SCH 400: Comparative study of transition elements

(Prerequisite SCH 301)

Course Description
General definition of a transition element. Mineralogy, metallurgy and general properties of transition elements.
Stability of various oxidation states of d-elements (i) along the series and (ii) down the groups as illustrated
various types of oxo and halo species formed. Binary compounds, chemistry of lower and higher oxidation states,
structures of stable compounds. Industrial and biological roles of some transition elements.

Course Outline
 Transition element- a general definition
 Mineralogy and metallurgy
 General properties of transition elements
 Stability of various oxidation states of d-block elements
o along the series  Illustrated by the types of oxo- and halo- species formed.
o down the groups  Reasons for the observed variations

 Formation of cluster and condensed oxo species

 Practical applications of selected oxides such as TiO2 in paints, MnO2 in making dry cells CrO2 in making
magnetic tapes, Cr2O3 and CoO in ceramics
 Selected catalytically important reactions catalyzed by transition metals or transition metal compounds:
o Ziegler-Natta Polymerization of olefins over TiCl4/AlEt3 catalyst
o Hydrogenation of oils over Nickel catalyst
o The Haber-Bosch process etc

Course Objectives
The main objectives of this unit are:
1) To describe the chemistry of the transition elements
2) To explain the principles that underlie the chemistry of the transition elements
3) To highlight the catalytic, alloy, and other industrial uses of the transition elements
4) To highlight the biological roles of the transition metals

Suggested references
1. J. D. Lee, Concise Inorganic Chemistry, 5th ed., Blackwell science Ltd, Oxford UK, 1996
2. N. N. Greenwood and A. Earnshaw, Chemistry of the elements, 2nd ed., Butterworth-Heinemann, Oxford UK.,
1997.
3. N. N. Greenwood and A. Earnshaw, Chemistry of the elements, 3rd ed., Butterworth-Heinemann, Oxford UK.
4. Any relevant college Inorganic Chemistry Textbook.

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UNIT 1
Transition elements
Introduction
This is one of the core units under inorganic chemistry. It is concerned with the chemistry of elements that occupy
the 10 groups that lie between the s-block and the p-block of the periodic table. This course will involve the study
of the general properties of the elements down the groups and a cross the series (Fig 1). It will also cover the
chemistry of the elements of the first transition series (those from Sc to Zn) compared with that of the second and
third transition series. The industrial and other applications of the elements and/or their compounds will also be
explored.

Definitions
IUPAC: A transition element is an element whose atom has an incomplete d sub-shell, or one which can give rise
to cations with an incomplete d sub-shell1.

Zinc, cadmium, and mercury are excluded from the transition metals, because they have a d10 configuration even
in their most common oxidation state. Only a few transient species of these elements that leave ions with a partly
filled d sub-shell have been formed, and mercury(I) only occurs as Hg22+, which does not strictly form a lone ion
with a partly filled sub-shell, and hence these three elements are inconsistent with the definition 2. They do form
ions with a 2+ oxidation state, but these retain the (n-1)d10 configuration. However, Cu, Ag and Au qualify as
transition elements because their M2+ ions contain incomplete d sub-shells.

Broader definition: A transition element is one whose atom has a partially filled d or f sub-shell or which can
give rise to cations with a partially filled d or f sub-shell. This therefore, includes the f-block elements (also
known as the inner transition elements, see Fig. 1).

In this course we shall concentrate in the chemistry of the d-block elements contained in periods 4-6 shown in the
table below. Period seven elements starting with Rutherfordium (Rf) are synthetic elements (do not occur
naturally) with fairly short half-lives and will not be studied in this course.

2
Figure 1: Sections of the Periodic Table (http://en.wikipedia.org/wiki/Periodic_table)

3
The Periodic Table of Elements

4
 The Periodic Table of Elements
including ground state electronic configurations

Figure 2: The standard periodic Table (From: http://en.wikipedia.org/wiki/Periodic_table, slightly modified)

5
Notes:
1. The four periods (4 – 7) in which the d-block elements occur represent the successive addition of
electrons to the d atomic orbitals of the atoms. In this way, the transition metals represent the
transition between group 2 elements and group 13 elements.
2. The three important series for this course include those filling 3d, 4d and 5d orbitals, respectively.
Those in the fourth series are discussed with the f-block elements.
3. The third transition series begins at La with outer electron configuration 5d6s2. At this point the 4f
sub-shell becomes slightly more stable than the 5d sub-shell such that through the next 14 elements,
electrons enter the 4f sub-shell until at Lu it becomes full.The15 elements from 57La to 71Lu have
very similar chemical and physical properties, those of La being prototypical. The elements are
therefore, known as the Lanthanides. The similarity comes from the fact that the f orbitals are
buried in the atoms and ions. Thus, the electrons that occupy them are largely screened from the
surroundings by the overlying shells (5s and 5p) of electrons. As a result the reciprocal interactions
with the 4f electrons and the surroundings of the atom or ion are of relatively little chemical
significance. Thus, the chemistry of the lanthanides is quite homologous.

4. The fourth transition series begins with Rf. Before these is another set of 15 elements starting with
Actinium with electron filling the 5f sub-shell. Because there is not much difference between the 5f
and 6d sub-shells until after four or five electrons have been added to the actinium configuration
([Rn]6d17s2), the electron configuration of these elements is not easily predictable. After the
addition of about five electrons to the actinium configuration, the 5f becomes more stable than the
6d. The elements from 95Am onwards have homologous chemistry. Generally these 15 elements are
referred to as Actinides. Their chemistry is halfway between that of the d-block elements and the
lanthanides. The 5f orbitals are not as well shielded as the 4f but they are also not so exposed as the
d-orbitals of the d-block elements.

Although the transition elements have many general chemical similarities, each one has a detailed
chemistry of its own. The closest relationships are usually to be found among the three elements in each
vertical group in the periodic table, although within each group the element of the first series usually
differs more from the other two than they differ from each other. Most of the first series elements are
more familiar and technically important than the heavier members of their vertical group.

Common characteristic properties of transition elements

1) They are all metals with good electrical and thermal conductivities. They also have high
tensile strengths, density and melting and boiling points. These may be attributed to the
ability of the d orbital electrons to delocalise within the metal lattice in metallic bond
formation.
2) Most of them display numerous oxidation states which vary in steps of 1 rather 2 as is
usually the case with those main group elements which exhibit more than one oxidation
state.
3) They have an unparalleled propensity for forming coordination compounds with Lewis
bases.

Other less common properties include:

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 1) Majority form coloured compounds
2) At least one of their compounds has an incomplete d-electron sub-shell.
3) They or their compounds are often good industrial or even biological catalysts.
4) They form compounds which are often paramagnetic

1. Formation of coloured compounds

Many ionic and covalent compounds of transition elements are coloured in contrast to those of s and p-
block elements which are often white. When light passes through a material some wavelengths off the
light are absorbed. If the wavelengths absorbed fall within the visible region of the electromagnetic
spectrum, the transmitted light is coloured with the complementary colour to the colour of the light
absorbed (see Table 1).

Table 1: Colour of absorbed light and the complementary colour of solutions of absorbing material

Colour of solution Clear Violet Blue/blue Green yellow Orange Red red-
green purple
Absorbed colour Ultra yellow Orange/red Purple Violet Blue Blue/green green
violet
 (nm) of absorbed <400 400 500 530 580 610 680 700
light

The mechanism of absorption of radiation in substances has been discussed in SCH 301. It is all caused
by electronic transitions which may be possible in a material due to:
(a) Polarization
For example, NaCl, NaBr and NaI are all ionic and colourless. AgCl, is also colourless but on the
other hand AgBr is pale yellow and AgI is yellow. The colour arises because Ag+ polarizes the
halide ions making ligand-to-metal charge transfer easy and of low energy (in the visible range).
The distortion of the electron cloud in AgX (X = Br I) implies greater covalent contribution to the
bonding between the metal and the halide anion. This is also why Ag2CO3 and Ag3PO4 are coloured
yellow and Ag2O and Ag2S are black.

(b) Incomplete d or f sub-shell (remember crystal field theory in SCH 301)

This is the main cause of colour in most transition metal ions. When a metal ion is placed in a
ligand field, the degeneracy of the d or f orbitals is lifted creating, in their simplest form, two sets of
orbitals of different energy. Thus in a transition ion with a partly filled d sub-shell it is possible to
promote electrons from one d level to another of higher energy. This corresponds to a fairly small
energy difference and so the energy absorbed is within the visible region. The colour of a complex
depends on:
a) The nature of the metal ion, specifically the oxidation state of the metal e.g. Fe 2+ is pale-
green while Fe3+ is rusty brown
b) The arrangement of the ligands around the metal ion (for example geometric isomers can
display different colours).

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 c) The nature of the ligands surrounding the metal ion. The stronger the ligands then the
greater the energy difference between the split high and low d groups. For example
[Ni(NH3)6]2+ is blue while [Ni(H2O)6]2+ is green, etc.

Some transition metal compounds in high oxidation states and in which all d electrons of the metal have
been used for bonding are white. This is expected as it is not possible have d-d electronic transitions.
Examples include TiO2, ZnSO4 etc. Yet in some still the compounds are coloured because as the
oxidation number increases the compound become more covalent and can undergo charge transfer
transitions. For example, VO2+, VO43-, CrO42-, MnO4- are all deeply coloured. This because charge
transfer transitions always produce intense colours since the restrictions of the Laporte and spin
selection rules do not apply to transition between atoms.

2. Variable oxidation states

Transition elements show multiple stable oxidation states, which change in units of one, e.g. Fe 3+, Fe2+,
Cu2+, and Cu+. The metals can use the penultimate nd and valence (n+1)s electrons for bonding without
a high energetic penalty.

The oxidation states may be related to their electronic configurations (see Table 2).

Table 2: Oxidation states of the first transition series elements

Element Sc Ti V Cr Mn Fe Co Ni Cu Zn
Outer electronic 3d14s2 3d24s2 3d34s2 3d44s2 3d54s2 3d64s2 3d74s2 3d84s2 3d94s2 3d104s2
structure 3d54s1 3d104s1
Oxidation states 1 1
2 2 2 2 2 2 2 2 2 2
3 3 3 3 3 3 3 3 3
4 4 4 4 4 4 4
5 5 5 5 5
6 6 6
7

The outer electronic structures follow smoothly from Ca [Ar]4s2 except for Cr and Cu whose
expected structure is underlined and the observed one indicate below it. In these two elements the s
electron moves into the d sub-shell because of the additional stability associated with the half-filled
orbitals created.

When only s electrons are used for bonding the elements shows oxidation state +2 except for Cr and
Cu which show +1. Higher oxidation states are obtained when varying numbers of d electrons are
also involved in bonding. For example, manganese has two 4s electrons and five 3d electrons,
which can be used for bonding giving +2, +3, +4, +5, +6 and +7 states.

It is clear from Table 2 that among the first five elements the correlation between the electronic
structure and maximum oxidation states in simple compounds in complete. In the highest (group)
oxidation states of the first five elements, all of the s and d electrons are used for bonding.
Therefore their properties depend only on the size and valency. In this they show some similarities
with elements of the main groups in similar oxidation states. For example, SO42- (Gp 16) and CrO42-
(Gp 6) are isostructural (i.e. have similar structure) as are SiCl4 (Gp 14) and TiCl4 (Gp 4).

