydride which is not quite stoichiometry, the number
of hydrogen atoms per atoms of scandium being nearer to 2. Its formula
may be written as ScH2. This compound contains hydrogen in the form
of hydride ion, H−. The compound probably contains one Sc3+ per two
H− ions. The third electron of Sc is present in the conduction band. That
is why solid ScH2 is a conductor of electricity.
Scandium carbide ScC2:
It obtained by heating the oxide with carbon at a high temperature of
about 1000 oC.

Sc2O3 + 7C → 2ScC2 + 3CO

It is an acetylide, as it reacts with water liberating acetylene. It has been

shown by conductivity and magnetic measurments that scandium
carbide is an ionic compound having Sc+ and C2− ions.
Titanium (Ti)
Occurrence:
Titanium constitutes about 0.58% by mass of the earth’s crust. It is the
10th most abundantly occurring elements in the earth’s crust. However,
its deposits are not very rich in the elements. The commercially useful
deposits for the extraction of the element are scare. The important ores
are rutile (TiO2) and ilmenite (FeTiO3).

Extraction:
1) By reduction process: Reduction of TiO2 in rutile ore on heating
with carbon is not satisfactory as it leads to the formation of stable
titanium carbide. Heating in air also leads to formation of titanium
nitride. Production of titanium on a large scale is, therefore, possibly by
converting oxide in rutile ore in to titanium tetrachloride, TiCl 4 and then
reducing the later with magnesium. This process of extraction is known
as Kroll process. In the actual process, chlorine is passed over rutile,
heated to about 900 oC with carbon.
TiO + C + 2Cl → TiCl + CO
The vapours of TiCl4 are condensed to get it in liquid state (B.P 136
o
C). It is purified by fractional distillation and then reduced by passing
it in vapour state over magnesium heated to 800 oC.

TiCl4 + 2Mg → Ti + 2MgCl2

The TiCl4 vapours continue attacking magnesium till nearly 85% of the
metal has reacted. Titanium is chipped off from the reactor
mechanically. The residual magnesium and magnesium chloride are
removed from the metal chips by leaching with dilute HCl.

2) By electrolysis in an inert atmosphere: Titanium can also be

prepared by the electrolysis of the ionic compounds, TiCl 2 in the fused
state. Sodium chloride and potassium chloride are added to lower the
M.P.
Chemical properties of Titanium:

i) Action with air: On exposure to air at ordinary temperature,

titanium reacts with oxygen and nitrogen to form a thin protective
surface coating of oxide and nitride. This coating protects the metal
from corrosion. It remains stable in air even at 400 oC.
ii) Combination with non-metals: At high temperature, the metal is
quite reactive. It combines with non-metals like oxygen, nitrogen,
halogens, carbon, boron and silicon. The compounds like TiN, TiC,
TiB are interstitial compounds. These are hard and have refractory
properties.
iii) Action of acids: Titanium is passive and resists attack by acids.
The passivity is due to formation of protective surface coating of oxide
and nitride. The metal dissolves slowly in hot concentrated
hydrochloric and nitric acids. It explodes with fuming nitric acid. It
dissolves in hydrofluoric acid giving hexafluoro complex compound.
Ti + 4HF → TiF4 + 2H2
TiF4 + 2HF → H2[TiF6]
iv) Action of alkalies:
The metal is not attacked by alkalies even at elevated temperature.

Application of Titanium:
Pure titanium is an extremely strong metal even stronger than iron due
to formation of a protective surface coating of oxide and nitride, it is
resistant to corrosion. Its mechanical properties are better than those of
steel. Due to its mechanical strength, lightness and resistant to
corrosion, the metal is of great technical importance. It is used as a
structural material in the fabrication of supersonic aircrafts, jet engines,
turbine engines and marine equipment. It is also used for hardening of
steel. Carbides of titanium used as a refractory material, its nitride in
the fabrication of high speed tools and its oxide as a white pigment.
Compounds of Titanium:
Titanium (II) oxide, TiO:
It is obtained by heating TiO2 with Ti. It is a non-stoichiometry
compound with composition TiO0.75. It changes readily to TiO2. Due to
this reaction, it acts as a strong reducing agent. For instance, it readily
reduces water to hydrogen. It is basic and ionic in character.
TiO + H2O → TiO2 + H2
Titanium (II) chloride, TiCl2:
It can be prepared by the reduction of titanium tetrachloride with
titanium metal.
TiCl4 + Ti → 2TiCl2
It can also be obtained by the disproportionation of Ti(III) chloride.
2TiCl3 → TiCl2 + TiCl4
Titanium tetrachloride is volatile and can be easily removed by
distillation. It also undergoes disproportionation giving titanium (IV)
chloride and titanium.
2TiCl2 → TiCl4 + Ti
Anhydrous TiCl3 is prepared by passing vapours of TiCl4 mixed with
excess of hydrogen through a red hot tube heated to about 650 oC.
2TiCl4 + H2 → 2TiCl3 (violet powder) + 2HCl
The hydrated titanium chloride exists in two forms having different
colours. These two forms have the formulae [Ti(H2O)6]3+ + 3Cl− and
[Ti(H2O)5 Cl]2+ + 2Cl−.
The anhydrous titanium oxide, Ti2O3, can be obtained by heating TiO2
to 1000 oC in a stream of hydrogen. It has the corundum structure; it is
highly stable and is attacked only by nitric acid.
2TiO2 + H2 → Ti2O3 + H2O
The titanium hydroxide, Ti(OH)3, is more basic than Ti(OH)4. In
general, Ti(III) compounds are more ionic than Ti(IV) compounds.
Ti(III) exist in aqueous solution as the blue violet [Ti(H2O)6]3+ complex
ion. Ti(III) compounds have strong reducing properties as they have a
tendency to change to Ti(IV) compounds. Ti(III) reduces
permanganates to Mn2+ ion.
Ti2O3 + O → 2TiO2
Ti3+ is used for the volumetric estimation of Fe3+ where NH4SCN is
used as an indicator. It gives red color as long as Fe3+ is present in the
solution.
FeCl3 + TiCl3 + H2O → FeCl2 + TiOCl2 + 2HCl
Ti3+ is also used for the estimation of organic nitrites where methylene
blue is used as an indicator. When a very slight excess of Ti 3+ is
generated, methylene blue is reduced and is rendered colorless.
RNO2 + FeCl3 + 6Ti3+ + 4H2O → RNH2 + 6TiO22+ + 6H+
Titanium (IV) oxide, TiO2 is the most important oxide of titanium, it
occurs in nature as rutile which is an important ore of titanium. It
dissolves in alkalies yielding titanates.
TiO2 + 2NaOH → Na2TiO3 + H2O
It heated with carbon in a stream of chlorine, it gives titanium
tetrachloride.
TiO2 + 2C + 2Cl2 → TiCl4 + 2CO
When Na2O is fused with TiO2, Na2TiO3 is formed. When Na2TiO3 is
heated in an atmosphere of hydrogen, non-stoichiometric compounds of
the formulae approximating to Na0.2-0.25TiO2 are formed. These compounds
are known as titanium bronze. Ti(IV) chloride can be prepared in the
laboratory by passing chlorine over a hot mixture of titanium dioxide and
carbon.
TiO2 + C + Cl2 → TiCl4 + CO2
TiCl4 gets readily hydrolyzed by water yielding titanium dioxide.
TiCl4 + 2H2O → TiO2 + 4HCl
If water is not present in excess, hydrolysis takes place only to a limited
extent, yielding titanium oxochloride, TiOCl2. TiCl4 is reduced to metallic
titanium on treatment with Mg or Na. TiCl 4 dissolves in concentrated HCl
yielding chloro complexes having formulae [TiCl 5(H2O)]− and [TiCl6]2−.
TiCl4 is a strong Lewis acid and accept electrons from strong oxygen
donors like ethers, alcohols and esters yielding addition compounds of the
type (R2O)TiCl4 and (R2O)2TiCl4. When TiCl4 is added to Al(C2H5)3 in
hexane, it yield a brown solid known as Ziegler-Natta catalyst, which is
employed in the conversion of ethane to straight chain polymer
 Vanadium (V)
Occurence: Its abundance is about 0.02% by mass of the earth’s crust.
Nearly ninty minerals containing vanadium are known but, since
concentrated deposits are very few, its extraction is not very
economical. Most important minerals are patronite (V 2S5), Vanidinite
[Pb5(VO4)3Cl] and carnotite [K(UO2)VO4.3/2H2O].
Extraction: Pure metal can be prepared only by reduction of its
compounds such as vanadium pentachloride (VCl5). The chlorides are
prepared more easily by working with ferro-vanadium, an alloy of iron
and vanadium.
Preparation of vanadium pentoxide: The vanadium ore, generally the
sulphide ore (patronite), is roasted in air and then fused with a mixture
of sodium carbonate and sodium nitrate when sodium vanadate, NaVO3
is formed. It is extracted with water and the solution treated with
ammonium chloride when ammonium vanadate, NH4VO3 separates out
as an orange colored precipitate, which on heating yields vanadium
pentoxide.
o
Preparation of Ferro-vanadium alloy: The alloy contains 35-45% of
vanadium. It is obtained by heating a mixture of vanadium pentoxide
and iron oxide with carbon in an electric furnace using carbon
electrodes. Some lime or fluorspar is added as a flux.
Preparation of Vanadium metal:
A fairly satisfactory process, known as the Jantesh process, for
preparing vanadium metal, consists in heating Ferro-vanadium alloy in
a current of chlorine when vanadium tetrachloride, VCl 4 is obtained as
a dark red liquid. This is separated from ferric chloride, also formed in
the reaction, by distillation and reduced by heating the vapour with
hydrogen at 600 oC.
2VCl4 + 4H2 (heated at 600 oC) → 2V + 8HCl
An alternate process known as the Beard and Crook’s process consists
in reduction of vanadium pentoxide with metallic calcium in an inert
atmosphere of helium or argon. Some iodine is also added. V2O5 reacts
with calcium and the reaction is being exothermic produces a high
temperature.
V2O5 + 5Ca → 2V + 5CaO
Chemical properties of Vanadium:

i) Vanadium is unreactive towards minerals acids at ordinary

temperatures. It dissolves in hot nitric acid, concentrated sulphuric acid
and aqua regia to form meta vanadic acid, HVO3.
V + 5HNO3 → 2H2O + 5NO2 + HVO3

ii) When fused with alkalies, it gives the corresponding vanadate

evolving hydrogen.
2V + 6NaOH + 2H2O → 2Na3VO4 + 5H2

iii) When heated with non-metal, it combines with oxygen forming

vanadium pentoxide, mixed with lower oxides.
4V + 5O2 → 2V2O5
iv) It combines with nitrogen at high temperature yielding vanadium
nitride, VN, which is an industrial compound. It also forms a sulphide
V2S3 by passing CS2 over V2O5.

v) It combines with halogens on heating giving compounds like VF5,

VCl4, VBr3 and VI3. These are co-valent volatile compounds and get
easily hydrolyzed by water.

vi) It reacts with carbon at high temperature to forms carbides, VC and

VC2. The first is an interstitial compound, white and hard. The second
one is an ionic compound and reacts with water liberating acetylene.
Compounds of Vanadium
Vanadium (II) oxide, VO is prepared by reducing V2O5 with H2 at about
2000oC. It is soluble in water. The addition of alkalies to its aqueous
solution yields the precipitate of V(OH)2, whereas the addition of acids
yield a water soluble violet colored complex [V(H2O)6]2+.