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In the last five elements, the d5 configuration is exceeded and it appears that the tendency of all the
d electrons to participate in bonding decreases towards Zn. Thus, the maximum oxidation state of
Fe is +6. However, the second and third transition series elements in the Fe group attain a
maximum oxidation state of +8 in RuO4 and OsO4, respectively (see Fig. 3) This is among the
highest for isolable compounds. The difference between Fe and the other heavier elements Ru and
Os is attributed to the increased atomic size down the group.

The underlined oxidation states, +2 and +5, in Sc and Co have doubtful existence. It is worth noting
also that in addition to the shown oxidation states, the elements also show oxidations state 0 in
elemental form. Some of the elements like V and Cr form complexes in oxidation state zero or
below. The low oxidation states in complexes occur with  bonding ligands such as CO and
dipyridyl.

Similar but not identical trends in oxidation states occur in the second and third transition series
elements. The main differences are as follows:
1. In group 8 (iron group) the second and third row elements show a maximum oxidation state
of +8 instead of +6 for Fe.
2. The electronic structures of the 2nd and 3rd rows do not always follow the pattern of the first
row. For example, in group 6 Cr and Mo have d5s1 outer configuration but W has the
expected d4s2 structure. The structures of group 10 elements are:
Ni 3d8 4s2
Pd 4d10 5s0
Pt 5d9 6s1
The d levels are complete at copper, palladium and gold in their respective series.

Ni Cu 3d104s1 Zn 3d10 4s2

Pd 4d10 5s0 Ag Cd 4d10 5s2
Pt Au 5d106s1 Hg 5d10 6s2

Pd, Cu, Ag and Au behave as typical transition elements even though the d sub-shells are full. For
example, in their most common oxidation states they have incompletely filled d levels; (Cu(II) has
a d9 configuration and Pd(II) and Au(III) have d8 configurations).

Working out electronic configurations

Example

Work out the electronic configuration of Fe2+.

Solution

 Write out the configuration of the ion [Ar] 3d6 4s2

 Remove the number of electrons – remembering that the 4s go first.

So the electronic configuration of Fe2+ is [Ar] 3d6.

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 Stability of the various oxidation states
Stable compounds are those that have the following characteristics:

i) They exist at room temperature

ii) They are not oxidized by the air
iii) They are not hydrolyzed by water or water vapour and
iv) They do not disproportionate or decompose at normal temperatures.
Stable oxidation states can be seen in the various isolable oxides, fluorides, chlorides, bromides and
iodides of the elements. The possible halides for the transition elements are summarized in Table 3
below. There are differences in the stability of the various possible oxidation states that exist for the
elements in the three transition series. In general the 2nd and 3rd row elements exhibit higher
coordination numbers and their higher oxidation states are more stable than the corresponding first
row elements.

As you will notice from the table below, the highest oxidation state available to an element is
generally usually found among its compounds with oxygen and fluorine which are the most
electronegative elements. Thus an examination of the binary fluorides and oxides of the transition
elements should reveal their maximum chemically attainable oxidation states.

Table 3: Simple Binary transition metal oxides

Element Sc Ti V Cr Mn Fe Co Ni Cu Zn
Oxidation state 1 - - - - - - - - Cu2O
2 - TiO VO - MnO FeO CoO NiO CuO ZnO
3 Sc2O3 Ti2O3 V 2O 3 Cr2O3 Mn2O3 Fe2O3 Co3O4 - - -
4 - TiO2 VO2 CrO2 MnO2 - - NiO2 - -
5 - - V 2O 5 - - - - - -
6 - - - CrO3 - - - - - -
7 - - - - Mn2O7 - - - - -

Element Y Zr Nb Mo Tc Ru Rh Pd Ag Cd
Oxidation state 1 - - - - - - - - Ag2O -
2 - - NbO - - - PdO AgO CdO
3 Y 2O 3 - - - - - Rh2O3 Pd2O3 - -
4 - ZrO2 NbO2 MoO2 TcO2 RuO2 RhO2 PdO2 - -
5 - - Nb2O5 Mo2O5 - - - - -
6 - - - MoO3 TcO3 - - - - -
7 - - - - Tc2O7 - - - - -
8 - - - - - RuO4 - - - -

Element La Hf Ta W Re Os Ir Pt Au Hg
Oxidation state 2 - - - - ReO - - - - HgO
3 La2O3 - - - Re2O3 - Ir2O3 Pt2O3 Au2O3 -
4 - HfO2 TaO2 WO2 ReO2 OsO2 IrO2 PtO2 - -
5 - - Ta2O5 Re2O5 - -
6 - - WO3 ReO3 OsO3 IrO3 PtO3 - -
7 - - - - Re2O7 - - - - -
- - - - - OsO4 - - - -

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 Table 4: Simple binary transition metal fluorides1

Element Sc Ti V Cr Mn Fe Co Ni Cu Zn
Oxidation state 1 - - - - - - - - - -
2 - - VF2 CrF2 MnF2 FeF2 CoF2 NiF2 CuF2 ZnF2
3 ScF3 TiF3 VF3 CrF3 MnF3 FeF3 CoF3 - - -
4 - TiF4 VF4 CrF4 MnF4 - - - - -
5 - - VF5 CrF5 - - - - - -
6 - - - CrF6 - - - - - -
7 - - - - - - - - - -
Element Y Zr Nb Mo Tc Ru Rh Pd Ag Cd
Oxidation state 1 - - - - - - - - AgF -
2 - - - - - - - PdF2 AgF2 CdF2
3 YF3 ZrF3 NbF3 MoF3 - RuF3 RhF3 - - -
4 - ZrF4 NbF4 MoF4 - RuF4 RhF4 PdF4 - -
5 - - NbF5 MoF5 - RuF5 RhF5 - - -
6 - - MoF6 TcF6 RuF6 RhF6 - - -
7 - - - - - - - - - -
8 - - - - - - - - - -

Element La Hf Ta W Re Os Ir Pt Au Hg
Oxidation state 1 - - - - - - - - - Hg2F2
2 - - - - - - - - - HgF2
3 LaF3 - - - - - IrF3 - AuF3 -
4 - HfF4 - - ReF4 OsF4 PtF4 - -
5 - - TaF5 - ReF5 OsF5 IrF5 PtF5 AuF5 -
6 - - - WF6 ReF6 OsF6 IrF6 PtF6 - -
7 - - - - ReF7 - - - - -
- - - - - - - - - -

The following observations can be made from the tables:

i) The first five elements to the left of each transition series can attain the maximum possible
oxidation state (or group oxidations state) while at the right of the series oxidation state +2
becomes dominant. This may be attributed to the increase in the third and higher ionization
energies with increasing atomic number across the series and the increasingly ‘core-like’
nature of the d orbitals.
ii) In the first series the maximum oxidation state attained with oxygen is +7 in Mn2O7 while
with fluorine the maximum is +6 with CrF6. On the other hand, in the 2nd and 3rd series the
maximum oxidation state attained with oxygen is +8 in RuO4 and OsO4, respectively while
with fluorine the maximum oxidation state attained is +7 in ReF7.

Binary compounds with the less electronegative chlorine show a slightly different range of
oxidation states. Therefore, for comparison, the chlorides are summarized below

1
Fluorides with non-integer oxidation states have been omitted.

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 Table 5: Simple binary transition metal chlorides
Element Sc Ti V Cr Mn Fe Co Ni Cu Zn
Oxidation state 1 - - - - - - - - CuCl
2 - TiCl2 VCl2 CrCl2 MnCl2 FeCl2 CoCl2 NiCl2 CuCl2 ZnCl2
3 ScCl3 TiCl3 VCl3 CrCl3 MnCl3 FeCl3 - - - -
4 - TiCl4 VCl4 CrCl4 - - - - - -
- - - - - - - - - -

Element Y Zr Nb Mo Tc Ru Rh Pd Ag Cd
Oxidation state 1 - - - - - - - - AgCl -
2 - ZrCl2 Nb6Cl14 MoCl2 - RuCl2 - PdCl2 - CdCl2
3 YCl3 ZrCl3 NbCl3 MoCl3 - RuCl3 RhCl3 - - -
4 - ZrCl4 NbCl4 MoCl4 TcCl4 - - PdCl4 - -
5 - - NbCl5 MoCl5 - - - - - -
6 - - - MoCl6 TcCl6 - - - - -

Element La Hf Ta W Re Os Ir Pt Au Hg
Oxidation state 1 - - - - - - - - AuCl Hg2Cl2
2 - - Ta2Cl5 WCl2 - OsCl2 - PtCl2 - HgCl2
3 LaCl3 - TaCl3 WCl3 ReCl3 OsCl3 IrCl3 - AuCl3 -
4 - HfCl4 TaCl4 WCl4 ReCl4 OsCl4 PtCl4 - -
5 - - TaCl5 WCl5 ReCl5 - - - - -
6 - - - WCl6 ReCl6 - - - - -

You can see that among the third row elements a greater range of oxidation states is found with the
chlorides than with the fluorides.

Contributions from Covalency

The formation and stability of higher oxidation state compounds may not be fully explained by ionic
bonding alone. The contribution to bonding from covalency is also important because ionic bonding
alone could not provide the energy needed to form the high oxidation state ions. From the Bon-Lande
equation,
N o Az  z  e 2  1 
U  1  
4 o ro  n 
Where,
εo = permittivity of free space = 8.854 x10-12 Fm-1,
A = the Madelung constant which depends on the geometry of the crystal
No = the Avogadro constant = 6.023 x 1023 mol-1
Z+, Z- are the charges on the cations and anions, respectively.
ro = the equilibrium inter-ionic distance
e = the charge on an electron
n = the Born exponent

lattice energies for ionic bonding vary with the product of the cation and anion ionic charges inversely
with the distance between ions in the lattice. Thus a high oxidation state ion with a larger z+ and a
smaller r+ should give rise to a larger lattice energy. There will also be contributions from the additional
EAs involved, but these effects must be set against the additional BDEs which may be involved and the
rapidly increasing magnitude of the higher IE values.

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As the oxidation state increases, the cost in increased total ionization enthalpy cannot be met from a
purely ionic bonding model and covalent interactions must contribute. For example, in OsO4, although
the formal oxidation state of Os is +8, it is not reasonable to assume that the molecule contains Os 8+,
just as we would not normally describe CO2 as containing C4+.

As the cationic charge increases and the ionic radius decreases, the cation becomes more and more
polarizing and hence more and more able to distort the electron cloud around the counter ion such that
the appropriate bonding model becomes less ionic and more covalent. This effect is enhanced where
there is a large and more highly charged anions which are more polarizable.

Where contribution from covalency is limited or absent as in the case of the lanthanides, high oxidation
states are not possible. In the lanthanide Ln3+ ions the 5d orbitals are empty and electrons in the core-
like 4f orbitals are unable to enter into covalent bonding to any significant extent. Thus even though the
sum of the 1st, 2nd, and 3rd IEs is lower for the lanthanides than the early d-block elements oxidation
state +3 is the maximum which can normally be attained, because the bonding is predominantly ionic.

Standard Reduction Potentials

Stability especially of the low oxidation states may also be revealed by electrode reduction potentials.
For example, the reduction potentials of the M2+ and M3+ ions of the first transition series is given in
Table 6

Table 6: Standard reduction potentials and colours of some ions of first transition series elements
Ti V Cr Mn Fe Co Ni Cu
2+
M + 2e- = M - -1.19 -0.91 -1.18 -0.44 -0.28 -0.24 +0.34
3+ 2+
M + e- = M -0.37 -0.25 -0.41 +1.59 +0.77 +1.84 - -
2+
Colour M (aq) - Violet Sky Pale Pale green Pink Green Blue
blue pink green
Colour M3+(aq) Violet Blue Violet Brown v. Pale Blue - -
purple
Negative value means the reduction is unfavourable while a positive value means the reduction is
favourable2.