V2O5 + 3H2 (heated at 2000oC) → 2VO + 3H2O

Vanadium (II) chloride, VCl2 is obtained by reducing VCl4 vapours with

hydrogen in a red hot tube.

VCl4 + H2 → VCl2 + 2HCl

The vanadous ion V2+ is a strong reducing agent thus the violet solution
of VCl2 soon turns green because of its oxidation to trivalent state with
evolution of hydrogen (reduction of water).
Vanadium (II) sulphate, VSO4.7H2O is prepared by the electrolytic
reduction of vanadium pentoxide dissolved in sulphuric acid in the
presence of sulphur trioxide till the solution turns violet. It is soluble in
water and forms red violet monoclinic crystals which are isomorphous
with FeSO4.7H2O. The double salt, VSO4(NH4)2SO4.6H2O is
isomorphous with Mohr’s salt, FeSO4(NH4)2SO4.6H2O. It is strong
reducing agent. The violet coloured aqueous solution containing V2+ in
the form of [V(H2O)6]2+ becomes green due to oxidation of [V(H2O)6]3+
ion to [V(H2O)6]3+ with the liberation of hydrogen (reduction of water).

[V(H2O)6]2+ + H+ → [V(H2O)6]3+ + 1/2H2

Vanadium (V) Oxide, V2O5 is obtained as a red or orange solid on

thermal decomposition of ammonium meta vanadate, NH4VO3.

2NH4VO3 → V2O5 + 2NH3 + H2O

It should be colourless, but actually it is orange-red in colour due to
defect in solid state by which charge transfer transition in the visible
region are possible. It dissolves in acid solution to give salt of VOCl 2,
vanadyl chloride and VCl5, vanadium pentachloride.

V2O5 + 6HCl → 2VOCl2 + 3H2O + Cl2

V2O5 + 10HCl → 2VCl5 + 5H2O

It dissolves in alkalies giving vanadates.

V2O5 + 6NaOH → 3Na3VO4 + 3H2O

On reduction, it gives lower oxides.

It used as catalyst in the conversion of SO3 from SO2.

Vanadium (V) fluoride, VF5 can be obtained, when it combines with

fluorine at high temperature (300 oC).

2V + 5F2 → 2VF5

It may also prepared by heating VF4 at 600 oC in an atmosphere of

nitrogen.

It is volatile white solid melting at 19.5oC. When heated in air, it

changes in to oxifluoride.
VF5 is polymeric in solid and liquid phases consisting of VF6 octahedral
units joined together through V-F-V bridges as below:

In gaseous phase, VF5 is monomeric and probably has trigonal

bipyramidal structure.

Vanadium (V) oxotrichloride, VOCl3 as well oxotribromide, VOBr3 can

be prepared by halogenating V2O3.

V2O3 + 3X2 → 2VOX3 + O2

V2O3 + 3Cl2 → 2VOCl3 + O2
Vanadium oxotrichloride can be prepared by passing chlorine over a
mixture of vanadium pentoxide and carbon at red hot.

V2O5 + 3C + 3Cl2 → 2VOCl3 + 3CO

VOF3 can be prepared by treating vanadium oxotrichloride with

hydrofluoric acid in the cold.
VOCl3 + 3HF → VOF3 + 3HCl

The oxohalides are simple covalent compounds and are readily

hydrolysed.

VOCl3 + 2H2O → HVO3 + 3HCl

The fluorides and oxofluorides forms complexes with other metallic

fluorides.
VF5 + 2KF → K2[VF7]
VOF3 + 3NaF → Na3[VOF6]
 Chromium (Cr)
Occurrence:
It does not occur free in nature. In combined state, it occurs as chromite
ores, FeCr2O4 or FeO.Cr2O3. It also occurs as crocoisite, which is lead
chromate, PbCrO4. Chromium forms nearly 0.037% of earth’s crust.
Extraction:
The most important source for the extraction of chromium is the
chromite ore, FeO.Cr2O3. The concentrated ore is mixed with excess of
sodium carbonate and roasted in a reverberatory furnace in a free
supply of air, the chromium oxide present in the chromite ore is
converted in to sodium chromate (Na2CrO4)
4FeO.Cr2O3 + 8Na2CO3 + 7O2 → 8Na2CrO4 + 2Fe2O3↓ + 8CO2↑
Chromite ore (from air) Soluble Insoluble

The sodium chromate solution treated with sulphuric acid to converted

in to dichromate.
2Na2CrO4 + H2SO4 → Na2Cr2O7 + Na2SO4 + H2O
The solution is concentrated when the less soluble Na 2SO4 crystallises
out leaving behind the more soluble Na2Cr2O7 in solution. The solution
is further concentrated to get solid Na2Cr2O7 which is heated with
carbon to yield sodium chromite.
Na2Cr2O7 + 3C → Na2Cr2O4 (sodium chromite) + 3CO

Sodium chromite treated with water to give ppt of chromium oxide,

Cr2O3.
Na2Cr2O4 + H2O → Cr2O3(ppt) + 2NaOH

Chromic oxide, Cr2O3 is finally reduced to chromium by the

aluminothermic process. In this process, chromic oxide is mixed with
powdered aluminium in the proportion of 3:1 in a large size refractory
crucible of low thermal conductivity embedded in a bucket full of sand.
The sand helps to minimize the loss of heat by radiation.
Cr2O3 + 2Al → Al2O3 + 2Cr (92%); ΔH= −468.6 KJ
Ferrochrome:
It contains, 75% chromium and 25% iron, it is prepared by reducing
chromite ore with carbon in an electric furnace. It is extensively used
for alloying with iron to make special steel.
FeO.Cr2O3 + 4C → Fe + 2Cr + 4CO

Chemical properties of chromium:

It burns with excess of oxygen at about 2000oC forming green coloured
chromic oxide.
4Cr + 3O2 → 2Cr2O3
It reacts with nitrogen at elevated temperature, giving chromium
nitride.
Chromium does not attacked by water at ordinary temperature but it
decomposes steam at red heat to give chromic oxide and hydrogen.
2Cr + 3H2O → Cr2O3 + 3H2
Chromium dissolves in dilute acids slowly in cold but more rapidly on
heating, evolving hydrogen and giving blue solution of chromium(II)
salts.
Blue chromium (II) salt changed in to green chromium (III) salts due
to oxidation in air.
4CrCl2 + 4HCl + O2 → 4CrCl3 + 2H2O

With hot concentrated sulphuric acid, Cr gives chromium (III)

sulphate and SO2.
2Cr + 6H2SO4 → Cr2(SO4)3 + 6H2O + 3SO2

Concentrated nitric acid renders the metal passive due to the formation
of an insoluble surface layer of chromium (III) oxide as a result of
surface oxidation. Heated chromium combines with fluorine or dry
chlorine giving chromium (III) fluoride or chloride. Chromium acts as
good reducing agent in finely divided states.
2Cr + 3F2 → 2CrF3
2Cr + 3Cl2 → 2CrCl3
Compounds of chromium:
Anhydrous CrCl2, CrBr2 and CrI2 can be prepared in the following
manner at 500oC.
2CrX3 + H2 → 2CrX2 + 2HX

These dihalides get readily oxidized in air to CrX3. Aqueous solution

of Cr(III) ion is slightly acidic on account of hydrolysis.
[Cr(H2O)6]3+ ↔ [Cr(H2O)5OH]2+ + H+

When a base is added to an aqueous solution containing Cr(III) ions, a

dirty green ppt of hydrated chromium (III) hydroxide, Cr(OH)3.xH2O
results.
Cr3+ + 3OH− (aqueous medium) → Cr(OH)3 hydrated

The ppt dissolves when excess of base is added giving a deep green
solution which is characteristics of chromite ion.
Cr(OH)3 + 3OH− → [Cr(OH)6] 3−
Chromium (III) chloride, CrCl3 is obtained in anhydrous state by
passing chlorine either over heated chromium or over a mixture of
chromium(III) oxide and carbon heated strongly.
Cr2O3 + 3C + 3Cl2 → 2CrCl3 + 3CO

It can also be obtained by passing sulphur chloride vapour over hot

chromium (III) oxide.
2Cr2O3 + 6S2Cl2 → 4CrCl3 + 3SO2 + 9S

It can dissociate when heated above 1300oC.

2CrCl3 ↔ 2CrCl2 + Cl2

It forms three crystalline hexahydrate, all having the molecular formula

CrCl3.6H2O. There structure formulae are.
[Cr(H2O)4Cl2]Cl.2H2O ---- Dark Green ---- α-variety
[Cr(H2O)5Cl]Cl2.H2O ---- Light Green ---- γ-variety
[Cr(H2O)6]Cl3 ---- Greyish blue ---- β-variety
The hexa aqua ion [Cr(H2O)6]3+ is also present in chrome alum,
K2SO4.Cr2(SO4)3.24H2O which should also be written as
[K(H2O)6]2[Cr(H2O)6]2(SO4)4 or as [K(H2O)6][Cr(H2O)6](SO4)2. Some of
the common complexes of chromium are [Cr(NH3)6]3+, [Cr(NH3)5Cl]2+,
[Cr(NH3)3Cl3], [Cr(Oxalate)3]3− etc.
Chromium (III) oxide, Cr2O3 obtained by heating ammonium
dichromate. It is a green solid used as pigment and also as catalyst in a
number of reactions.
(NH4)2Cr2O7 → Cr2O3 + N2 + 4H2O

Chromium (IV) oxide, CrO2 is prepared by following manner.

CrO3 + H2 → CrO2 + H2O

It is ferromagnetic black coloured materials which are extensively used

in making recording tapes.
CrF4 can be prepared from its elements at elevated temperature.
Chromium (VI) oxide, CrO3 is a parent substance of number of
compounds in which the oxidation state of Cr is +6. It is obtained by
the action of concentrated sulphuric acid on a concentrated solution of
potassium dichromate.
K2Cr2O7 + 2H2SO4 → 2KHSO4 + H2O + 2CrO3

It is red crystalline solid which volatilizes at 110 oC and melts with

some decomposition at 190oC. On heating at 250oC, it decomposes
readily evolving oxygen.
4CrO3 → 2Cr2O3 + 3O2

It is readily soluble in water giving a red colour solution which is

highly acidic and contain a number of chromic acids. It is powerful
oxidizing agent. Some of the oxidizing reactions are represented below:
2CrO3 + 3H2S + 3H2SO4 → Cr2(SO4)3 + 3S + 6H2O
2CrO3 + 6FeSO4 + 6H2SO4 → Cr2(SO4)3 + 3Fe2(SO4)3 + 6H2O
2CrO3 + 3SnCl2 + 12HCl → 2CrCl3 + 3SnCl4 + 6H2O
It reacts with gaseous hydrogen chloride to give chromyl chloride.
CrO3 + 2HCl → CrO2Cl2 + H2O

It dissolves in alkalies to give chromates

CrO3 + 2NaOH → Na2CrO4 + H2O

Yellow chromate ion gives orange dichromate ion upon acidification.

2CrO42− + 2H+ → Cr2O72− + H2O

Aqueous solution of CrO3 yields chromic acids (monochromic acids)

CrO3 + H2O → H2CrO4

Higher chromic acid formed by condensation of 2 or 3 or more

molecules of chromic acid with the elimination of water.
2H2CrO4 → H2Cr2O7 (dichromic acid) + H2O
3H2CrO4 → H2Cr3O10 (trichromic acid) + 2H2O
Chromate ion has a tetrahedral structure with Cr atom lying at the
centre. Dichromate ion consists of two such tetrahedral.

Potassium dichromate, K2Cr2O7 is prepared by adding sulphuric acid to

a saturated solution of potassium chromate.
2K2CrO4 + H2SO4 → K2Cr2O7 (potassium dichromate) + K2SO4 + H2O

It is manufactured by mixing hot saturated solution of sodium

dichromate and potassium chloride.
Na2Cr2O7 + 2KCl → 2NaCl + K2Cr2O7

On strong heating, it decomposes to give chromic oxide and oxygen.

4K2Cr2O7 → 4K2CrO4 + 2Cr2O3 + 3O2
Potassium dichromate when heated with concentrated H2SO4 and
sodium chloride, gives red vapour of chromyl chloride.
K2C2rO7 + 4NaCl + 6H2SO4 → 2KHSO4 + 4NaHSO4 + 2CrO2Cl2 +
3H2O

It reacts with hydrochloric acid evolving chlorine.

K2Cr2O7 + 14HCl → 2KCl + 2CrCl3 + 7H2O + 3Cl2

Potassium dichromate is a powerful oxidizing agent, some typical

oxidation reactions are given below.
Cr2O72− + 6I− + 14H+ → 2Cr3+ + 7H2O + 3I2
Cr2O72− + 6Fe2+ + 14H+ → 2Cr3+ + 7H2O + 6Fe3+
Cr2O72− + 3SO32− + 8H+ → 2Cr3+ + 4H2O + 3SO42−
Cr2O72− + 3H2S + 8H+ → 2Cr3+ + 7H2O + 3S
Cr2O72− + 3SO2 + 2H+ → 2Cr3+ + H2O + 3SO42−
On addition of an alkali, the orange colour of potassium dichromate
solution changes to yellow due to the formation of potassium chromate.
On acidifying, the colour again changes to orange red owing to the
formation of dichromate.
2K2CrO4 + 2H2SO4 → 2K2Cr2O7 + K2SO4 + H2O

In dichromate solution, the Cr2O72− ions are in equilibrium with CrO42−.

Cr2O72− (orange red) + H2O ↔ 2CrO42− (yellow) + 2H+

Solution of chromates or dichromates treated with dil H 2SO4 and H2O2

formed blue coloured chromic peroxide.
2CrO42− + 2H+ + H2O2 → CrO(O2)2 (Blue) + 3H2O

Lead chromate, PbCrO4 (chrome yellow) is prepared by adding a

solution of sodium dichromate to a solution to lead nitrate or acetate.
Na2Cr2O7 + Pb(NO3)2 → 2PbCrO4
Manganese (Mn)
Occurrence: Manganese occurs relatively abundantly as it constitutes
about 0.085% of the earth crust. Among the heavy metals, it occurs next
to iron. The most important of these deposits are the oxides MnO 2
(pyrolusite), Mn2O3 (braunite) and Mn3O4 (hausmannite).
Extraction: Manganese is obtained from its oxide ore by reduction
with carbon or aluminium. The concentration of the ore in this case is
not needed as the naturally occurring pyrolusite or hausmannite usually
contains over 90% of MnO2 or Mn3O4.
1) Reduction of the oxide with carbon: The Mn3O4, on strong heating
with carbon, yields manganese. The manganese obtained in this manner
is not pure. It is contaminated with carbon.
Mn3O4 + 4C → 3Mn + 4CO
2) By aluminothermic process: MnO2 first converted in to Mn3O4
(mangnomangnic oxide) upon heating to redness. Then it reduced on
heating with aluminium powder. It is purified by distillation under
reduced pressure.
Physical properties: Manganese is a grey metal and exists in three
allotropic forms which are stable over various temperature ranges. Its
M.P. is 1245oC and B.P. is 2150oC. It is paramagnetic.
Chemical properties:
1) Reaction with Non-metals: Upon heating, Mn reacts with non-
metals vigorously. It combines with fluorine yielding MnF2 and MnF3.
It burns in chlorine to give the chloride MnCl2 and combine with
nitrogen to give nitride Mn3N2. It combines with oxygen to give various
oxides, with sulphur, forms MnS, with carbon forms carbide, Mn2C.
2) Reaction with acids: Manganese is fairly electropositive (oxidation
potential is 1.05V). It dissolves readily in dilute acids evolving
hydrogen
Mn + 2H+ → Mn2+ + H2
3) Action of water: Manganese decomposes water even in cold with
the evolution of hydrogen. Upon heating rate of decomposition
increases.
Mn + 2H2O → Mn(OH)2 + H2
Uses of manganese: About 80% of manganese produced, used in
manufacturing of manganese steel. Mn when added to steel performs
two functions. Id added in small amount, it acts as scavenger (cleaning
agent). When added in large amount up to 14%, it imparts special
hardness and toughness to the steel.
Chemistry of Mn(II): Mn2+ ion is fairly stable and does not change in
to higher oxidation state easily. Infact, its potential for the reaction is
negative being −1.51V. The solution of Mn(II) ions in neutral and
acidic medium can remain unaffected even on prolonged exposure to
oxygen. Mn(II) ion is not reducing agent.
Mn2+ → Mn3+ + e−
Complexes of Mn(II): Complexes such as Mn(ClO4)2.6H2O and
[Mn(H2O)6]2+ contains Mn2+. These complexes are octahedral and pink
in colour. They are readily attacked by oxidizing as well as reducing
agents. Complexes such as [Mn(CN)6]4− and [Mn(CN)5NO]3− are low
spin complexes with only one unpaired electron (B.M=1.8 to 2.1).
They can easily oxidized.
[Mn(CN)6]4− → [Mn(CN)6]3− + e−
Chemistry of Mn(III):
Mn(III) ion can be easily reduced, it acts as a strong oxidizing agent. It
is so strong that it can evolve oxygen even from water. In aqueous
solution, Mn(III) ion undergoes disproportionation to give Mn(II) and
Mn(IV).
2Mn3+ + 2H2O → Mn2+ + MnO2 (S) + 4H+

Complexes of Mn(III) are [Mn(CN)6]3− and [Mn(C2O4)]3− are obtained

as:
Mn3+ + 6CN− → [Mn(CN)6]3− Low spin complex
Mn3+ + 3(C2O4)2− → [Mn(C2O4)]3− High spin complex

Basic acetate of Mn(III), i.e [Mn3O(CH3COO)6(H2O)3]+ is also known.

It is used for oxidation of toluene to phenol.
Chemistry of Mn(IV):
Manganese in +4 oxidation state exists in MnO2, which is commonly
prepared by heating Mn in oxygen. The oxide is insoluble in water and
reacts with hot concentrated H2SO4 and HCl to release Cl2 and O2
respectively.
2MnO2 + 2H2SO4 → 2MnSO4 + 2H2O + O2
MnO2 + 4HCl → 2MnCl2 + 2H2O + Cl2

When fused with NaOH, it gives Na2MnO4, which is a green solid.

MnO2 is strong oxidizing agent and commonly used in oxidation of
organic compounds. It can also be used in preparation of potassium
permanganate.
MnO2 (fused with NaOH and KNO2) → K2MnO4
2K2MnO4 + 2H2O (electrolytic oxidation) → 2KMnO4 + 2KOH + 2H2

MnO2 is also used as catalyst in the laboratory preparation of oxygen

from KClO3. Complexes of Mn(IV) are exist such as K2[MnF6],
Chemistry of Mn(V):
Manganese (V) compounds are very unstable. Only compound is
known, i.e K3MnO4. It is obtained by reacting an aqueous solution of
KMnO4 with K2SO3. K3MnO4 is bright blue compound which is quite
unstable.
KMnO4 + K2SO3 + H2O → K3MnO4 + H2SO4

Chemistry of Mn(VI):
In +6 state, Mn exist as MnO42−. The ion stable only in highly alkaline
solutions. In acidic medium, it changes readily in to permanganate ion
in which Mn exist +7 states.
3MnO42− + 4H+ → MnO2(S) + 2MnO4− + 2H2O

Mangnate ion changes in to permanganate ion even by passing CO2 in

its solution.
3MnO4− + 2H2O + 4CO2 → MnO2(S) + 2MnO4− + 4HCO3−
Chemistry of Mn(VII): Manganese (VII) is best known as permanganate
ion, MnO4−. It is one of the strongest oxidizing agents. The aqueous
chemistry of Mn(VII) is infact the chemistry of MnO 4−.
Potassium permanganate: It is one of the most important compound of
Mn(VII). Its preparation from potassium manganite may be represented as:
3K2MnO4 + 2H2SO4 → 2K2SO4 + 2KMnO4 + MnO2↓ + 2H2O
MnO2 is removed by filtration. Solid manganese (IV) oxide is fused with
potassium hydroxide and the melt is well stirred in contact with air.
2MnO2 + 4KOH + O2 → 2K2MnO4 + 2H2O
The mass is extracted with water when a green solution of potassium
manganate is obtained. The chlorine gas is passed to oxidise potassium
manganite in to potassium permanganate.
2K2MnO4 + Cl2 → 2KMnO4 + 2KCl
The solution is concentrated when the less soluble potassium
permanganate separates out leaving the more soluble potassium chloride in
solution. During electrolysis, the manganite ion is oxidized to the
permanganate ion in the anodic compartment.
MnO42− → MnO4− + e−
Chemical properties: When heated in alkaline solution, it decomposes
evolving oxygen.
2KMnO4 → K2MnO4 + MnO2 + O2
4KMnO4 + 4KOH → 4K2MnO4 + 2H2O + O2
On treatment with concentrated H2SO4, it gives manganese (VII) oxide,
which decomposes explosively on heating.
2KMnO4 + H2SO4 → Mn2O7 + K2SO4 + H2O
Potassium permanganate is a powerful oxidizing agent in aqueous
medium depends upon whether reaction carried out in alkaline, neutral
or acidic medium.
a) In alkaline solution: Permanganate ion is first reduced to manganite
ion and then to insoluble manganese (IV) oxide.
Iodides are oxidized to iodates by alkaline potassium permanganate.
Alkaline potassium permanganate also oxidizes ethylene to glycol and
toluene to benzoic acid.
2MnO4− + H2O + I− → 2MnO2 + 2OH− + IO3−
C2H4 + H2O + O → HO-CH2-CH2-OH
C6H5-CH3 + 3O → C6H5COOH + H2O

b) In neutral solution: It reduced directly to MnO2.

2MnO4− + H2O → 2MnO2 + 2OH− + 3O

Hydrogen sulphide is oxidized to sulphur and sodium thiosulphate is

oxidized to sodium sulphate and sulphur by the action of neutral
KMnO4.
2MnO4− + H2S → 2MnO2 + 3S + 2H2O + 2OH−
2MnO4− + 3S2O32− + H2O → 2MnO2 + 3SO42− + 3S + 2OH−
c) In acidic solution: KMnO4 is reduced to manganese (II) ion and
five atoms of oxygen.