Note
The fact that transition elements have variable valences/oxidation states means that in some of their
compounds the metal ions may have unpaired d electrons making the compounds paramagnetic.

Interpretation of Eº values
You will notice that some reduction potential values are negative while others are positive. A large
negative value of Eº implies that the reduced form of the couple is a good reducing agent. For
example, the Eº value for the couple V2+/V = -1.19 V, which means that V is a good reducing agent
when compared with Cu in the Cu2+/Cu couple where Eº = +0.34V.

A large positive value of Eº implies that the oxidized form of the couple is a good oxidizing agent.

2
ΔGo = -nEoF determines whether a reaction is spontaneous or not. When ΔGo for a reaction is negative such a
reaction is spontaneous.

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For example the Eº value for the reduction of Co3+ to Co2+ is 1.84 V. It shows that the Co3+ is a
good oxidizing agent. Its reduction half reaction is

Co3+ + e- → Co2+ Eº = +1.84

The oxidized form of a couple will oxidize the reduced form of a second couple if the Eº value of
the first couple is more positive than that of the second couple. For example considering the two
half-reactions:
H2O2(aq) + 2H+(aq) + 2e- 2H2O(l) Eo = +1.76 V

Fe3+(aq) + e- Fe2+(aq) Eo = +0.77 V

Hydrogen peroxide will oxidize iron(II) according to the overall reaction:

H2O2(aq) + 2H+(aq) + 2Fe2+ 2Fe3+(aq) + 2H 2O(l)

The overall Eº value is +1.76 - 0.77 = 0.99 V, which being positive makes the Gibbs energy change
negative and the reaction thermodynamically feasible. It is however, important to note that although
a reaction is thermodynamically feasible, it might be slow for kinetic reasons.

3. Catalytic Activity
Transition metals form good homogeneous or heterogeneous catalysts. This may be because they
are able to form numerous oxidation states, and as such, are able to form unstable intermediate
compounds during a reaction providing an alternative route with a lower overall activation energy.
In other cases the metal may provide a suitable reaction surface that coordinates the reactants
allowing them to react.
Examples,
Table 7: Some transition metals elements/compounds used in catalysis

Catalyst Application
TiCl3 Ziegler-Natta catalyst in production of polyethene
V 2O 5 Converts SO2 to SO3 in the contact process
MnO2 Catalyst to decompose KClO3 to give O2
Fe In the Haber-Bosch process for making NH3
FeCl3 Production of CCl4 from CS2 and Cl2
FeSO4 and H2O2 Fenton’s reagent for oxidizing alcohols to aldehyde
PdCl2 Wacker process for converting C2H4 to CH2CHO
Pd Hydrogenation reactions e.g. phenol to cyclohexanone
Pt In car exhaust fumes converters
Cu Direct process for manufacture of (CH3)2SiCl2 used to make silicones

Some transition elements are required as cofactors in enzymes that catalyse certain reactions in
living organisms. They form either metalloenzymes or metalloproteins. Examples of these
metalloenzymes and metalloproteins include the following:

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 Table 8: Metalloenzymes and metalloproteins (metalloproteins in brackets)

Metal Enzyme/metalloprotein Biological function

Mo Xanthine oxidase Metabolism of purines
Nitrate reductase Utilization of nitrates
Mn2+ Arginase Urea formation
Phosphotransferases Adding or removing PO43-
Fe2+ or Fe3+ Aldehyde oxidase Oxidation of aldehydes
Catalase Decomposes H2O2
Cytochromes Decomposes H2O2
Ferredoxin Electron transfer
(Haemoglobin) Photosynthesis
Succinic dehydrogenase O2 transport in higher animals
Aerobic oxidation of carbohydrates
Fe and Mo Nitrogenase Fixation or dinitrogen
Co Glutamic mutase Metabolism of amino acids
Ribonucleotide reductase Biosynthensis
Cu+ or Cu2+ Amine oxidase Oxidation of amines
Ascorbic oxidase Oxidation of ascorbic acid
Cytochrome oxidase Principal terminal oxidase
Galactose oxidase Oxidation of galactose
Lysine oxidase Elasticity of aortic wall
Dopamine hydroxylase Producing noradrenaline to generate nerve impulses in the brain
Tyrosinase Skin pigmentation
Ceruloplasmin Utilization of Fe
(Haemocyanin) O2 transport in invertaebrates
Plastocyanine photosynthesis
Zn2+ Alcohol dehydrogenase Metabolism of alcohol
Alkaline phosphatase Releasing PO43-
Carbonic anhydrase Regulation of PH and CO2 formation
Carboxypeptidase Digestion of proteins

4. Ability to form complexes

You learnt in SCH 301 that transition metals form the most number of coordination complexes.
This tendency in transition elements to form complexes with Lewis bases (i.e. electron donors) is
unparalleled. For example Co forms more complexes than any other element, e.g.
Co3+ + 6NH3 → [Co(NH3)6]3+
Fe2+ + 6CN- → [Fe(CN)6]4-

There are two main reasons why the elements are so good at forming complexes. First, they form
small highly charged ions that attract and hold ligands. Second, they possess vacant low energy
orbitals that accept the lone pairs of electrons donated by the ligands.

On the basis of the stability of complexes they form, transition metals just like their s and p-block
counterparts can be categorized into class-a or b-acceptors. The first half of the transition elements
as well as the lanthanides, actinides form their most stable complexes with ligands in which the
donor groups are N, O or F. These are class a acceptors and correspond to the ‘hard acids’. In
contrast the metals Rh, Ir, Pd, Pt, Ag, Au, and Hg form their most stable complexes with ligands in
which the heavier elements of groups 15, 16 and 17 are the donor groups and belong to class b
acceptors. They correspond to ‘soft’ acids. The rest of the metals belong to a/b class and have
‘intermediate’ nature.

15
 Periodic Trends in Physical and Chemical Properties
(a) Atomic (covalent) radii/pm (Inorganic Chemistry, by G. Miessler and D.A. Tarr pg 45 3rd ed)

Table 9: Calculated covalent atomic radii in pm

Sc Ti V Cr Mn Fe Co Ni Cu Zn
144 132 122 118 117 117 116 115 117 125
Y Zr Nb Mo Tc Ru Rh Pd Ag Cd
162 145 134 130 127 125 125 128 134 148
La * Hf Ta W Re Os Ir Pt Au Hg
169 144 134 130 128 126 127 130 134 149

14 Lanthanide elements

Atomic radii show a slight contraction at the beginning of the series, but towards right of the series
the size slightly increases. On going from right to the left, extra protons are placed in the nucleus
and extra orbital electrons are added to penultimate d orbitals. The orbital electrons shield the
nuclear charge 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
pulls all of the electrons more strongly causing a contraction in size.

Atoms of the transition elements are smaller than those of Group 1 or 2 in the same period. This is
partly because of the usual contraction in size across a horizontal period discussed above, and partly
because the orbital electrons are added to the penultimate d shell instead of the outer shell of the
atom.

Note:
Once the orbitals have electrons in them, the 4s orbital has a higher energy than the 3d - quite the
opposite of their order when the atoms are being filled with electrons. That means that it is the 4s
electrons which can be thought of as being on the outside of the atom, and so determine its size. It
also means that the 3d orbitals are slightly closer to the nucleus than the 4s - and so offer some
screening3.

Down the groups the atomic radii generally increase due to the increase in the number of electron
sub-shells. This effect seems to offset the increase in nuclear charge with increasing atomic
numbers. The elements in the first group show the expected increase in size Sc → Y → La.
However, in the subsequent Groups (4 – 12) there is an increase in radius of 0.1 → 0.2 Å between
the first and second member, but hardly any increase between the second and third elements. This
trend is also observed in the ionic radii. This is attributed to Lanthanide contraction – the general
decrease in atomic radii of the f-block lanthanide elements between the 2nd and 3rd transition series.

Interposed between La and Hf are the 14 lanthanide elements, in which the antepenultimate 4f sub-

3
Tabulated values are calculated for ideal molecules with no polarity. Because the polarity, chemical structure
and physical state of molecules change drastically from one compound to another, it is difficult to obtain
consistent data for all measures of atomic sizes including the van der Waals radius. Thus, the values given are
sufficient for a general comparison.

16
shell of electrons is filled. There is a gradual decrease in size of the 14 lanthanide elements from Ce
to Lu. The contraction in size from one element to another is fairly small but the additive effect
over the 14 lanthanide elements is about 0.2 Å. This is called the lanthanide contraction. The
contraction reduces the size of the last four elements in the series below that for Y in the preceding
transition series. It effectively cancels almost exactly the normal size increase on descending a
group of transition elements.

Explanation of Lanthanide Contraction

In multi-electron atoms, the decrease in radius brought about by an increase in nuclear charge is
partially offset by increasing electrostatic repulsion among electrons. Particularly, a "shielding
effect" operates: i.e., as electrons are added in outer shells, electrons already present shield the outer
electrons from nuclear charge, making them experience a lower effective charge on the nucleus.
The 4f electrons are poorest at shielding the outer electrons from the nucleus. The shielding effect
exerted by the inner electrons decreases in order s > p > d > f. Usually, as a particular sub-shell is
filled in a period, atomic radii decreases. This effect is particularly pronounced in the case of
lanthanides, as their 4f sub-shells are being filled across the period and they are less and less able to
shield the outer (5th and 6th) shell electrons. Thus the shielding effect is less able to counter the
decrease in radius caused by increasing nuclear charge.

Effects of Lanthanide contraction

As a result of the increased attraction of the outer shell electrons across the lanthanide period, the
following effects are observed:

 The atomic radii of the lanthanides are smaller than would normally be expected.
 The ionic radii of the lanthanides decrease from 1.17 Å (La 3+) to 1.00 Å (Lu3+) in the lanthanide
period.
 The third row of d block elements have only marginally larger atomic radii than the second
transition series. Thus, the covalent and ionic radii of the second and third transition series
elements are similar. As a result they have similar lattice energies, solvation energies and
ionization energies. Thus the differences in properties between the first and second transition
series are much greater than the differences between the second and the third series. The effects
are less pronounced towards the right of the d-block.
 The radii of the elements following the lanthanides are smaller than would be expected if there
were no f-transition metals.
 There is a general trend of increasing Vickers hardness, Brinell hardness, density and melting
point from cerium to lutetium (with ytterbium being the most notable exception). Lutetium is
the hardest and most dense lanthanide and has the highest melting point.
Each of these effects is sometimes referred to as the lanthanide contraction

Ionic radii follow the trends of the atomic radii. For each elements, ionic radii decrease with
increasing oxidation state. Thus the metal ions become more and more polarizing with increase in
oxidation state.

Question
Using your Knowledge of Fajans’ rules, explain how ionic radius influences the
covalent or ionic nature of a compound. How would you expect the basicity of an
oxide to vary with oxidation state of a given metal?