2MnO4− + 6H+ → Mn2+ + 3H2O + 5O

2KMnO4 + 3H2SO4 → K2SO4 + 2MnSO4 + 3H2O + 5O
2MnO4− + 16H+ + 10Fe2+ → 2Mn2+ + 8H2O + 10Fe3+
2MnO4− + 16H+ + 5C2O­42− → 2Mn2+ + 8H2O + 10CO2
2MnO4− + 6H+ + 5SO­32− → 2Mn2+ + 3H2O + 5SO­42−
2MnO4− + 16H+ + 10I− → 2Mn2+ + 8H2O + 5I2
2MnO4− + 16H+ + 10X− → 2Mn2+ + 8H2O + 5X2
2MnO4− + 16H+ + 5S2− → 2Mn2+ + 8H2O + 5S
2MnO4− + 5SO2 + 2H2O → 2Mn2+ + 5SO­42− + 4H+
CH3CH2OH + O → CH3CHO + H2O
 Iron (Fe)

Occurrence:
Iron occurs seldom in native form. Some ballistic rocks are said to
contain it in small quantities in free states. It is believed that the inner
core of earth consists largely of metallic iron. In combined state iron
occurs very abundantly constituting about 4.7 percent of the earth’s
crust. It is fourth in most abundant amongst all elements, the first three
being oxygen, silicon and aluminium. The most important ores of iron
are oxides, carbonates and sulphides. Magnetite (Fe3O4), Haematite
(Fe2O3), Lymonite or hydrated ferric oxide (Fe2O3.3H2O), Siderite or
Spathic iron ore (FeCO3), Iron pyrite (FeS2).

Varieties of Iron:
There are three commercial varieties of iron which are put to different
industrial uses. They are cost iron, wrought iron and steel. Differences
because of carbon and phosphorus content.
 Cast Iron (Pig Iron):

Extraction:
Cost iron chiefly extracted from haematite ore by heating in the
presence of coke and lime stone in a blast furnace. Cast iron contain
2.6 to 4.3% C, 0.7 to 3% Si and small quantities of P, S and Mn.

C + O­2 → CO2
CO2 + C → 2CO
3CO + Fe2O3 → 2Fe + 3CO2
CO + Fe3O4 → 3FeO + CO2
CO + FeO → Fe + CO2
Wrought Iron: It is pure form of iron, it contain only 0.5% impurities in
which carbon present in 0.2%.
Manufacturing: It is obtained by purifying cast iron by the process
known as puddling (meaning stirring). The cast iron is heated on the hearth
of a reverberatory furnace (puddling furnce) lined with haematite (Fe 2O3).
The cast iron is melted and stirred. The haematite supplies the oxygen
required to oxidise the C, Si, Mn and P.
3C + Fe2O3 → 3CO + 2Fe
3Si + 2Fe2O3 → 4Fe + 3SiO3
Carbon monoxide escapes. Manganous oxide and silica combines to form
manganous silicate (slag). Phosphorus pentaoxide combines with
haematite to form ferric phosphate slag.
MnO + SiO2 → MnSiO3 (slag)
P2O5 + Fe2O3 → 2FePO4 (slag)
Steel: The carbon content of steel is intermediate between that of cast iron
and wrought iron. It varies between 0.1 to 1.5%. The hardness of steel
increases with increase in carbon contents. Steel usually contain
manganese as well sometimes, other elements such as Cr, Si, Ni, W, V and
Physical properties of iron:
Pure iron is grey white lusturous metal melting at 1536oC. It boils at
about 3000oC. Its specific gravity is 7.86 and specific heat 0.11. It
possesses strong magnetic properties (ferromagnetism) which it loses
when heated above 766oC. The metal exhibits allotropy. It exhibits in
three forms (α-iron, γ-iron and δ-iron), which differ from one another in
crystalline shape only.

Chemical properties of iron:

1) Action of air (Rusting of iron):
When exposed to air or moisture, iron gets readily oxidized to a
hydrous oxide, known as rust of iron. It consists mainly of hydrated
iron oxide, 2Fe2O3.3H2O together with small quantity of FeCO3.
Electrochemical theory of rusting: Rusting is an electrochemical
phenomenon and takes place due to local action. When impure iron
comes in contact with water containing CO2, an internal voltaic cell is
set up. The iron and other impurities acts like electrode while water
containing CO2 acts as electrolytes. Iron passes in to solution as Fe 2+
more readily.
Fe + 2H+ → Fe2+ + H2
The ferrous ion in aqueous solution get oxidized in the presence of air
to Fe3+ ion also generating hydroxyl ions and precipitating out as ferric
hydroxide.
4Fe2+ + O2 + 2H2O → 4Fe3+ + 4OH−
Fe3+ + 3OH− → Fe(OH)3 (Rust)
Protection of iron from rusting: Iron is protected from rusting by
coating it with zinc or by painting or white washing it with lime. Iron
pipes are protected by heating and then dipping in a solution of coal tar.
A good method consists in electroplating iron with metals like Ni or Cr.
An alternative method is galvanizing iron rods or sheets or wires by
2) Action of water: Iron displaces hydrogen from steam at high
temperature.
3Fe + 4H2O → Fe3O4 + 4H2
Iron displaces less electropositive metals such as Cu, Ag etc from their
salts.
Fe + CuSO4 → FeSO4 + Cu
Iron dissolves in dilute HCl or H2SO4 liberating hydrogen.
Fe + 2HCl → FeCl2 + H2
Fe + H2SO4 → FeSO4 + H2
Iron dissolves in dil HNO3 forms ammonium nitrate and when placed in
highly concentrated HNO3, it becomes passive.
4Fe + 10HNO3 → 4Fe(NO3)2 + NH4NO3 + 3H2O
Oxides of iron: Ferric oxide reacts with Na2CO3 to give sodium ferrite.
Fe3O4 is a mixed oxide and written as FeO.Fe2O3.
Fe2O3 + Na2CO3 → 2NaFeO2 + CO2
Iron (II) in aqueous solution exists as [Fe(H 2O)6]2+. This ion is pale green
in colour and can be readily oxidized even of exposure to air in to Fe 3+.
2Fe2+ + 1/2O2 + 2H+ → 2Fe3+ + H2O
Solution of Fe2+ ion is treated with an alkali, it precipitates out as Fe(OH) 2.
It is white substance, immediately turns dark brown due to its oxidation to
iron (III) state in the presence of air, in alkaline medium.
4Fe(OH)2 + O2 + 2H2O → 4Fe(OH)3
Fe2+ ion is strong reducing agent. It reduces Hg 2+ to Hg+, Sn4+ to Sn2+ and
MnO4− to Mn2+ and so on.
Hg2+ + 2Fe2+ → Fe3+ + Hg+
Sn4+ + 2Fe2+ → Sn2+ + 2Fe3+
MnO4− + 8H+ + 5Fe2+ → Mn2+ + 5Fe3+ + 4H2O
Iron (II) chloride combine with ammonia gas yielding the hexa amine
complex which contains the complex hexa amine ion, [Fe(NH3)6]2+. The
Potassium ferrocyanide, K4[Fe(CN)6]:

Preparation:
Hydrogen cyanide present in coal gas passes through a washer
containing FeSO4 and KOH and produced potassium ferrocyanide.
HCN + KOH → KCN + H2O
6KCN + FeSO4 → K4[Fe(CN)6] + K2SO4
Another commercial method for preparation of potassium ferrocyanide
is the passing of coal gas containing HCN over the mixture of ferrous
and ferric hydroxide. Ferrous and ferric hydroxides absorb the HCN
and purify the coal gas. Following reaction takes place.
Fe(OH)2 + 2HCN → Fe(CN)2 + 2H2O
Fe(OH)3 + 3HCN → Fe(CN)3 + 3H2O
3Fe(CN)2 + 4Fe(CN)3 → Fe4[Fe(CN)6]3 (ferric ferrocyanide-prussian
blue)
Prussian blue complex boiled with lime, yield calcium ferrocyanide.
Fe [Fe(CN) ] + 6Ca(OH) → 3Ca [Fe(CN) ] + 4Fe(OH)
Calcium ferrocyanide passes in to solution to which some K2CO3
added.
3Ca2[Fe(CN)6] + 2K2CO3 → 2CaCO3 + K4[Fe(CN)6]

Calcium carbonate removed by filtration and solution evaporated to

obtain the crystal of potassium ferrocyanide.
In the laboratory, potassium ferrocyanide obtained by mixing a solution
of iron(II) sulphate with that of potassium cyanide until a small amount
of precipitate iron(II) cyanide remains undissolved.
FeSO4 + 2KCN → Fe(CN)2 + K2SO4
Fe(CN)2 + 4KCN → K4[Fe(CN)6]
Chemical properties: It is very stable compound which in solution
ionizes as:
K4[Fe(CN)6] → 4K+ + [Fe(CN)6]4−
When heated, it decomposes to give iron carbide, potassium cyanide and
nitrogen.
K4[Fe(CN)6] → 4KCN + FeC2 + N2
When boiled with dil H2SO4, hydrogen cyanide evolved. On treatment with
hot concentrated H2SO4, CO is evolved.
2K4[Fe(CN)6] + 3H2SO4 → K2Fe[Fe(CN)6] + 3K2SO4 + 6HCN
K4[Fe(CN)6] + 6H2SO4 + 6H2O → 3(NH4)2SO4 + 2K2SO4 + 6CO + FeSO4
It combines with cupric salts to form reddish brown precipitate of cupric
ferrocyanide.
K4[Fe(CN)6] + 2Cu2+ → 4K+ + Cu2[Fe(CN)6] (reddish brown)
It reacts with ferric salts to give a blue precipitate of ferric ferrocyanide
called Prussian blue.
3K4[Fe(CN)6] + 4Fe3+ → Fe4[Fe(CN)6]3 + 12K+
Ferrocyanide ion can be oxidized in to ferrocyanide ion on treatment with
chlorine.
Potassium ferricyanide, K3[Fe(CN)6]:
It can be prepared by the oxidation of potassium ferrocyanide by
chlorine or hydrogen peroxide.
2K4[Fe(CN)6] + Cl2 → 2K3[Fe(CN)6] + 2KCl
2K4[Fe(CN)6] + H2O2 → 2K3[Fe(CN)6] + 2KOH
Chemical properties:
It can be readily reduced in to potassium ferrocyanide in alkaline
solution.
2K3[Fe(CN)6] + 2KOH → 2K4[Fe(CN)6] + H2O + [O]
On adding an Fe(III) salt to potassium ferrocyanide, a dark blue
precipitate of Prussian blue is obtained.
Fe3+ + [Fe(CN)6]4− → Fe[Fe(CN)6] –
FeCl3 + K4[Fe(CN)6] → K{Fe[Fe(CN)6]} + 3KCl
Potassium ferric ferrocyanide
 Cobalt (Co)

Occurrence: It constitutes about 0.002% of the earth’s crust. It occurs

in combination with sulphur and arsenic. The chief ores are:
i) Speiss cobalt or smaltite, CoAs2
ii) Cobalt glance or cobaltite, CoAsS
iii) Cobalt bloom, Co2(AsO4).8H2O
iv) Linnacite, Co3S4
Extraction: The extraction of cobalt from its ores involves the
following steps:
a) Roasting and smelting of ores: The ore is finely powdered and then
roasted when most of the sulphur and arsenic are volatilized off. It is
then mixed with lime stone and sand and smelted in a small blast
furnace. The iron present in the ore rises above as ferrous silicate slag.
The rest of the metals separated in to two layers, the upper layer known
as speiss consisting mainly of arsenite of nickel, cobalt, iron and copper
and the lower layer consisting of impure silver.
b) Roasting the speiss with NaCl: The speiss is separated, ground and
roasted with sodium chloride in a reverberatory furnace. Most of the
arsenic and sulphur are driven off while the metals are converted in to
thin chloride.
c) Separation of iron and copper: The roasted mass is extracted with
water and lime is added to precipitate iron, arsenic and antimony.
Copper that goes in to the filtrate is removed by adding sodium
carbonate while nickel and cobalt remain in solution as chlorides.
Silver, if present is extracted by cyanide process.
d) Separation of nickel by cobalt: Cobalt is precipitated out as cobalt
(III) hydroxide, almost free from nickel, from the solution of chlorides
of cobalt and nickel on the addition of lime and bleaching powder.
CoCl2 + Ca(OH)2 → Co(OH)2 + CaCl2
2Co(OH)2 + H2O + CaOCl2 → 2Co(OH)3 + CaCl2
Nickel that remains in solution can be precipitated as basic carbonate
on the addition of sodium carbonate. Cobalt (III) hydroxide ignited as
follow:
12Co(OH)2 → 4Co3O4 + 18H2O + O2
e) Reduction of Co3O4: Co3O4 is reduced to the metal cobalt either by
heating with carbon and lime stone in an electric furnace or by means
of aluminium (Goldschmidt process).
Co3O4 + 4C → 3Co + 4CO
Co3O4 + 8Al → 9Co + 4Al2O3
f) Refining: The metal is refined electrolytically using solution of
cobalt ammonium sulphate as the electrolyte. Impure metal is made the
anode while the pure cobalt acts as the cathode.
Chemical properties: It is slowly attacked by dil HCl and dil H2SO4
evolving hydrogen and forming cobalt (II) salts.
Co + H2SO4 → CoSO4 + H2
Co + 2HCl → CoCl2 + H2
It is readily attacked by dil HNO3. It is rendered passive on treatment
with concentrated HNO3.
3Co + 8HNO3 → 3Co(NO3)2 + 2NO + 4H2O
Co3+ ion is strong oxidizing agent and therefore, gets itself reduced to
cobalt(II) state easily. It can oxidises water to oxygen readily.
 Nickel (Ni)

Occurence:
It is found in nature mainly in combination with arsenic, antimony and
sulphur. The chief ore of nickel are:
i) Pentlandite- a copper, nickel and iron sulphide (22% nickel).
ii) Garnierite- a double silicate of nickel and magnesium,
NiMgSiO3.H2O
iii) Kupfer nickel-NiAs
iv) Nickel glance- NiAsS
Pentlandite ore constitute the principal source of nickel.

Extraction: It involves following steps.

a) Concentration of the ores: The Sudbury ore deposits contain about
14% of pentlandite mixed with other metallic ores. The first step is to
separate the pentlandite. This is done by the usual froath floatation
process.
b) Roasting: The concentrated ore is then roasted in tall furnaces about
9 meter height and 6.5 meter wide. This continues for 8-10 weeks when
most of the iron (II) sulphide is converted in to iron (II) oxide and
sulphur dioxide.
2FeS2 + 5O2 → 2FeO + 4SO2
Cobalt (II) and Nickel (II) sulphides present in the ore remain almost
unaffescted.
c) Smelting: The roasted material is mixed with coke and quartz and
then smelted in a blast furnace. Most of the iron (II) sulphide, which
escaped oxidation during roasting, is now converted in to iron (II)
oxide. Any iron (III) oxide that might have been produced during
roasting is also reduced by coke to iron (II). The entire amount of iron
(II) oxide is converted in to iron (II) silicate slag on interaction with
silica.
FeO + SiO2 → FeSiO3 (slag)
The slag being lighter floats above the heavier impure sulphides of
nickel and cobalt together with a little bit of iron. This heavier mass is
known as matte.
d) Bassemerisation:
The matte is heated in a Bassemer converter having a basic lining and
fitted with tuyeres to admit hot air under pressure. A silicious flux is
added and the hot blast of air is blown through. The remaining iron (II)
sulphide is oxidized to iron (II) oxide which combines with silica to
form iron (II) silicate slag and is easily skimmed off. The bassemerised
matte, thus obtained contains around 56% of Ni, 25-30% of Cu, 15-
16% of S and 0.2-0.4% of Fe.
e) Conversion of bassemerised matte in to pure nickel:
Pure nickel can be extracted from bassemerised Ni-Cu matte by either
the Mond process or by electrolytic process.
The Mond process: The matte is first roasted in order to convert nickel (II) and
copper (II) sulphides to respective oxides. The oxide mixture is digested with
dilute sulphuric acid at 80oC. Copper (II) oxide dissolves giving copper (II)
sulphate.
CuO + H2SO4 → CuSO4 + H2O
Nickel (II) oxide remains as such. It is dried and introduced at the top of a
reducing tower maintained at a temperature of 200 oC. A current of water gas (CO
+ H2) is led up the tower which reduces the oxide of the metallic state.
NiO + H2 → Ni + H2O
NiO + CO → Ni + CO2
The crude nickel containing copper and iron as impurities is led in to another
tower called volatilizing tower, maintained at 50 oC. A current of CO is passed up
through the tower when volatile nickel carbonyl, Ni(CO) 4 is formed. The carbonyl
vapours are then led through another tower, called decomposer, filled with nickel
shots and heated to 150-180oC where the carbonyl decomposes to give pure Ni
and CO.
Ni(CO)4 → Ni + 4CO (carbon monoxide)
The CO can be used again. Nickel obtained by this process is 92.8% pure. It may
be further refined electrolytically using nickel (II) ammonium sulphate as the
electrolyte. Impure nickel is made the anode while pure nickel is used as the
Chemical properties of nickel:
It reacts with steam at a high temperature giving hydrogen.
Ni + H2O (steam) → NiO + H2
Nickel is more inert to chemical oxidation than iron and cobalt. It
evolves hydrogen from dilute mineral acid.
Ni + H2SO4 → NiSO4 + H2
Ni + 2HCl → NiCl2 + H2
When added to concentrate HNO3, the metal becomes passive like
iron and cobalt. It readily dissolves in aqua regia. It resists the attack
of alkalies. It is attacked by halogens forming metal halides.
Ni + Cl2 → NiCl2
 Copper (Cu)
Occurrence: Copper constitutes only 0.0001% of earth’s crust. Its ores
however are concentrated and therefore can be easily be worked for its
extraction. The principal ores are the sulphides and oxides.
Sulphide ores: copper glance (Cu2S), copper pyrites (CuFeS2)
Oxide ores: cuprite (Cu2O), Malachite {Cu(OH)2.CuCO3}
Extraction: Copper is extracted mostly from copper pyrites. The
concentrated ore is roasted in a current of air in a reverberatory furnace
when a part of the sulphur is removed as sulphur dioxide and impurities
of arsenic and antimony are removed as volatile oxides. A mixture
chiefly consisting of copper (I) and iron (II) sulphides is left behind.
2CuFeS2 + O2 → Cu2S + 2FeS + SO2
The roasted ore is then mixed with some coke and sand, heated strongly
in a blast furnace (smelting). Most of the iron sulphide is converted in
to the oxide which is removed as a slag.
2FeS + 3O2 → 2FeO + 2SO2
FeO + SiO2 → FeSiO3 (slag)
The molten mixture of Cu2S and FeS obtained above is transferred to a
bassemer converter and a blast of air mixed with sand is blown through
the molten mass. The following reaction takes place.
2FeS + 3O2 → 2FeO + 2SO2
FeO + SiO2 → FeSiO3 (slag)
2Cu2S + 3O2 → 2Cu2O + 2SO2
2Cu2O + Cu2S → 6Cu + SO2
The molten copper thus obtained is about 99% pure. It is called blister
copper because of blistered appearance due to the escape of gaseous
bubbles during cooling of the molten metal. It is used as such for many
purposes such as in the manufacturing of pipes, boilers etc.

Chemical properties of copper: It is not attacked by dry air at

ordinary temperatures. But when heated to redness in air or oxygen, it
first forms Cu2O and then CuO. If temperature is too high CuO again
changes in to Cu2O.
2Cu + O2 (air) at red hot → Cu2O + O2 → 2CuO
In presence of moisture and atmospheric CO2, copper converted in to
green layer of basic carbonate, CuCO3.Cu(OH)2. This layer protects
rest of the metals from further action. In the presence of air, mineral
acids dissolve the metal forming corresponding salt and water.
Cu + 2HCl + 1/2O2 (air) → CuCl2 + H2O
Cu + H2SO4 + 1/2O2 (air) → CuSO4 + H2O
Mineral acids possessing oxidizing properties (nitric and conc H 2SO4)
readily attack copper, yielding in each case the copper (II) salts, water
and a reduction product of the acid.
Cu + 2H2SO4 (conc) → CuSO4 + 2H2O + SO2
3Cu + 8HNO3 (dil) → 3Cu(NO3)2 + 4H2O + 2NO
Cu + 8HNO3 (conc) → 3Cu(NO3)2 + 2H2O + 2NO2
Copper combines with chlorine and other halogens to form halides.
Cu + Cl2 → CuCl2
Copper dissolves in aqueous ammonia in the presence of air or
oxygen, owing to formation of the complex ion, [Cu(NH3)4]2+.
It dissolves in aqueous solution of potassium cyanide yielding the
complex, [Cu(CN)4]2−. Copper displaces silver and mercury from solutions
of their salts.
Cu + 2AgNO3 → Cu(NO3)2 + 2Ag
Cu + 2Ag+ → Cu2+ + 2Ag
Cuprous oxide, Cu2O is dissolved in dil sulphuric acid, the product is
copper (II) sulphate and not copper (I) sulphate.
Cu2O (s) + 2H+ → 2Cu+ + H2O
2Cu+ → Cu2+ + Cu(s)
Cuprous chloride is added with KCl as follow:
CuCl + KCl → K[CuCl2]
Cuprous chloride dissolves in aqueous ammonia, the ammonical cuprous
chloride absorb CO.
CuCl + CO → CuCOCl
CuCl is heated in a stream of ethylene, it forms the stable compound.
CuCl + C2H4 → Cu(C2H4)Cl
Cuprous iodide can be prepared by reduction of cupric salt by iodide ions.
2Cu2+ + 4I− → 2CuI + I2
When KI is added to a solution of CuSO4, a ppt of CuI mixed with I2 is obtained.
2Cu2+ + 2I− → 2Cu+ + I2
2Cu+ + 2I− → 2CuI
When KCN is added to a solution of CuSO4, first the insoluble CuCN is obtained
which dissolves in excess of KCN to give the complex potassium
tetracyanocuprate(I), K3[Cu(CN)4].
2Cu2+ + 2CN− → 2Cu+ + C2N2
2Cu+ + 2CN− → 2CuCN (ppt)
CuCN + 3CN− → [Cu(CN)4]3− (soluble)
Solution of Cu(II) salts are acidic due to hydrolysis.
2Cu2+ + H2O ↔ [Cu(OH)]+ + H+
When a base added to a solution containing Cu2+ ions, a light blue coloured ppt of
Cu(OH)2.
Cu2+ + 2OH− → Cu(OH)2
If some aqueous ammonia is added in Cu(OH)2, it dissolves in and giving an intense
blue solution due to formation of complex.
Cu(OH)2 + 4NH3 → [Cu(NH3)4]2+ + 2OH−
The copper ammonia complex decomposes on the addition of acids.
[Cu(NH3)4]2+ + 4H+ → Cu2+ + 4NH4+
The complex also decomposes on heating to liberate ammonia gas.
 Zinc (Zn)

Occurence: Zinc occurs mainly in combined state, the most important

ore being zinc blend, ZnS. The other ores are calamine (ZnCO3), Zincite
(ZnO) and silicious zinc (Zn2SiO4.H2O).
Extraction: Zinc blend and calamine are only ores of commercial
interest.
a) Concentration: The ore is first crushed to fine powder and then
concentrated by froth floatation process.
b) Roasting: The concentrated ore is roasted in a current of air in a
rotary shaft furnace at 900oC to convert the sulphide in to the oxide.
2ZnS + 3O2 → 2ZnO + 2SO2
High temperature calcination of zinc blende is necessary to decompose
any zinc sulphate which may be formed during roasting.
2ZnSO4 → 2ZnO + 2SO2 + O2
Roasting in the case of calamine is not necessary. Simple heating
converts the ore in to ZnO and eliminates moisture.
ZnCO → ZnO + CO
c) Reduction: The oxide obtained above is mixed with crushed coke
and heated to 1400-1450oC in fire clay retorts when the oxide is
reduced to the metal. Zinc being volatilize distils over and is
condensed.
ZnO + C → Zn + CO
ZnO + CO → Zn + CO2
d) Refining: Zinc obtained in the above process contaminated with
cadmium, pure zinc can be obtained by fractional distillation. The metal
can also be refined by electrolysis. In electrolytic refining, impure is
made of anode and pure zinc plates are made the cathode in an
electrolytic cell. Zinc sulphate solution mixed with a little H2SO4 is
used as a electrolytes. When electrical current passed, pure zinc is
deposited on the cathode.