17
(b) Reactivity of the metals
Many of the metals are sufficiently electropositive to react with mineral acids, liberating H 2. A few
however, have low standard electrode potentials (less negative) and remain unreactive or noble.
This noble character is most pronounced for the platinum group of metals (Ru, Rh, Pd, Os, Ir and
Pt). Noble character is favoured by high enthalpies of sublimation, high ionization energies and low
enthalpies of solvation. The smaller atoms have high ionization energies but these are offset by the
high solvation enthalpies of the corresponding smaller ions.

(c) Density
Transition metals have generally high densities (> 5 gcm-3 except Sc 3.0 gcm-3 and Y and Ti 4.5
gcm-3). The densities increase across the periods (See Table 10). This is due to their small atomic
volumes compared to the Group 1 and 2 elements. Their increased nuclear charge is poorly
screened and so attracts all the electrons more strongly. In addition, the added electrons occupy the
inner d orbitals.

Table 10: Densities of the solid and liquid elements (in g cm-3) (J.D. Lee Concise Inorganic Chemistry 5th ed)

Sc Ti V Cr Mn Fe Co Ni Cu Zn
3.00 4.50 6.11 7.14 7.43 7.87 8.90 8.91 8.95 7.14
Y Zr Nb Mo Tc Ru Rh Pd Ag Cd
4.50 6.51 8.57 10.28 11.5 12.41 12.39 11.99 10.49 8.65
La Hf Ta W Re Os Ir Pt Au Hg
6.17 13.28 16.65 19.3 21.0 22.57 22.61 21.41 19.32 13.53

The densities increase as well down the Groups. This is because the volume increases more slowly
compared to the atomic masses especially due to the lanthanide contraction between the 2 nd and 3rd
series.

(d)Melting points
Table 11: Melting points of transition elements (in K)

Sc Ti V Cr Mn Fe Co Ni Cu Zn
1814 1941 2183 2180 1519 1811 1768 1728 1357.7 692.7
Y Zr Nb Mo Tc Ru Rh Pd Ag Cd
1799 2128 2750 2896 2430 2607 2237 1828 1234.9 592.2
La Hf Ta W Re Os Ir Pt Au Hg
2506 3290 3995 3459 3306 2739 2041.4 1337.33 234.3

The melting points and the molar enthalpies of fusion of the transition metals are both high in
comparison to main group elements (Table 11). This arises from strong metallic bonding in
transition metals which occurs due to delocalization of electrons facilitated by the availability of
both d and s electrons. Zn, Cd and Hg have exceptionally low melting points because the d shell is
full and the d electrons do not participate in metallic bonding.
(e) Electronegativity

18
Electronegativity is a measure of the ability of an atom to attract electrons (or electron density)
towards itself in a covalent bond. Several measures of electronegativity have been proposed by
several people including L. Pauling, R.S. Mulliken, E. Rochow and R.T. Sanderson and give
roughly parallel scales.

Generally electronegativity increases as you go from left to right across the periodic table and
decreases as you go down the periodic table (see Table 11). As you go across a period from left to
right, the atoms of each element all have the same number of energy levels and the same number of
shielding electrons. Thus, the factor that predominates is the increased effective nuclear charge.
When the nuclear charge increases, the attraction for electrons in the outermost energy level also
increases and that means the electronegativity will increase.

Apart from the other element forming the molecule, the other factors that determine
electronegativity are the coordination number and oxidation state of an element. The higher the
oxidation state the higher the electronegativity.

Table 12: Electronegativities of transition elements according to the Pauling scale

Sc Ti V Cr Mn Fe Co Ni Cu Zn
1.36 1.54 1.63 1.66 1.55 1.83 1.88 1.91 1.90 1.65
Y Zr Nb Mo Tc Ru Rh Pd Ag Cd
1.22 1.33 2.60 2.16 1.90 2.20 2.28 2.20 1.93 1.69
La Hf Ta W Re Os Ir Pt Au Hg
1.1 1.30 1.50 2.36 1.90 2.20 2.20 2.28 2.54 2.0
Notes:
1. There are some high values in the middle of the transition group. Those elements have
fairly high electronegativities for metals. The reason for that ties in with the arrangement
of electrons and the fact that the atoms are using d orbitals. The way that the d orbitals are
shielded is different than the way that s and p orbitals are shielded so there is some
variation in the transition metals that is not as easily explained as the general trend.
2. Electronegativity is usually calculated, and therefore, it is not strictly an atomic property,
but rather a property of an atom in a molecule.
(f) Ionization energy /Potential
Defined as the energy required to remove one mole of electrons from one mole of isolated gaseous
atoms or ions. It is an indicator of the reactivity of an element. Elements with low ionization
energy tend to be reducing agents. [ionization energy units = kJ/mol; ionization potential units =
electron volts, eV) i.e. energy for the reaction

Mn+ → M(n+1)+ + e- n = 0,1,…

When n = 0 we have first ionization energy, n = 1, 2nd ionization energy, etc.

In moving across the series of metals from scandium to Mn a small change in the values of the first
(as well as second) ionization energy is observed (Table 13). This is due to the increase in effective
nuclear charge which overrides the effect of the underlying (n-1)d electrons. Between Mn and Cu
there is a slight decrease. This is due to the build-up of electrons in the immediately underlying (n-
1)d sub-shells that efficiently shields the 4s electrons from the nucleus and minimizing the increase
in effective nuclear charge from element to element. Zn, Cd and Hg have the highest I.E in their

19
respective periods. This is due to the extra stability associated with their completely filled orbitals
(write the electron configurations of the three elements).

Table 13: First ionization energies of transition elements in kJ/mol

Sc Ti V Cr Mn Fe Co Ni Cu Zn
633.1 658.8 650.9 652.9 717.3 762.5 760.4 737.1 745.5 906.4
Y Zr Nb Mo Tc Ru Rh Pd Ag Cd
600 640.1 652.1 684.3 702 710.2 719.7 804.4 731.0 867.8
La Hf Ta W Re Os Ir Pt Au Hg
538.1 658.5 761 770 760 840 880 870 890.1 1007.1

Down the groups the trend is not regular. Between the first and the second series elements the
expected decrease in 1st I.E is observed. This is attributed the increase in atomic sizes and reduction
in effective nuclear charges. In the elements following La the I.E increase instead of decreasing.
These elements have smaller than expected atomic radii due to lanthanide contraction. The valence
electrons in these elements experience higher then expected effective nuclear charges because they
come after 4f orbital which shield the nucleus ineffectively.

Question
Explain how first ionization energy is related to the
(i) Metallic character of an element
(ii) Stability of a compound. For example, would you expect K 2[PtCl6] to
be more or less stable than K2[NiCl6]

(g) Electron affinity

The electron affinity, Eea, of an atom or molecule is the energy required to detach an electron from a
singly charged negative ion, i.e., the energy change for the process
X- → X + e−
An equivalent definition is the energy released (Einitial − Efinal) when an electron is attached to a
neutral atom or molecule. The sign convention for Eea is the opposite to most thermodynamic
quantities: a positive electron affinity indicates that energy is released on going from atom to anion.

Table 14: Electron affinities of d-block elements (kJ/mol)

Sc Ti V Cr Mn Fe Co Ni Cu Zn
18.1 7.6 50.6 64.3 0 15.7 63.7 112 118.1 0
Y Zr Nb Mo Tc Ru Rh Pd Ag Cd
29.6 41.1 86.1 71.9 53 101.3 109.7 53.7 125.6 0
La Hf Ta W Re Os Ir Pt Au Hg
48 0 31 78.6 14.5 106.1 151 205.3 222.8 0

Eea generally increases across a period in the periodic table in a similar manner as the ionization
energies. However, the electron affinity values are much smaller that those of I.E because electron
removal from a negative ion is easier than removal from a neutral atom.

20
A trend of decreasing Eea going down the groups in the periodic table would be expected. The
additional electron will be entering an orbital farther away from the nucleus, and thus would
experience a lesser effective nuclear charge.

(h) Magnetic properties

Many compounds of transition elements are paramagnetic, because they contain partially filled
electron shells. If the magnetic moment is measured, the number of unpaired electrons can be
calculated.

Paramagnetism and diamagnetism

When a substance is placed in a magnetic field H, the intensity of the magnetic field in the
substance may be greater or less than H. If the field in the substance is greater than H, the substance
is said to be paramagnetic and it allows the magnetic lines of force to travel through it more easily
than through a vacuum. Thus, paramagnetic materials area attracted by a magnet (they attract lines
of force and move to the stronger part of the field). Paramagnetism arises as a result of unpaired
electron spins in the atom. E.g all complexes of Cr (mostly in +2 and +3 states) are paramagnetic
while all Zn complexes and compounds are diamagnetic. This property helps in distinguishing
between low-spin and high-spin octahedral complexes.

If the field in a substance is less than H, the substance is said to be diamagnetic. Such substances
are repelled by a magnet (i.e. they repel lines of force and move from a stronger to a weaker part of
the magnetic field). In diamagnetic compounds all the electron spins are paired. Usually the
paramagnetic effect is much greater than the diamagnetic effect.

Ferromagnetism and antiferromagnetism

Ferromagnetism is a special case of paramagnetism in which the moments on individual atoms
become aligned and all point in the same direction (Paramagnetism is often a property of an
individual species such as Fe3+, while ferromagnetism is a property of an aggregate of atoms or
ions). When this happens the magnetic susceptibility is greatly enhanced compared with what it
would be if all moments behaved independently. Alignment occurs when materials are magnetized.
For example, Fe, Co and Ni can form permanent magnets upon magnetization.

Antiferromagnetism arises by pairing the moments in adjacent atoms which point in opposite
directions. This gives a magnetic moment less than would be expected for an array of independent
ions. This property occurs in several salts of Fe2+, Mn2+ and Gd3+.

Since ferromagnetism and antiferromagnetism depend on orientation, they disappear on solution of

the material.

Measurement of magnetic susceptibilities

Magnetic susceptibility is the measurable quantity and there are two main methods used: the
Faraday and the Gouy methods. The Faraday method is useful for measurements on a very small
single crystal, but there are practical difficulties because the forces are very small. The Gouy
method is more often used using the Gouy balance. The volume susceptibility κ, is determined by
weighing a sample in and out of a magnetic field. This is then used to calculate the molar
susceptibility the magnetic moment  the total spin S, and eventually n the number of unpaired
electrons responsible for the paramagnetism. Paramagnetic materials will weigh more in a magnetic
field being attracted by the same. On the other hand diamagnetic materials will be repelled by the

21
magnetic field and hence weigh less in the field. It is the change in mass of the material that is used
to work out the force acting on the compound and finally converted to the molar susceptibility.

The information obtained from the magnetic moment of a transition metal includes

(a) Number of unpaired electrons in an atoms

(b) The orbitals occupied
(c) Sometimes the structure of the complex or molecule.

If the magnetic moment is entirely due to the spin of unpaired electron s, then it is given in Bohr
magnetons by the equation:
μ s  4S(S  1) .μ B
where S is the total spin quantum number = number of unpaired electrons x ms, and μB s the Bohr
magneton.
This equation is related to the number of unpaired electrons n by the equation:
μ s  n(n  2) .μ B
The unpaired electron gives rise to a magnetic field because of its spin, and also because of orbital
angular momentum. The general equation for the magnetic moments of the first row of transition
metal ions is:
μ( S  L)  4 S(S  1)  L( L  1) .μ B
where S is the total of the spin quantum numbers, and L is the resultant of the orbital
angular momentum quantum numbers of all the electrons in the molecule.