Chemical properties of zinc: When Zn is heated in air to about 500oC,

it burns to form a white cloud of zinc oxide which settles to form a
wooly flocks generally called “Philosophers wool”.
Pure zinc can not be reacts with water but impure zinc decomposes
steam quite readily with the evolution of hydrogen.
Zn + H2O → ZnO + H2
It forms basic carbonate in moist air which dulls its lusture and forms a
bluish grey film on its surface.
4Zn + 3H2O + 2O2 + CO2 → ZnCO3.3Zn(OH)3
Pure zinc does not reacts with dilute mineral acids but it reacts readily
on the the surface of other metal and evolving H2.
Zn + 2H+ → Zn2+ + H2
The reaction with sulphuric acid depends on the concentration of the
acid and the temperature of the reaction. if the acid is dilute and cold,
zinc sulphate and hydrogen are formed.
Zn + H2SO4 → ZnSO4 + H2
Concentrated sulphuric acid when heated with zinc gives SO2.
Zn + 2H2SO4 → ZnSO4 + 2H2O + SO2
The reaction with nitric acid is also complicated. If the acid is very
dilute, ammonium nitrate result.
If the acid is moderately strong, nitric oxide is formed.
3Zn + 8HNO3 → 3Zn(NO3)2 + 2NO + 4H2O
If the acid is concentrated and hot, nitrogen dioxide is the chief
product.
Zn + 4HNO3 → Zn(NO3)2 + 2NO2 + 2H2O
Zinc reacts with moderately strong alkalies on heating and forms
soluble zincates.
Zn + 2NaOH → Na2ZnO2 +H2
Zinc like magnesium forms addition compounds with alkyl halide. The
compound decomposes on heating.
Zn + C2H5I → ZnC2H5I
2ZnC2H5I → Zn(C2H5)2 + ZnI2
Zinc hydroxide is amphoteric. It dissolved in dilute acids forming salts.
Zn(OH)2 + 2HCl → ZnCl2 + 2H2O
It dissolves in alkalies and forming the complex ion [Zn(OH) 4]2−
Zn(OH)2 + 2NaOH → Na2[Zn(OH)4]
A precipitate of Zn(OH)2 dissolves in NH3 by the formation of
complex ion.
Zn(OH)2 + 4NH3 → [Zn(NH3)4](OH)2
Zinc hydroxide also dissolves in cyanide solution giving the complex
[Zn(CN)4] 2−
Zn(OH)2 + 4KCN → K2[Zn(CN)4] + 2KOH
Zinc ion is colourless. It undergoes slight hydrolysis in water giving
acidic solution.
Zn2+ + H2O ↔ Zn(OH)+ + H+
When base is added to a solution of Zn2+ ion, a precipitate of Zn(OH)2
obtained.
Zn2+ + 2OH− ↔ Zn(OH)2 (ppt)
 The f-block elements (The inner transition elements)

The f-block elements are those which have partly filled f-subshell of
the third to the outermost (antepenultimate), i.e., (n-2) energy shells in
their elementary or ionic state. These elements are also called inner
transition elements and are divided in to two series:

i) The lanthanide series

ii) The actinide series

In lanthanides, it is the 4f-subshell which is being successively filled

while in actinides, it is the 5f-subshell which is being successively
filled.
 The Lanthanide Series
Lanthenum (Z=57) and the next fourteen elements (Z=58-71) which follow
it are called lanthanides or lanthanones. These fifteen elements closely
resemble one another and form a distinct group with lanthanum as the
prototype, hence the name lanthanides or lanthanones. The reason why
they resemble lanthanum so closely lies in their electronic configuration.
The configuration of lanthanum is [Xe]5d 16s2. In the succeeding fourteen
elements, 14 electrons are successively added to the empty 4f-subshell of
the lanthanum configuration. Thus, while in cerium, the element
immediately following lanthanum, one 4f-electron is added to the
lanthanum configuration, in lutetium, the last element of the series,
fourteen 4f-electron are added to the lanthanum configuration. Hence the
configuration of cerium and lutetium are [Xe]4f 15d16s2 and [Xe]4f145d16s2
respectively. Since the number of electrons in the outermost, as well as the
penultimate shell, remains the same, all the fifteen lanthanides resemble
one another very closely. Strictly speaking, only 13 elements from Ce to
Yb are f-block elements because in lanthanum (5d 16s2) the 4f-subshell is
completely empty while in lutetium (4f145d16s2), the 4f-subshell is
completely filled.
 Occurence:
the lanthanides were originally called rare earth elements. The word
‘earth’ was used because they occurred as oxides and the word rare was
used because their occurrence was believed to be very scare. Now
many more elements occur even more rarely than the lanthanides.
Hence, although they are not abundant by any means, they are not
considered to be rare in the sense in which this word was used before.
Their substantial deposits occur in several countries, particularly in
India. The most commonly occurring lanthanides is cerium which
constitutes about 3x10−4% of the erath’s crust. Monazite sand is the
most important mineral containing lanthanides, it is essentially a
lanthanide orthophosphate. Some monazite deposits contain appreciable
amount of thorium also. In some cases the concentration of thorium
may amount to as much as 30%.
The abundance with which these elements occur in the earth’s crust is shown
below:
Elements Symbol Atomic no. Abundance (ppm) No. of isotopes

Lanthanum La 57 0.7 1
Cerium Ce 58 66 4
Prascodymium Pr 59 9.1 1
Neodymium Nd 60 40 7
Promethium Pm 61 4.5x10-20 0
Samarium Sm 62 7 7
Europium Eu 63 2.1 2
Gadolium Gd 64 6.1 7
Terbium Tb 65 1.2 1
Dysprosium Dy 66 4.5 7
Holmium Ho 67 1.4 1
Erbium Er 68 3.5 6
Thulium Tm 69 0.5 1
Ytterbium Yb 70 3.1 7
Lutetium Lu 71 0.8 2
It is interesting to note that elements with even atomic numbers are
relatively more abundant and also have a larger number of isotopes.
The elements with odd atomic numbers are less abundant and do not
have more than two isotopes. Promethium (Z=61) does not occur in
nature. It has been made artificially by radioactive disintegration.

Properties of Lanthanides:

1) Electronic configuration:
Electronic configuration of lanthanides is given in table.
Elements Atomic no. Electronic configuration Alternative probable Oxidation
configuration states

La 57 [Xe]5d16s2 +3
Ce 58 [Xe]4f15d16s2 [Xe]4f26s2 +3,+4
Pr 59 [Xe]4f25d16s2 [Xe]4f36s2 +3,+4
Nd 60 [Xe]4f35d16s2 [Xe]4f46s2 +2,+3,+4
Pm 61 [Xe]4f45d16s2 [Xe]4f56s2 +3
Sm 62 [Xe]4f55d16s2 [Xe]4f66s2 +2,+3
Eu 63 [Xe]4f65d16s2 [Xe]4f76s2 +2,+3
Gd 64 [Xe]4f75d16s2 [Xe]4f76s2 +3
Tb 65 [Xe]4f85d16s2 [Xe]4f96s2 +3,+4
Dy 66 [Xe]4f95d16s2 [Xe]4f106s2 +3,+4
Ho 67 [Xe]4f105d16s2 [Xe]4f116s2 +3
Er 68 [Xe]4f115d16s2 [Xe]4f126s2 +3
Tm 69 [Xe]4f125d16s2 [Xe]4f136s2 +2,+3
Yb 70 [Xe]4f135d16s2 [Xe]4f146s2 +2,+3
Lu 71 [Xe]4f145d16s2 [Xe]4f145d16s2 +3
There are some doubts regarding these configurations. This arises from
the complexity of the electronic spectra of these elements. According to
one view, the configurations are given in column 3. According to the
later view, the configurations are as given in column 4. As can be seen
according to the later view, the solitary 5d electron shifts in to 4f
subshell in all cases except in gadolinium (Z=64) where such a shift
destroys the symmetry of a half filled f subshell and in lutetium (Z=71)
where the f-subshell has already been completely filled and can not
accommodate any additional electrons. These days, the later view is
more accepted.

All the lanthanides have been allotted one single position in the
periodic table on account of the great similarity in their electronic
configurations and chemical properties.
2) Oxidation states: The common oxidation state of all the lanthanides
is +3. Lanthanum shows +3 oxidation states through the loss of both of
the 6s electrons and also the solitary d-electron. The configuration of
La3+ ion evidently, is that of xenon which is highly stable. It is very
difficult, therefore to remove another electron from this structure.
Hence, a higher oxidation state for lanthanum is not possible. In other
words, it is not possible, ordinarily, to have La4+ ion. Similarly,
gadolinium and lutetium also form only the tri positive M 3+ ions. This is
because the removal of three electrons yields the stable [Xe]4f 7
configuration for Gd3+ ion in which the f-subshell is exactly half filled
and the stable [Xe]4f14 configuration for Lu3+ ion in which the f-
subshell is fully filled. In these cases therefore any oxidation state other
than +3 would not occur. In other lanthanides, other oxidation states, +2
and +4 is particular, also occurs. But these states are always less stable
than the +3 states which is characteristics of this family. The outer
electronic configurations of lanthanides in different oxidation states are
given in table. The configurations of neutral atoms also included in the
table for easy reference.
Element Oxidation Outer electronic configuration of
s states
M M2+ M3+ M4+
La +3 [Xe]5d16s2 -------- [Xe]5d06s0 --------
Ce +3,+4 [Xe]4f26s2 ------- [Xe]4f16s0 [Xe]4f06s0
Pr +3,+4 [Xe]4f36s2 -------- [Xe]4f26s0 [Xe]4f26s0
Nd +2,+3,+4 [Xe]4f46s2 [Xe]4f46s0 [Xe]4f36s0 [Xe]4f26s0
Pm +3 [Xe]4f56s2 --------- [Xe]4f46s0 --------
Sm +2,+3 [Xe]4f66s2 [Xe]4f66s0 [Xe]4f56s0 ---------
Eu +2,+3 [Xe]4f76s2 [Xe]4f76s0 [Xe]4f66s0 ---------
Gd +3 [Xe]4f75d16s2 --------- [Xe]4f75d06s0 -------
Tb +3,+4 [Xe]4f96s2 -------- [Xe]4f86s0 [Xe]4f76s0
Dy +3,+4 [Xe]4f106s2 -------- [Xe]4f96s0 [Xe]4f86s0
Ho +3 [Xe]4f116s2 -------- [Xe]4f106s0 -------
Er +3 [Xe]4f126s2 --------- [Xe]4f116s0 --------
Tm +2,+3 [Xe]4f136s2 [Xe]4f136s0 [Xe]4f126s0 --------
Yb +2,+3 [Xe]4f146s2 [Xe]4f146s0 [Xe]4f136s0 --------
Lu +3 [Xe]4f145d16s2 -------- [Xe]4f146s0 --------
The +2 and +4 oxidation states are shown by those elements which by
doing so attain the stable f0, f7 and f14 configurations. For eg., cerium
(Ce) and terbium (Tb) attain f0 and f7 configurations respectively when
they go in to +4 oxidation state, as shown below:
Ce4+: [Xe]4f0 Tb4+: [Xe]4f7

Similarly europium and ytterbium acquire the f7 and f14 configuration

respectively. When they change in to +2 oxidation states, as shown
below:
Eu2+: [Xe]4f7 Yb2+: [Xe]4f14

These facts explain why these elements exercise oxidation states other
than +3 as well. This argument however does not hold well when we
find that samarium and thulium also show oxidation state of +2, even
though the M2+ ions have f6 and f13 configurations, respectively.
Sm2+: [Xe]4f6 Tm2+: [Xe]4f13
3) Ionic Radii: Lanthanide contraction:
The radii of M3+ ions, which are the most stable, are given below:

Ion Radius(Å) Ion Radius(Å)

La3+ 1.15 Tb3+ 1.00
Ce3+ 1.11 Dy3+ 0.99
Pr3+ 1.09 Ho3+ 0.97
Nd3+ 1.08 Er3+ 0.96
Pm3+ 1.06 Tm3+ 0.95
Sm3+ 1.04 Yb3+ 0.94
Eu3+ ------ Lu3+ 0.93
Gd3+ 1.02
Above table shows very clearly how ionic size decreases as we move
along the lanthanide series from lanthanum to lutetium. It will be seen
that on going from La2+ to Lu3+, the ionic radius shrinks from 1.15 Å to
0.93 Å. The steady decrease in ionic size all along the series amounting
in all to 0.22 Å is called the lanthanide contraction.
 Consequences of lanthanide contraction:
It is an important factor causes the separation of lanthanides from one
another. The radius of La3+ ion is 0.21 Å larger than Yb3+ ion which lies
immediately above it in periodic table. On that basis, if the fourteen
lanthanides had not occurred between Zr and Hf, the atomic radius of
Hf4+ ion should have been greater than that of Zr4+ ion (which lies
immediately above it) by about 0.2 Å. But the occurrence of lanthanide
contraction of about the same order almost exactly cancels the expected
increase. The result is that Hf4+ and Zr4+ ions have almost identical radii
being 0.8 Å and 0.81 Å respectively. Zirconium (Zr=40) and Hofnium
(Hf=72) have therefore almost identical chemical properties. It is thus a
direct consequence of lanthanide contraction that elements of the
second and third transition series resemble each other much more
closely than do the elements of the first and second transition series.
 Cause of lanthanide contraction:
The lanthanide contraction although more pronounced, is similar to the
contraction that was encountered in d-block (transition) elements. The
cause is also the same in both cases. As we move through the
lanthanide series, 4f electrons are being added one at each step. The
mutual shielding effect of f-electrons is very little, being even smaller
than that of d-electrons. This is due to the shape of f-orbitals. The
nuclear charge however increases by one at each step. Hence the inward
pull experienced by the 4f-electrons increases. This causes a reduction
in the size of the entire 4fn shell. The sum of the successive reductions
gives the total lanthanide contraction.
 4) Colour:
Some of the trivalent ions of lanthanides are coloured in the solid state
as well as in aqueous solution. These colours are shown below. The
colour appears to depend upon the number of unpaired f-electrons. The
colours of ions containing xf electrons is about the same as those with
(14-x)f electrons. This shows that the 4f orbitals are the main cause of
colour. The absorption band in the visible region of electronic spectra
of rare earth ions in their compounds arise because of the absorption of
light in the visible range resulting in the transition of electrons of the
ion from the lower energy f-orbitals to the higher energy f-orbitals. A
rare earth ion thus appears to be of the colour which is complementary
to the colour of the light absorbed. This type of change in the
arrangement of f-electrons due to absorption of light is called f-f
transition.
Ion No. of 4f- Colours Ion No. of 4f- Colours
electrons electrons

La3+ 0 Colourless Tb3+ 8 Pale pink

Ce3+ 1 Colourless Dy3+ 9 Yellow
Pr3+ 2 Green Ho3+ 10 Pale yellow

Nd3+ 3 Lilac Er3+ 11 Pink

Pm3+ 1 Pink Tm3+ 12 Pale green
Sm3+ 5 Yellow Yb3+ 13 Colourless
Eu3+ 6 Pale pink Lu3+ 14 Colourless
Gd3+ 7 Colourless
 5) Magnetic properties:
The La3+, Lu3+, Ce4+ and Yb2+ ions which have 4f0 or 4f14 electronic
configurations are diamagnetic. The rest of the trivalent lanthanide ions
which contain unpaired electrons in the 4f orbitals are paramagnetic.
The magnetic properties of the lanthanides are different from those of
the transition elements. In general, the magnetic moments arise from
two type of motion of electron. The spin motion of electron around its
own axis produces magnetic moment called spin magnetic moment
while the orbital motion of electron around the nucleus produces
magnetic moment called orbital magnetic moment. The observed
magnetic properties of a substance are thus the result of both the spin
and the orbital magnetic moment. In the case of compounds of
transition elements (d-block elements), the d-electrons of the metal ions
interact strongly with the electrons of the ligands surrounding the metal
ion. Due to the electric field of the ligands, the orbital motion of the
electrons gets restricted and thereby the orbital magnetic moment of
these electrons gets almost quenched.
The magnetic moment of d-block elements thus arises mainly from the
contribution of spin motion of the electrons. The simple relationship
based on the spin contribution of the electrons.
μ=√n(n+2)
Where n is the number of unpaired electrons, roughly accounts for the
magnetic properties of d-block elements. However, the above
relationship is not valid in the case of f-block elements. In these
elements, the 4f orbitals are well shielded from the surroundings by the
overlapping 5s and 5p subshell. As a result the electric field of the
ligands surrounding the ion does not restrict the orbital motion of the
electrons. Thus, orbital contribution, which was ignored in the case of
d-block elements. The magnetic moment in such cases is given by the
relationship.
μ=g√J(J+1)
Where J is the total angular momentum quantum number.
 6) Oxidation potential:
The standard oxidation potentials of lanthanides for the half reactions
are given below:
M(s) → M3+ + 3e−
Elements Eo (Volts) Elements Eo (Volts)
La 2.52 Tb 2.39
Ce 2.48 Dy 2.35
Pr 2.47 Ho 2.32
Nd 2.44 Er 2.30
Pm 2.42 Tm 2.28
Sm 2.41 Yb 2.27
Eu 2.41 Lu 2.25
Gd 2.40
The values are quite high and are in accord with their electropositive character. There
is, however, a trend towards slight decreases in the oxidation potential (or
electropositive character). This evidently, is consistent with the slight decreases in the
ionic radius due to lanthanide contraction.
 7) Chemical reactivity:
The lanthanides differ from only one another only in the number of 4f
electrons. Since these electrons are very effectively shielded from
interaction with other elements by the overlapping 5s, 5p and 6s electrons,
they show very little differences in their chemical reactivity. The
lanthanides are highly reactive, silvery white metals which turnish readily
on exposure to air. In finely divides state, they all burn in air giving the
sesquioxide of the formula M2O3, except Cerium which gives CeO 2.
Ytterbium, however resists the action of air even at 1000 oC due to the
formation of a protective coating of its oxide.
The lanthanides combine with hydrogen. The reaction is exothermic;
however, initial heating to 300oC is necessary to start the reaction. The
heat of the reaction is sufficient to keep the reaction going thereafter; the
resulting hydrides MH2 and MH3 are stable.
The lanthanides also react with other non-metals like halogens, sulphur,
phosphorus, nitrogen, carbon and silicon forming corresponding
compounds. They decompose water evolving hydrogen slowly in cold but
rapidly on heating. They have strong electropositive character as indicated
by their high oxidation potential.
 8) Complexes:
Lanthanide ions, in spite of the high charge (+3), have low charge
density because of their large size. They can not cause much
polarization and consequently they have weak tendency to form
complexes. Their complexes with unidentate ligands are very few.
However complexes with a few chelating ligands such as β-diketones,
oximes and EDTA are fairly common. The lanthanides do not form
complexes with π-bonding ligands such as CO, NO, CNR etc. the
tendency to form complexes and their stability increases with
increasing atomic number. Advantage is taken of this fact in their
separation from one another.
Extraction of a mixture of lanthanides from monazite sand:
Monazite sand is the best known mineral containing the lanthanide
elements. It is essentially a mixture of phosphate, RPO4 (where R
stands for a lanthanide element) containing up to 12% of thorium
together with small amount of zirconium, iron and titanium in the form
of silicates. The mineral is digested with hot conc H2SO4 at 200oC in the
form of paste when the phosphates change in to the corresponding
sulphates. The paste is separated by centrifugation and treated with cold
water. The sulphates are more soluble in cold water than in hot water
and therefore, pass in to solution. Silica (SiO2), zircon (ZrSiO4) etc.,
being insoluble, get eliminated. Thorium left in solution is removed as
insoluble phosphate on diluting and adjusting pH of the solution in the
alkaline range.
The solution containing now only sulphates of the lanthanide elements
is treated with sodium sulphate. This results in dividing the lanthanides
in to two groups. The light lanthanides (La to Sm) are thrown down as
the double sulphate having variable composition while the heavier
lanthanides (Gd to Lu) remain in solution (as simple sulphates). The
precipitated double sulphates are treated with hot NaOH, when they are
converted in to a mixture of oxides and hydroxides. The mixture is
washed to remove the sodium sulphate formed in the process and dried
in air at 100oC. Cerium gets oxidized to cerium oxide, CeO2, during the
drying process and therefore gets separated by itself; the method is
summarized up in the following flow sheets.
The lanthanides are then separated from various techniques as discussed below:
Separation of lanthanides:
a) Repeated fractional crystallization: Formation of simple salts like nitrates,
sulphates, bromates, oxalates as well as double salt like
2La(NO3)3.3Mg(NO3)2.24H2O, which forms nice crystals, have been made use of
in the separation of the lanthanide elements. Advantage is taken of slight
differences in their solubilities in water.
b) Solvent extraction: The partition coefficients of the salts of these metals
between water and organic solvents are slightly different. To take an example, the
partition coefficient of Gd(NO3)3 between water and normal butyl alcohol is 1.06
times greater than that of La(NO3)3 by continuous extraction with water from a
solution of these salts in butyl alcohol.
c) Fractional crystallization: If only a small amount of a precipitating agent is
added to a mixture of lanthanide salts, the substance having the lowest solubilities
product will precipitate out first. Thus, if sodium hydroxide is added to a solution
of lanthanide nitrate, La(OH)3, which is the weakest base and has lowest
solubility product is precipitated first, while La(OH) 3, which has the highest
solubility product, is precipitated last. A partial separation takes place in this
manner. However, by redissolving the precipitate, the process can be repeated a
number of times until complete separation are affected.
 The Actinide Series
Transuranic elements: A number of elements beyond uranium, i.e.,
beyond atomic number 92 have been prepared in the laboratory through
nuclear reactions. These elements are known as transuranic elements.
They are all f-block elements.
Preparation of transuranic elements: It was found by Seaborg at the
University of California that when uranium is bombarded with neutrons
of a certain critical velocity, one neutron is captured per atom of
uranium giving rise to an element of a higher mass number.
92 U238
+ 0 n1
→ 92 U 239
+ γ-rays
This new isotopes of uranium is much more radioactive than the natural
uranium. It emits a beta particle and gives a new element of atomic
number 93 which does not occur in nature. This element is named
neptunium.
92 U239
→ 93 Np 239
+ −1 e 0