In many compounds of the first transition series elements, the orbital contribution is quenched by
the electric fields of the surrounding atoms. Thus, the orbital contribution can be ignored so that the
observed magnetic moment may be considered to arise only from unpaired spins. In a few cases
however, the calculated magnetic moments are found to be significantly lower than the
experimentally determined moments. For example, Co2+ complexes with configurations (t2g)5(eg)2
show higher experimental magnetic moments than the calculated moments and this suggests that
there is an orbital contribution.

In the 2nd and 3rd series transition elements, and particularly in the lanthanide elements, the orbital
motion is not prevented or quenched. Thus, the orbital contribution must be included in the
calculations. In some cases there is coupling between the spin contribution S and the orbital
contribution L (spin orbit coupling or Russel-Saunders coupling) to give a new quantum number J.
In this case a more complicated formula is used:
μ  g J(J  1) .μ B
S ( S  1)  L( L  1)  J ( J  1)
where g  1 
2 J ( J  1)

22
Differences between the first row and the other two rows

Radii.
An important feature is that the filling of the 4f orbitals through the lanthanide elements causes a
steady contraction, called the lanthanide contraction in atomic and ionic sizes. The atomic and
ionic sizes of the second and third series are almost the similar

Oxidation states.
For the heavier transition elements, higher oxidation states are in general much more stable than for
the elements of the first series. Thus the elements Mo, W, Tc and Re form oxo anions in high
valence states which are not especially reduced, whereas the analogous compounds of the first
transition series elements, when they exist, are strong oxidizing agents. RuO4, WF6 and PtF6 have
no analogous among the lighter ones. The II and III oxidation states complexes and aquo ions are
important for first series but not so for heavier ones.

Oxidation states.
Aquo ions of low and medium valence states are not in general well defined or important for any of
the heavier transition elements, and some, such as Zr, Hf, and Re, do not seem to form any simple
cationic complexes. For most of them anionic oxo and halo complexes play a major role in their
aqueous chemistry although some, such as Ru, Rh, Pd and Pt, do form important cationic
complexes.

Metal-metal bonding and cluster compounds.

Heavier transition elements are prone to form strong M-M bonds than their congeners in the first
series. In the first transition series M-M bonding only occurs in metal carbonyl compounds such as
Mn2(CO)10, Fe2(CO)9, Co2(CO)8, Fe3(CO)12 and Co4(CO)12 and in carbocylate complexes such as
[Cr2(CH3COO)4(H2O)2].

In the second and third row elements M-M bonds are much more common:

i) They form carbonyls with M-M bonds similar to those from the first transition series such
as Ru3(CO)12, Os3(CO)12, Rh4(CO)12 and Rh4(CO)12 and a type not formed by the first
transition series Rh6(CO)16.

ii) The metals Mo, Ru and Rh form binuclear carboxylate complexes such as
[Mo2(CH3COO)4(H2O)2] which are similar to Cr(II) acetate.

iii) The halide ions [Re2Cl9]2- and [Mo2Cl9]3- also have M-M metal bonds.

iv) The lower halides of several of several elements have a group of three or six metal atoms
bonded together and are called cluster compounds. The elements, in their respective
groups, are:

Nb Mo

Ta W Re

[Nb6Cl12]2+ and [Ta6Cl12]2+ have unusual structures. Both contain six metal atoms arranged as a
cluster at the corners of an octahedron, with 12 halogen atoms bridging across the corners. The
species formed by Nb and Ta, have no V analogues at all, and similarly the Tc 2Cl83- and Re2Cl82-

23
ions have no manganese analogues.

Magnetic properties.
Whereas a simple interpretation of magnetic susceptibilities of the compounds of first transition
series elements usually gives the number of unpaired electrons and hence the oxidation state and d
orbital configuration, more complex behaviour is often encountered in compound of the heavier
elements.

24
 UNIT 2
Metallurgy
This is the science and technology of extracting metals from their natural sources and preparing them
for practical use. It involves the following steps:
i) Mining the ore from the ground
ii) Concentrating the ore or preparing for further treatment. This entails crushing the ore and
removing the gangue (the useless earth and rock material).
iii) Reducing the ore to the free metal
iv) Refining or purifying the metal
v) Mixing the metal with other elements to obtain the desired properties - making alloys i.e
metallic materials that are composed of two or more elements.

Metallurgical Processes
There are three main processes in metallurgy:
i) Pyrometallurgy
ii) Hydrometallurgy
iii) Electrometallurgy

(i) Pyrometallurgy
This involves application of high temperatures to reduce the mineral. The methods involved in this
process are:

a) Calcination – the heating of an ore to bring about its composition and the elimination of a
volatile product such as CO2 or H2O. Example,

PbCO3(s) 
PbO(s) + CO2(g)
Most carbonates decompose reasonably rapidly at temperatures in the range of 400 to 500 o C.
CaCO3 requires a temperature of about 1000o C. Most hydrated minerals lose H2O at
temperatures on the order 100 to 300o C.

b) Roasting – a thermal treatment that causes chemical reactions between the ore and the furnace
atmosphere. Reactions such as oxidation or reduction followed by calcination may occur. For
example, oxidation of sulphide ores to metal oxides:

2ZnS(s) + 3O2(g) → 2ZnO(s) + 2SO2(g)

2MoS2(s) + 7O2(g) → 2MoO3 + 4SO2(g)

HgS(s) + O2(g) → Hg(g) + SO2(g) (usual for sulphides of less active metals).

In many instances the roasting is done in a reducing atmosphere and this yields the metal. For
example, CO produces a reducing atmosphere under which metal oxides are reduced to the
corresponding metals. Example,

PbO(s) + CO(g) → Pb(l) + CO2(g)

This is not applicable to very active metals as the are either not reduced by Co of they form
intractable carbides.

25
 c) Smelting – A melting process in which the materials formed in the course of chemical reactions
separate into two or more layers. The two layers mostly formed are the molten metal (either
single metals or a mixture of more than one) and the slag. The slag consists of the molten
silicate minerals with aluminates, phosphates, fluorides etc. It is formed when a basic metal
oxide such as CaO reacts at high temperatures with molten silica, SiO2:

CaO(l) + SiO2(l) → CaSiO3.

Note
Pyrometallurgical operations require large quantities of energy and are often are often a source of
atmospheric pollution.

(ii) Hydrometallurgy
In this method the metal is extracted from its ore by use of aqueous solutions. In this method the
most important process is leaching. This involves selectively dissolving the metal-containing
compound. Often the dissolving process involves formation of a complex ion. For example, during
the extraction of gold from poor grade ores, the crushed ore is placed on large concrete slabs, and a
solution of NaCN is sprayed over it. In the presence of CN- and air, the gold is oxidized and
dissolves, forming the stable Au(CN)2- ion:

4Au(s) + 8CN-(aq) + O2(g) + 2H2O(l) → 4Au(CN)2-(aq) + 4OH-(aq)

After the metal ion is selectively leached from the ore, it is precipitated from solution as the
free metal or as an insoluble ionic compound. Example’

4Au(CN)2-(aq) + Zn(s) → Zn(CN)42- (aq) + 2Au(s)

(iii) Electrometallurgy
This involves electrolysis f either molten salts or aqueous solutions. These methods are important
for obtaining the more active metals such as sodium, magnesium, and aluminium. These easily
reduce water. The standard reduction potentials of water under both acidic and basic conditions are
more positive than those of Na+ (Eored = -2.71V), Mg2+ (Eored = -2.37V), and Al3+ (Eored = -1.66 V):

2H+ (aq) +2e- → H2 (g) Eored = 000 V

2H2O(l) + 2e- → H2 (g) + 2OH- (aq) Eored = -0.83 V

To make such metals by electrochemical reduction, therefore, we must employ a molten-salt medium in
which the metal ion of interest iis the most readily educed species.

Summary
A transition element is one whose atom has an incomplete d subshell or whose atom
gives cation(s) with an incomplete d subshell. Sc and zinc do not qualify as transition
elements. They have no ion that has a partially filled d orbital.

Zinc

 Forms only one ion (other transition elements form 2 or more).

 Zn2+ has a completely full 3d sub-shell.

26
  Zn2+ has the following configuration 1s2 2s2 3s2 3p6 3d10 or [Ar] 3d10.

Scandium

 Forms only one ion (other transition elements form 2 or more).

 Sc3+ has no 3d or 4s electrons.
 Sc3+ has electronic configuration 1s2 2s2 3s2 3p6.

In making the ions of transition elements, the 4s electrons are removed first!

Transition Metal Questions

1. Write the electron configurations of the following d-block elements.

a) Vanadium
b) Manganese
c) Copper
d) Zirconium

2. Transition element and d-block are 2 terms that are easily confused..

a) Using the appropriate definitions, explain why Zn and Sc are not Transition metals.
b) What would the oxidation states of the ions of Sc and Zn be?

3. What are the oxidation states of the transition metal in each of the following compounds?

a) KMnO4
b) Na2CrO4
c) CrO3
d) MnO2
e) Na2Fe2O4
f) Mn2(CO)10

4. Write the electronic configuration of the following atoms or ions.

a) Fe
b) Mn2+
c) V3+
d) Cu+
e) Cu2+

27
 UNIT 3
Group 3 Elements, 21Sc, 39Y and 57La

Property Scandium (Sc) Yttrium (Y) Lanthanum(La) Actinium

1 2
Electron Configuration [Ar]3d 4s [Kr]4d15s2 [Xe]5d16s2 [Xe]6d17s2
Terrestrial abundance 25 ppm 31 ppm 35 ppm
Mineral Thortveitite, Sc2Si2O7 Associated with lanthanides
Atomic radius/pm 162 180 187 189
-3
Density/g cm 3.0 4.5 6.17
Electronegtivity 1.3 1.2 1.1

Introduction
The chemistry of these elements concerns the formation of a predominantly +3 oxidation state due to
the loss of all three valence electrons giving a well-defined aqueous cationic chemistry. Due to this
their chemistry is atypical of transition metal elements even though each of them is the first member of
a transition series. They have a limited coordination chemistry mostly limited to small ion Sc 3+ and
formation of variable oxidation states is very limited even though materials containing the metals in low
oxidation states can be prepared. A limited organometallic (mostly cyclopentadienyl) chemistry has
developed.

Extraction
These elements are also obtained from the products of nuclear fission and uranium ores. The heavier
metals due to their atomic and ionic sizes are closely associated with the lighter and heavier lanthanides
respectively. They are currently obtained by ion exchange, together with selective complexation and
solvent extraction.

Scandium is a hard, silvery, rough very dark metallic element that develops a slightly yellowish or
pinkish cast when exposed to air. It is not resistant to weathering when pure and is destroyed on
prolonged contact with most dilute acids. However, like some other reactive metals, this metal is not
attacked by a 1:1 mixture of nitric acid (HNO3) and hydrofluoric acid, HF.
Uses
Scandium
- Laser crystals and coatings
- The radioactive isotope Sc-46 is used in oil refineries as a tracing agent.
- Scandium iodide added to mercury-vapour lamps produces an efficient artificial light source that
resembles sunlight, and which allows good colour-reproduction with TV cameras.
- Aluminium-scandium alloys for minor aerospace industry components, and for unusual designs
sports equipment (bikes, baseball bats, firearms, etc) which rely on high performance materials.
Yttrium
- Basis for phosphors used to produce red colour on TV screens
- Garnets e.g. Y3Fe5O12 used in microwave filters in radar
Lanthanum
- The oxide used as an additive in high quality optical glasses- it imparts high refractive index.