Neptunium is also radioactive and emits a beta particle giving another

new element of atomic number 94 known as plutonium.
93Np → 94Pu239 + −1e0
239
Actually three isotopes of plutonium with mass numbers 236, 238 and
239 are formed. The next two elements, americium (Z=95) and cerium
(Z=96) were obtained by the bombardment of U238 with alpha particles,
as illustrated below.
92U + 2He4 → 94Pu241 + 0n1
238

Infact, two isotopes of plutonium with mass number 241 and 239 are
produced which undergo the following nuclear reactions.
94 Pu 241
→ 95 Am 241
+ −1 e 0

94Pu + 2He4 → 96Cm242 + 0n1

239

Californium (Z=98) was synthesized by the bombardment of cerium

with accelerated alpha particle. Two isotopes of the elements are
formed.
96 Cm 242
+ 2 He 4
→ 98 Cf 246
+ γ-rays
96Cm + 2He4 → 98Cf244 + 20n1
242

Einsteinium (Z=99) was obtained by the bombardment of an isotope of

californium of mass number 250 with neutron. The californium isotope
of mass number 253 obtained during the bombardment, yielding
 98 Cf250 + 0n1 → 98Cf251 + γ-rays
98Cf + 0n1 → 98Cf252 + γ-rays
251

98 Cf 252
+ 0 n 1
→ 98 Cf 253
+ γ-rays
98Cf → 99Es253 + −1e0
253

Fermium (Z=100) was obtained by the bombardment of einsteinium with

neutrons when the isotope of einsteinium of mass number 254 formed
during the process yielded fermium as a result of beta ray emission.
99Es + 0n1 → 99Es254 + γ-rays
253

99Es → 100Fm254 + −1e0

254

The next three elements namely, mendelevium (Z=101), niobium (Z=102)

and lawrencium (Z=103) were also synthesized through nuclear reactions, as
illustrated below.
99Es + 2He4 → 101Md256 + 0n1
253

96Sm + 6C12 → 102No254 + 40n1

253

98Cf + 5B11 → 103Lw257 + 40n1

250

The transuranic elements obtained as above were separated from their

respective target materials and the irradiated nuclear fuels by following
certain specialized techniques such as ion exchange, solvent extraction,
 Thorium (Th)
Occurrence:
It constitutes nearly 0.0012% of earth’s crust and is about three times
more abundant than uranium. The important minerals are; Thorianite
(thorium oxide), Thorite (thorium silicate), cheralite (silicates and
phosphates of Th, Ca and Ce) and monazite (phosphates of Ce, Y, La
and Th)

Extraction of thorium from monazite:

Indian monazite sand is of topmost grade in the world. Its chemical
composition is as follows:
ThO2=9.4%, CeO2=28.5%, U3O8=0.37% and P2O5=25.9%
Owing to the presence of rare earth impurities which in chemical
properties resemble thorium, the extraction of thorium becomes quite
difficult. The process of extraction involves following steps.
Concentration and formation of thorium dioxide:
The ore is freed from a major chunk of silicious impurities either by mechanical
washing or by magnetic separations and then treated with concentrated H 2SO4.
The resultant pasty mass is added to cold water, stirred thoroughly and then
allowed to stand. Impurities such as silica and unattacked minerals settle down.
The supernatant liquid which contains phosphate of thorium and rare earth’s
elements is syphoned off. The acid solution is partially neutralized by ammonia or
alkali hydroxide or magnesia mixture when thorium, being more electropositive
than the rare earths, gets precipitated as thorium phosphate along with
comparatively smaller amounts of phosphates of rare earths. The precipitate is
removed, dissolved in minimum quantity of acid and then neutralized as before to
again precipitate the phosphate of thorium. The process is repeated several times
and in this way the amount of phosphates of rare earths is reduced considerably.

The precipitate of thorium phosphate obtained as above is dissolved in nitric acid

(about 6 M) and treated with potassium iodate in the presence of hydrogen
peroxide when thorium gets precipitated as thorium iodate. The rare earth
phosphates remain in solution. The precipitate of thorium iodate is dissolve in
hydrochloric acid and reprecipitated as thorium oxalate to eliminate zirconium.
The thorium oxalate is then ignited to get thorium dioxide, ThO 2.
Preparation of thorium metal:
The preparation of thorium from thorium dioxide is rather difficult
because the metal is highly reactive in its molten state. The various
method employed for the recovery of the metal are briefly discussed
below.
1. Thorium dioxide, obtained as above, is heated at 950oC with calcium
in a steel bomb using CaCl2 as flux.
ThO2 + 2Ca → 2CaO + Th
2. In another method thorium dioxide is first converted in to thorium
chloride or thorium fluoride by heating with carbon in a current of
chlorine or fluorine.
ThO2 + 2C + 2Cl2 → ThCl4 + 2CO
ThO2 + 2C + 2F2 → ThF4 + 2CO
The thorium chloride or fluoride is then reduced with electropositive
metals such as Na, Ca and Mg.
ThCl4 + 4Na → Th + 4NaCl
ThF4 + 2Ca → Th + 2CaF2
Electrolytic method:
In this method, metallic thorium is obtained by electrolyzing a fused
mixture of ThF4-KCl-NaCl employing a solid cathode and a graphite
anode. Electrolysis is carried out at temperature of 800 oC employing a
current density of 70 ampere per kg of the electrolyte. Thorium is
deposited as a powder on the cathode and is scrapped of from time to
time. The powder is washed with dil HNO3, dried and converted in to
ingots.

Pure thorium can also be obtained by heating the crude metal powder in
iodine vapours to form volatile thorium iodide which is isolated and
thermally decomposed on an incandescent filament at about 1100-
1200oC to yield pure thorium.
Th(crude) + 2I2 T→hI4
ThI4 (1100-1200oC) → Th(Pure) + 2I2
 Uranium (U)
Occurrence: Uranium is widely distributed in a variety of rocks as well
as in sea water. The later contains about 2x10−6 g of uranium per litre.
Ores: Pitchblende or uranite and carnotite, furgusonite, samarskite,
autosite and uronophone.
Extraction of uranium: The first step in extraction of uranium is the
isolation of pure uranium oxide from the ores
Isolation of uranium oxide, U3O8 from uranium ores:
Uranium oxide from pitch blende: It is obtained by two processes.
First process: The first process involves the following steps:
The ore is crushed in a fine powder and concentrated by gravity
process. The concentrated ore is roasted in a reverberatory furnace in
the presence of excess air to remove sulphur and other volatile
impurities. The roasted ore which contain U3O8 is mixed with sodium
carbonate and sodium nitrate and the whole mass is heated to fusion
resulting in the formation of sodium urinate.
U3O8 + 3Na2CO3 + [O] → 2Na2UO4 + 3CO2
The fused mass is extracted with hot water and the solution is treated
with an excess of ammonium carbonate when impurities such as Al, Ni,
Co and Mn get precipitated as basic carbonates while uranium remains
in solution as ammonium uranyl carbonate, (NH4)4UO2(CO3)3.
The solution is neutralized with dilute H2SO4 and evaporated to dryness
when ammonium diuranate, (NH4)2U2O7, is obtained as a heavy yellow
precipitate. On calcination, the diuranate yields uranium oxide, U 3O8.
3(NH4)2U2O7 → 2U3O8 + 6NH3 + 3H2O + O2
Alternatively, the roasted ore (after step 2) is heated with dilute H2SO4
for about 16-24 hrs in the presence of an oxidizing agent, such as
MnO2, this oxidises the U3O8 present in the roasted ore to soluble
uranyl sulphate.
UO2SO4 + 3(NH4)2CO3 → (NH4)4UO2(CO3)3
When ammonium carbonate is added to the solution, ammonium uranyl
carbonate, (NH4)2UO2(CO3)3, is crystallized out which on ignition gives
U3O8.
UO2SO4 + 3(NH4)2CO3 → (NH4)4UO2(CO3)3 + (NH4)2SO4
Second process (Klaproth’s process): Pitchblende ore is treated with
HNO3 or aquaregia and the resulting solution is evaporated to dryness.
The dry mass is then extracted with HCl, the filtrate is then treated with
HNO3 and neutralized by ammonium carbonate. On boiling this
solution, uranium, zinc and cobalt get precipitated as oxides. The
precipitate is again treated with HCl when the oxide of zinc and cobalt
get dissolved leaving behind the oxide of uranium which is insoluble in
HCl.

Production of metal from oxide: From uranium oxide, U3O8, the

metal is obtained as follows:
The oxide is heated with charcoal or hydrogen when it is reduced to the
uranium dioxide, UO2. It can not be reduced further to uranium on
heating with hydrogen even at such a high temperature as 2500oC. The
dioxide is heated with chlorine when yellow crystalline uranyl chloride,
UO2Cl2, is obtained.
UO2 + Cl2 → UO2Cl2
Uranyl chloride is heated with carbon, while a stream of chlorine
continues to pass. This results in the formation of uranium
tetrachloride, UCl4, which sublimes readily.
UO2Cl2 + Cl2 → UCl4 + O2

Finally the UCl4 is heated with sodium to get metallic uranium.

UCl4 + 4Na → 4NaCl + U

Alternatively and more conveniently, UO2 obtained as above is treated

with HF to get UF4 which is reduced by magnesium to get the metal.
UO2 + 4HF (Heat) →UF4 + 2H2O
UF4 + 2Mg → U + 2MgF2 (slag)

Yet another method is to reduce the UO2 by CaH2 at 980oC or by Al.

3UO2 + 4Al → 3U + 2Al2O3
Chemical properties: It reacts with steam between 150-250oC to form
a mixture of oxide and hydride.
7U + 6H2O → 3UO2 + 4UH3
It dissolves readily in dilute HCl. In HNO3, it dissolves at a moderate
rate while in H2SO4 and HF, the rate of dissolution is very slow. It does
not react with alkalies. It reacts with hydrogen at 600 oC under pressure
to form the well-defined hydride, UH3.
The uranium trioxide, UO3 is obtained as:
a) By heating uranyl carbonate at 300 oC.
UO2CO3 → UO3 + CO2
b) By heating ammonium urinate at 250 oC for 30 hrs.
(NH4)2U2O7 → 2UO3 + H2O + 2NH3
c) By heating uranyl nitrate at 250 oC.
2UO2(NO3)2 → 2UO3 + 4NO2 + O2
UO3 is an amphoteric oxide dissolving in acids to form uranyl salts and in alkalies
to form urinates and diuranates.
UO3 + 2HCl → UO2Cl2 + H2O (Uranyl Chloride)
UO3 + H2SO4 → UO2SO4 + H2O (Uranyl sulphate)
UO3 + 2NaOH → Na2UO4 + H2O (Sodium uranate)
2UO3 + 2NaOH → Na2U2O7 + H2O (Sodium diuranate)
The U3O8 is obtained from the UO3 by heating at 700oC.
3UO3 → U3O8 + 1/2O2
Uranates are obtained by the fusion of uranium oxides with alkaline carbonates
these are orange or yellow in colour.
2UO3 + Li2CO3 → Li2U2O7 + CO2
Li2U2O7 + Li2CO3 → 2Li2UO4 + CO2