28
Physical properties
- They are rather soft silvery-white metals with hexagonal close packing (hcp) structures
- They are less electropositive than their predecessors but more electropositive that their successors

Chemical reactivity and trends

 Reactivity increases down the group e.g. La tarnishes in air more rapidly than Y as it forms a
protective oxide layer
 Burn in O2 to give M2O3
 React with halogens at room temp and other non-metals on heating
 Reduce water with evolution of H2 especially if finely ground
 Dissolve in dilute acid
 Strong acids give soluble salts while weak acids like HF, H3PO4 and H2C2O4 produce sparingly
or insoluble salts
 Sc3+ the smallest and least basic, mostly like Al3+ with its aqueous solutions appreciably
hydrolyzed and oxide having acidic properties
 Y3+ and La3+ show basic properties close to Ca
 Few organometallic compounds known
Simple Compounds

(i) Oxides
- M2O3 are white solids prepared directly from the elements.
- Basic with basicity increasing down the group
- La2O3 slakes in water like CaO
- These dissolve in acids to give the appropriate colourless diamagnetic salts (Explain why the salts
are colourless and diamagnetic)
(ii) Hydroxides
- M(OH)3 obtained s gelatinous ppts from aqueous solutions of the salts by addition of OH-.
- Sc(OH)3 dissolves in excess conc. NaOH to give Sc(OH)6]3-
- Y and La hydroxides are mainly basic. La(OH) 3 will absorb CO2 like Ca(OH)2
(iii) Halides
- MX3 best prepared by direct reaction of the elements
- Hydrated halides decompose on attempts to dry them. e.g. chlorides give Sc 2O3, YOCl and
LaOCl
- all very soluble in water except the fluorides-pptn of fluorides can be used as a qualitative test for
these elements
- Deliquescent
- SCF3 has ability to form complexes [ScF6]3- which can be precipitated as K+, NH4+ etc salts.

29
 Prepared by dry methods to avoid hydrolysis
(iv) Sulphates and nitrates
 All known but decompose to oxides on heating
Complexes
The coordination chemistry of the group 3 elements is poorly developed. They form weaker coordinate
bonds due to them having;
o Appreciably large ionic sizes even in the +3 oxidation state
o Greater electropositive character which inhibits covalent contribution to their bonding.
- These properties are more visible in La.
- Sc is a class-a acceptor and complexes most readily with chelating O-donor ligands.
- La and Y form complexes with S and N donor ligands such as dithiocarbamates and
dithiophosphinates
- Coordination numbers increase from 6 in Sc e.g. in [Sc(dmso)6], [Sc(bipy)3] etc to higher
coordination numbers in Y and La e.g. 8- coordinate [Y(OH)(H2O)2(pheh)2]2Cl4.2(phen).MeOH
and 10-coordinate [La(NO3)3(bipy)2]

References

(1) IUPAC Compendium of Chemical Terminology 2nd Edition 1997, R.B 43.
(2) Cotton, F. A.; Wilkinson, G.; Murillo, C. A. Advanced Inorganic Chemistry 6th ed.; Wiley
New York, 1999.

30
 UNIT 4
Group 4: Titanium, Zircconium and Hafnium

22 40 72
Property Ti Zr Hf
No of Natural isotopes 5 5 6
Electron configuration [Ar]3d24s2 [Kr]4d25s2 [Xe]4f145d26s2
Electronegativity 1.5 1.4 1.3
Atomic radius (pm) 147 160 159
Density (25o C)/g cm3 4.5 6.51 13.28
MP/oC 1667 1857 2222
BP/oC 3285 4200 4450
Common ores Ilmenite FeTiO3 Zircon ZrSiO4 MSiO4.xH2O (M = Hf, Th, Zr
Rutile TiO2 Baddeleyite, ZrO2

Introduction

These elements are classified as type a metals (hard acids) and are found as silicates and oxides in many
silicaceous materials. These are frequently resistant to weathering and often accumulate in beach
deposits that can be profitably exploited.

Because of the lanthanide contraction the ionic radii of Zr and Hf the same and as a result they are
virtually identical chemically. This is seen in their close association in nature.

Extraction of the metals

 The metals are not obtainable by reduction of the oxide with C because they form intractable
carbides. Even reduction with Na, Ca, or Mg cannot remove all the oxygen.
 The metals are very reactive at elevated temperatures and unless prepared in the absence of
oxygen they will get contaminated.

1. Titanium
- Main ores: FeTiO3 (ilmenite) and TiO2 (rutile).
- Kroll (after Wilhelm Kroll 1932) process used to extract Ti at red heat.

(a) From Rutile

TiO2 + 3C + 4Cl2 → 2TiCl4(g) + CO2 + 2CO (at 950o C)

TiCl4(g) + 2Mg → Ti(s) + 2MgCl2(s)
Solid MgCl2 removed at 1000 °C

(b) From ilmenite

FeTiO3 + 7Cl2 + 6C → 2TiCl4 + FeCl3 + 6CO (at 900o C)

The TiCl4 is fractionally distilled from the FeCl3 and other impurities and then reduced with molten
magnesium in a sealed furnace under Ar. Molten MgCl2 is tapped off periodically and after cooling,
residual MgCl2 and any excess Mg are removed by leaching with dilute HCl and water or by distillation

31
leaving titanium sponge. This is ground and washed with aqua regia and melted under argon or vacuum
and cast into ingots. Reduction with Na gives a more readily leached product.

2. Zirconium and Hafnium

 Zirconium is also produced commercially by the Kroll process.
 When metal with low O and N2 content is required the van Arkel-de Boer method is used.
Crude metal is heated in an evacuated vessel with a little iodine at about 200o C when ZrI4
volatilizes. A W or Zr filament is simultaneously heated to 1300o C which decomposed the ZrI4
to give pure Zr which is deposited on the filament.
 Hf is also produced in the same way as Zr but on a smaller scale.

From silicate ores the following reaction process is followed:

fused NaOH Na2SiO3 boiling water

ZrSiO4 ZrO2.xH2O + SiO2.H2O
Na2ZrO3
Sodium silicate
and zirconate HCl

ZrOCl2 + SiO2.H2O
Zirconyl chloride

NH3

Mg metal C +Cl2
Zr/Hf ZrCl4 ZrO2.xH2O (pure)

Figure 3: Extraction of Zr and Hf from Zircon
Uses of the metals
(a) Ti
It is a light, strong, lustrous, corrosion-resistant (including resistance to sea water and chlorine)
transition metal with a greyish colour.

Titanium can be alloyed with other elements such as iron, aluminium, vanadium, molybdenum and
others, to produce strong lightweight alloys for aerospace (jet engines, missiles, and spacecraft),
military, industrial process (chemicals and petro-chemicals, desalination plants, pulp and paper),
automotive, agri-food, medical (prostheses, orthopaedic implants, dental implants), sporting goods,
jewellery etc. When alloyed with small quantities of metals such as Al and Sn, it has the highest
strength to density ratio of any of the engineering metals.

About 95% of titanium ore extracted from the Earth is destined for refinement into titanium dioxide
(TiO2), an intensely white permanent pigment used in paints, paper, toothpaste, and plastics. It is also
used in cement, in gemstones, as an optical opacifier in paper, and a strengthening agent in graphite
composite fishing rods and golf clubs.

TiCl4: used as a Lewis Acid catalyst (Ziegler-Natta catalyst for polymerization of ethane and other
terminal alkenes).

(b) Zr

32
  Has a high corrosion resistance and in certain chemical plants it is preferred to stainless steel,
titanium and tantalum.
 Used in alloying in a variety of steels.
 Cladding for uranium dioxide fuel rods in water cooled nuclear reactors-for this it is alloyed
with 1.5% tin.
o It is ideal for this use due to its corrosion resistance, stability under irradiation, and
extremely low absorption of thermal neutrons. The small amount of Hf present has to
be removed because it has very high absorption of thermal neutrons (600 times more so
than Zr). This is achieved by solvent extraction taking advantage of the difference in
solubilities of the nitrates in tri-n-butyl phosphate or the thiocyanates in hexone (methyl
isobutyl ketone).
 Production of bullet-proof steels

(c) Hf
 Due to high neutron absorption ability it is used for reactor control rods in nuclear submarines.

Chemical reactivity and trends

 They are electropositive but less so than the group three elements.
 The most important oxidation state is +4. Most compounds in this oxidation state are covalent
though Zr and Hf have oxides which are more basic than Ti and give more extensive and less
hydrolysed aqueous chemistry- ionic sizes.
 They react directly at high temperature with most non-metals, particularly, O2, H2 reversibly)
and in the case of titanium, nitrogen (Ti burns in N2).
 The hydrides, borides, carbides, and nitrides are hard, refractory, nonstoichiometric materials
with metallic conductivities.
 Metals are pyrophoric when finely divided - care should be taken when machining these
elements.
 In massive form they are very resistant to corrosion due to formation of a dense adherent self-
healing oxide film.
 Except for HF (best solvent), mineral acids have little effect unless hot.
 Alkalis have no effect on the metals even when hot.
 Most important oxidation state is +4. Most compounds are covalent but Zr and Hf being larger,
have oxides that are more basic than that of Ti and which give rise to a more extensive and less
hydrolysed aqueous chemistry.

Summary of important reactions

MO2
MF62-
complex
O2 MCl4
HF
No Cl2
dilute acids M
action
hot aq alkali H2, N2, C, or B high temp
No MH2, MN, MC, MB
action (interstitial)
Figure 4: The principal reactions of Ti, Zr and Hf

33
Binary Compounds

1. The Halides
The tetrafluorides are white solids prepared by the action of anhydrous hydrogen fluoride on the
tetrachlorides.

TiCl4 + 4HF → TiF4 + 4HCl

They are not attacked by water. Excess fluoride gives excess complexes such as TiF 62-, ZrF62-
(octahedral), and ZrF73- (pentagonal bipyramidal).

TiF4, is white solid mp 284o C. It forms a polymer in the solid state consisting of corner sharing TiF6
octahedra. TiCl4 is colourless liquid mp -24o C while TiBr4 is an orange solid with mp 38o C and TiI4 is
a dark brown solid with mp 155o C. The tetrahalides of Zr and Hf, MX4 are all white solids.

MX4 (X = Cl, Br) are prepared by passing the halogen over heated dioxide in the presence of a reducing
agent such as C.
MO2 + C + 2Cl2 → MCl4 + CO2

Unlike the tetrafluorides, the all tetrachlorides are hydrolysed by water.

TiCl4 + 2H2O → TiO2.2H2O + 4HCl

MCl4 + 2H2O → MOCl2 + HCl (M = Zr or Hf)

Excess conc HCL gives octahedral complexes TiCl62-, ZrCl62- and HfCl62 which can be precipitated as
ammonium salts e.g. (NH4)2TiCl62.2H2O.

MI4 are prepared by iodination of the dioxide with aluminium triiodide at 130 – 400o C: MO2 + AlI3 =
3MI4 + 2Al2O3.

In gas phase probably all the tetrahalides form monomeric tetrahedral structures. The tetrahalides of Ti
except TiF4 have monomeric tetrahedral structures at stp. The most important of all the halides is TiCl 4.

TiCl4
 Colourless liquid (mp -36°C, bp 136 °C, pungent odor)
 Fumes in moist air (Why?)
 Vigorously and completely hydrolyzed by water

TiCl4 + 2H2O → TiO2 + 4HCl

 An intermediate in one of the processes of making TiO2

Used to produce Ziegler - Natta catalysts for the polymerization of ethene and other terminal alkenes
(see Fig.1).

34
 Figure 0.5 The Cossee-Arlman mechanism of polymerization of propene

The lower halides of these elements are all known except ZrF3 and HfF3. They are diamagnetic except
TiF3 suggesting that they could be containing M-M bonds. The lower halides of Ti are prepared by
reduction of the tetrachloride either with the metal or with hydrogen gas:

2TiCl4 + H2 2TiCl3 + 2HCl

colourless violet

Heat (disproportionate)

TiCl2 TiCl4 + TiCl2

red brown
The others Ti dihalides TiX2 (X= Br, I) can be similarly obtained. The dihalides are diamagnetic and
strongly reducing and decompose H2O.

Oxides
The most important include TiO2, ZrO2 and HfO2.

Titanium oxides
 TiO2, most important. Other non-stoichiometric phases have been reported by reduction of TiO 2.

35
 3 crystalline forms of TiO2 (rutile, anatase, brookite; all naturally occurring) are known
 TiO2 mainly used as a white pigment base in paints. The material used for this is prepared by the
sulphate or chloride process because the natural one is coloured due to impurities.
 In this it has replaced white lead 2PbCO3.Pb(OH)2 due to the fact that:
o White lead forms PbS (black) in industrial atmospheres during the production or weathering of
paint
o Pb is toxic
o TiO2 has exceptionally high refractive index in the visible region of the spectrum and is
chemically inert.
Pigment grade TiO2 may be prepared by either the sulphate or the chloride process because the
naturally occurring rutile is coloured by impurities like iron etc.

The Sulphate Process

Ilmanite (FeTiO3)

Digest with H2SO4

Sulphate 'cake'

Leach with water

Fe2(SO4)3 + TiOSO4

Add scrap Fe to reduce Fe3+

FeSO4 + TiOSO4

Filter Cool and vacuum evaporate

FeSO4.7H2O

TiOSO4
1. Boil to hydrolyze
2. Seed to produce anatase or rutile

TiO2.xH2O

Wash ans calcine at 800-900o C

Base pigment
Figure 6: The sulphate process of preparing pigment grade TiO2

36
Note
1. This process cannot use rutile due to its insolubility in H2SO4
2. Can operate on lower grade ores unlike the chloride process which will produce chloride
wastes from which chlorine cannot be recovered.
3. Accounts for 56% of all the TiO2 produced and the chloride process the rest

The Chloride process

Rutile

o
Coke and chlorine at 950 C

Crude TiCl4

Treat with H2S or boil to reduce

the volatile impurity VOCl3

Pure TiCl4

Heat in oxygen above 1000oC

Base pigment
Figure 7: The chloride process of TiO2 manufacture

Compounds with Oxoanions

 Normal salts of Ti4+ cannot be prepared from aqueous solutions as they yield basic hydrolyzed
species. Even for Zr4+ and Hf4+, normal salts like Zr(NO3)4.5H2O and Zr(SO4)2.4H2O can only
be isolated from sufficiently acidic solutions. Basic salts and anionic complexes are readily
isolated.
 Anhydrous nitrates can be prepared by the action of N2O5 on MCl4. Ti(NO3)4 forms as a white
sublimable highly reactive 8-coordinate compound (mp = 58o C), Zr(NO3)4 is isostructural but
Hf(NO3)4 sublimes at 100o C as the adduct Hf(NO3)4.N2O5
 Several oxo-metal(IV) compounds have been reported:
o Do not contain discrete MO2+ but are polymeric in solid state. E.g TiOSO4.H2O
consists of Ti-O-Ti-O- chains where each Ti is approximately octahedrally coordinated
to 2 bridging oxygen atoms, one water molecule and an oxygen atom from each of the
three sulphates.

Complexes of Group 4 elements

Oxidation state IV
 Diamagnetic (d0 species)
 Prone to hydrolysis

37
  Coordination no 6 most common for Ti but 7 and 8 are possible. 7 and 8 are common for Zr
and Hf

Ti(IV) Complexes
Aqueous chemistry
 There is no firm evidence for existence of Ti4+ ion in solution.
 they only have oxo species; basic oxo salts or hydrated oxides may be precipitated. e.g.
TiOSO4.H2O, (NH4)2TiO(C2O4)2.H2O. These have (Ti-O-Ti-O-)x chains.
 Spectroscopic evidence exists for TiO2+ in 2M HClO4. Complexes containing the T=O group
are, however, known (e.g. [Ti(TPP)O]).

Anionic complexes
 Dissolution of Ti(s) or hydrous oxides in HF affords fluoro complex ions, e.g. [TiF 6]2- (isolated
as crystalline salts).
 [TiCl6]2- may be isolated from solutions of TiCl4 saturated with HCl(g).

Adducts of TiX4
 TiX4 halides form adducts of the type TiX4L or TiX4L2 with bidentate and monodenate ligands
respectively.
 These are crystalline solids (usually octahedral) that dissolve in organic solvents. e.g. cis-
TiCl4(OPCl3)2 in Fig 8.

Peroxo complexes
 Aqueous solutions of Ti ions react with H2O2
 Form peroxide species, e.g. [Ti(O2)(OH)]+ (orange) below pH 1
 Reaction used for colorimetric determination of Ti or H2O2

Solvolysis of TiCl4
 Requires alcohols and produces alkoxide complexes
 The alkoxides are water-sensitive. They may be crystalline or liquid (can be distilled).

TiCl4 + 4ROH + 4R'NH2 = Ti(OR)4 + 4R'NH3Cl

 Primary alcohols usually give crystalline polymeric alkoxides, e.g., Ti(OC2H5)4 is a tetramer
(Fig 8).
 Often called “alkyltitanates” and are used to make heat-resisting paints, where eventual
hydrolysis occurs to form TiO2.

38
 Figure 8: Some complexes o Ti(IV)

Figure 9: The tetrameric structure of Ti(OC2H5)4

Titanium dialkylamides
 Not polymeric like Ti(IV) alkoxides
 Synthesized with lithium dialkylamides

TiCl4 + 4LiNR2 = Ti(NR2)4 + 4LiCl(s)

 Ti(IV) amides undergo insertion reactions; with CS2 giving dithiocarbamates.

Ti(NR2)4 + 4CS2 = Ti(S2CNR2)4

Ti(III) and Ti(II) Complexes

Titanium(III) chloride
 TiCl3 has several crystalline forms. The violet a form is made by reduction of TiCl4 vapor with H2
at 500-1200 °C.
 Reduction of TiCl4 by alkylaluminium(III) complexes in inert solvents gives a brown b form that
converts to the a form at 200-300 °C.
 The α form has a layer lattice with TiCl6 groups.

39
 The β-TiCl3 is fibrous with single chains of TiCl6 octahedra sharing edges (diagram at right).
 NB: β-TiCl3 is an important catalyst for the polymerization of olefins (Ziegler-Natta process).
 This catalyst is used by, e.g., SASOL (S. Africa) to synthesize poly(ethylene), poly(propylene), and
now poly(ethylene/pentene) copolymers.
 Synthetic rubbers are often produced with TiCl3 / AlEt3 and are copolymers of styrene, butadiene,
and a 3rd component (e.g. 1,4-hexadiene or dicyclopentadiene).
 Mechanism of polymerization is given below in Fig 7 (cf one given earlier).
 Key steps: reduction of Ti(IV) to Ti(III) by AlEt3 and then substitution of Cl− by Et− ion on surface
of the fibrous, heterogeneous catalyst system. Dissociation of Cl2 then gives the reactive catalyst.

Figure 10: Mechanism of polymerization of ethene over the Ziegler-Nattta catalyst

More on Zr and Hf
Atomic radii of Zr & Hf are nearly identical. Thus, they have similar chemistry and this explains the
small differences in solubilities, volatilities, etc. of compounds of Zr & Hf

The main differences from Ti are:

 Very few compounds with oxidation nos. below 4 (e.g., Zr3+ not common, but Ti3+ is common).
 The +4 ions have a high charge, no filled d-orbitals to dictate stereochemical preferences, and
are relatively large (0.74 & 0.75 Å)
 Coordination numbers of 7 and 8 are thus common (rather than 6)
 Coordination polyhedra are common with O2−and F− ligands:

[ZrF6]2− Octahedron; Li2ZrF6; CuZrF6.4H2O

[ZrF7]3− Pentagonal Bipyramid; Na3ZrF7
[ZrF8]4− Square antiprism; Cu2ZrF8.12H2O

40
Zr compounds
 All are white unless anion is colored (why?)

Binary Compounds
 The oxide ZrO2 is made by heating the hydrous oxide, which is precipitated on addition of
OH−to Zr(IV) solutions.
 ZrO2 – refractory material (mp 2710 °C), chemically highly resistant. Used for furnace linings,
crucibles, etc.
 The tetrachloride (ZrCl4) is made by reaction of ZrO2 with C and Cl2. It is Td in the vapor phase
but exhibits chains of ZrCl6 octahedra in the crystalline solid state.
 Like TiCl4, ZrCl4 is a Lewis acid & forms adducts with Cl−, POCl3, and ethers.
 ZrCl4 is only partly hydrolyzed by water at room temperature to give a stable oxide chloride,
ZrOCl2.

Aqueous Chemistry and Complexes

 ZrO2 is more basic than TiO2; virtually insoluble in excess base
 Lower tendency for complete hydrolysis => more aqueous chemistry for Zr(IV)
 It is doubtful if Zr4+ exists, even in strong acid solution
 Hydrolyzed ion (ZrO2+) is called the ‘zirconyl’ ion, but NB: Zr=O bonds do not exist!
 ZrOCl2.8H2O crystallizes from dilute HCl has the cation [Zr4(OH)8(H2O)16]8+. (The four Zr4+
ions lie in a distorted square, are bridged by pairs of μ-OH groups, and are 8-coordinate with
the apical waters.)

In conc. HF, only [ZrF6]2− is present in solution. Salts crystallizing from these solutions contain
[ZrF7]3−and [ZrF8]4− (Fig. 8)

Figure 11: Anionic complexes of Zr

 Other 8-coordinate Zr(IV) complexes are the carboxylate, Zr(O2CR)4, the acetylacetonate,
Zr(acac)4, the oxalate, Na4[Zr(ox)4], and the nitrate, Zr(NO3)4

41
 UNIT 5
Group 5: Vanadium, Niobium and Tantalum
23 41 73
Property V Nb Ta
No of Natural 2 1 2
isotopes
Electron [Ar]3d34s2 [Kr]4d35s2 [Xe]4f145d36s2
configuration
Electronegativity 1.6 1.6 1.5
Atomic radius 134 146 146
(pm)
Density (25o C)/g 6.11 8.57 16.65
cm3
MP/oC 1915 2468 2980
BP/oC 3350 4758 5534
Patronite VS4, vanadite Columbite or tantalite Columbite or
Common ore PbCl2.3Pb3(VO4)2 carnotite (Fe,Mn)M2O6 M = Nb, tantalite
K(UO2)(VO4).1.5H2O Ta. Pyroclore, (Fe,Mn)M2O6 M =
NaCaNb2O6F Nb, Ta

Introduction
This group contains vanadium, niobium and tantalum. Vanadium was named after Vanadis the
Scandivanian goddess of beauty by N.G. Sefström due to the richness and variety of colours found in its
compounds. Niobium and tantalum were found together. Tantalum was given the name by A.G.
Ekeberg due to its difficulty in dissolving in acids. Niobe was daughter of Tantalus, the mythical king
of Phrygia and since the two were found together niobium (also called columbium by C. Hatchett) was
named after Niobe.

The chemistry of Nb and Ta are similar due to the lanthanide contraction. Thus, they are mostly
associated with each other in nature (notice they have same atomic size). In fact their individual
identity was hindered because of their close chemical similarities.

Preparation and uses of the Elements

The flow diagram below shows the extraction of vanadium. 80% of the vanadium is used as an additive
to steel in which it forms V4C3 with any carbon present and this disperses to produce fine grained steel
with increased resistance to wear and is stronger at high temperatures. Such steels are used in the
manufacture of springs and high-speed tools.

Pure vanadium may also be obtained by reduction of VCl5 with H2 or Mg or by electrolysis of partially
refined vanadium in fused alkali metal chloride or bromide.

42
 Crushed ore or vanadium residue

roast with NaCl or Na2CO3

o
at 850 C

NaVO3 (sodium vanadate)

Leach with water and acidify with

H2SO4 to pH 2-3

Red cake (a polyvanadate)

fuse at 700oC

V2O5 (Black technical grade)

Ferrisilicon or Al or Fe or Fe ore
reduction with Ca
in an electric furnace in the presence
of line to remove SiO2 as a slag or Ca silicate

V Ferrovanadium (V/Fe alloy) (80% of all V produced)

Figure 12: Preparation of vanadium

Note: The metals are difficult to obtain pure due to their high reactivity with O2 and N2 at the
temperatures of production. In fact reported values of their bulk properties have often required
revision due to this.

Methods for extraction of Nb and Ta are varied and complicated. The ore is fused with alkali or
digested with acids to solubilize the metals. According to Marignac, dissolution in HF acid yields the
sparingly soluble K2TaF7 and the soluble K2NbOF5.2H2O. This affords a good degree of separation.
Presently, solvent extraction is used. For example, Ta can be extracted from dilute aqueous HF
solutions by methyl isobutyl ketone (MIBK). Increasing the acidity of the aqueous phase allows Nb to
be extracted into a fresh batch of MIBK. The metal complexes are then obtained from the organic
phases by stripping with water salts. After drying and conversion to M 2O5, the metals are obtained by
reduction of the pentoxides with Na, carbon or the metal carbide.

Uses
 V is used as an additive in steel. It forms V4C3 with any carbon present and this disperses to
produce a fine-grained steel which has increased resistance to wear and is stronger at high
temperatures. Such steel are used in the manufacture of springs and high speed tools (machine
tool bits and other cutters like power saws).
 Nb is used in the production of numerous stainless steels for use at high temperatures and
Nb/Zr wires used in superconducting magnets.
 Ta is used in construction of chemical plants, especially where it can be used as a liner inside
cheaper metals. This is because it has extreme corrosion resistance due to the formation of an
exceptionally tenacious film of oxide.
 Ta is also used in bone repair and internal suturing due to its complete inertness to body fluids.

43
  Ta is also used in manufacture of capacitors where the oxide film is an efficient insulator. It is
used as a filament or filament support although it has been superseded by tungsten.

Atomic and physical properties

 All are shiny silvery metals with typically bcc structures.
 They are comparatively soft and ductile when very pure. Impurities make then hard and brittle
 Smaller atomic sizes than their predecessors hence slightly less electropositive.
 Nb and Ta are virtually identical in size due to lanthanide contraction.
 They have high mp, bp and enthalpies of atomization due to stronger M-M bonds. These
quantities reach their maximum in this and the next group. In the first transition series V is the
last element before some of the (n-1)d electrons begin to enter the inert electron-core of the
atom and are therefore not available for bonding. As a result, it has the highest melting point in
the series and it is the last element whose compounds in the group oxidation state are not
strongly oxidizing. In the second and third transition series, the entry of (n-1)d electrons into
the electron core is delayed somewhat and it is molybdenum and tungsten whose melting points
are the highest.

Chemical Reactivity and Trends

 React with most non-metals frequently giving interstitial and non-stoichiometric products at
high temperatures.
 Generally resistant to corrosion due to the formation of surface films of oxides which are
particularly effective in the case of Ta.
 V and Nb are attacked by hot conc. mineral acids but are resistant to fused alkalis. Ta on the
other hand, unless heated, is attacked by only by oleum, HF or more particularly HF/HNO 3
mixture and fused alkalis.
 Lower oxidation states become unstable down the group. Thus the most stable oxidation state
for V is +4, but even +3 and +2 (which are admittedly strongly reducing) have well
characterized cationic aqueous chemistry (i.e. they form such ions as [V(H2O)6]3+and
[V(H2O)6]2+ in aqueous media). In contrast most of the chemistries of Nb and Ta are confined
to the group oxidation state +5. They provide no counterparts to the cationic chemistry of V in
the +2 and +3 oxidation states.
 In vanadium, the +4 oxidation state is predominantly found as VO2+ (vanadyl) ion. It is the
most stable diatomic cation known and retains its identity throughout a wide variety of
reactions and forms many complexes. For Nb and Ta this is best represented by their halides.
 In low oxidation states Nb and Ta for a series of cluster compounds based on octahedral M 6X84+
or M6X126+ units. These are formed as a consequence of the strength of metal-metal bonding in
this part of the periodic table (reflected by high mp and enthalpies of atomization).

Compounds of Vanadium Niobium and Tantalum

These elements form various binary compounds (compounds where the element combines with one
other element in whole number ratios). Binary hydrides, borides, carbides and nitrides are obtained by
interaction of the elements at high temperature and have been discussed in SCH 300. They are hard,
refractory and non-stoichiometric materials with high conductivities.

Oxides

Oxidation state +5 +4 +3 +2
V V2O5 VO2 V2O3 VO
Nb Nb2O5 NbO2 - (NbO)
Ta Ta2O5 TaO2 - (TaO)

44
M2O5 are probably the most important with V2O5 being the most useful and most studied. Their stability
increases down the group. They are all amphoteric with V 2O5 being more so than the rest.

V2O5
 Amphoteric
o It is soluble in acids giving salts of the VO2+ (dioxovanadium) cation.
o It dissolves in alkalis to give colourless solutions which contain the orthovanadate ion
VO43- at high pH. At intermediate pHs a series of hydrolysis-polymerization reactions
occur yielding isopolyvanadates.
o It is sparingly soluble in water to give pale yellow acidic solutions
 Mild oxidizing agent

Preparation
The best method involves decomposition of NH4VO3
Heat
NH4VO 3 V2O5 + 2NH3 + H2O

The other method involves reaction of V with excess O2 which gives V2O5 as the ultimate compound.
This is however contaminated with lower oxides and is therefore not a good preparative method.

 V2O5 losses oxygen reversibly. This may be the reason why it is such a versatile catalyst. For
example, it catalyses oxidation of SO2 to SO3 in the contact process of manufacturing H2SO4. It
catalyses oxidation of many organic compounds in O2 of H2O2.

Nb2O5 and Ta2O5

 Relatively much more stable than V2O5 and difficult to reduce (inert).
 Attacked by conc. HF
 Dissolve in fused alkali

Dioxides
VO2
 Blue solid with rutile structure
 Obtained by reduction of V2O5 with CO, SO2 or fusion with oxalic acid.
 Amphoteric in nature
o dissolves in non-oxidizing acids to give salts of the blue vanadyl cation VO 2+.
o Dissolve in alkalis to give the yellow brown vanadate (IV) (hypovanadate) ion V 4O92-
or at high pH [VO4]4-. Intermediate pHs produce polyanions.

NbO2 and TaO2 are little studied. Obtained by reduction of pentoxides with reducing agents like H2.

V2O3
 Obtained by further reduction of VO2 with H2, CO or C
 Has corundum structure
 Entirely basic dissolving in acids to give blue or green solutions of V 3+ which are strongly
reducing.

Extra reading
Monoxides, sulphides etc of group 5 elements.

45
Vanadates, Niobates and Tantalates

Vanadates
Perhaps vanadates are the most important of this class of compounds. They are obtained by dissolving
V2O5 in alkali hydroxide. They range from very simple to very complex vanadates and vary in colour
depending on the pH of the solution. For example, V2O5 dissolves in NaOH to give colourless solutions
containing oxo species VO43-. On acidification to pH 6.5 the solution turns bright orange and remains so
until pH 2 when a brown pt of V2O5 is formed. This dissolves in more acid giving VO2+. Thus in
strongly basic solutions the predominant species is VO43- while in strongly acidic medium the
predominant species is VO2+.

Between these two extremes several species exist, the nature of which is still controversial. They are
formed due to a series of hydrolysis-polymerization reactions. The resultant species are called
isopolymetallates or isopolyanions (Isopolyvanadates). The equilibria involved in their formation as
well as their stoichiometries and structures have bee confused and disputed. This may be because:

 Some equilibria are reached only slowly (possibly months in some cases) and it is likely that
much of the reported work has been done under non-equilibrium conditions.
 Often in early work, solid species were crystallized from solution and their stoichiometries, quite
unjustifiably as it turns out, were used to infer stoichiometries of species in solution.
 When a series of experimental measurements has been made it is usual to see what combination
of plausible ionic species will best account for the observed data. However, the greater the
complexity of the system, the greater the number of apparently acceptable models there will be,
and the greater the accuracy required if the measurements are to distinguish reliably and
unambiguously between them.

The potential application of these metallates is in catalysis either as catalysts or catalyst supports.

Niobates and Tantallates

Fusion of the M2O5 (M = Nb and Ta) with excess alkali hydroxides or carbonates followed by
dissolution in water produces solutions of isopolyanions. These are however not as extensive as those of
vanadium. For example, the presence of MO43- in strongly alkaline solutions is uncertain. Below pH ~7
for Nb and pH ~10 for Ta precipitation of hydrous oxides occurs.

LiNbO3 and LiTaO3 have been found to be attractive than quartz as frequency filters in communication
devices.

Halides and Oxohalides

Table 22.6 gives a summary of the known halides of the group 5 elements. Notice the following
observations fro:
1. There are no VX5 (X = Cl, Br, I). It only forms VF5. This is because V5+ is too strong an
oxidizing agent to coexist with the large Cl-, Br-, and I- anions. It has high polarizing power
while the anions are easily polarizable. Nb and Ta are less polarizing and can give all the
halides including MI5 (the only elements to do so apart from protactinium). F- is a hard base
and can stabilize high oxidation states.
2. V does not form VI4 for the same reason as above.
3. There are no MX2 (M = Nb, Ta; X = F, Cl, Br and I). This is because the metals form strong
metal-metal bonds such that to separate the metal atoms and keep them apart requires high
energy and many ligands.

46
 4. There are no known TaF4, and TaI3

 The MX5 are prepared by direct action of the halogens on the metal. They are all relatively
volatile, hydrolysable solids in which the metals attain octahedral coordination by halide
bridges. For example, VF5 is a viscous liquid because it forms infinite chains with V-F-V
bridges (Fig 22.4 a), NbF5 and TaF5 form tetramers similar to MoF5 and WF5 (Fig 22.4b)
while the pentabromides and pentachlorides of Nb and Ta form dimers (Fig 22.4 c)
 The colours of the pentahalides vary from white fluorides yellow chlorides, orange
bromides to brown iodides due to L→M charge transfer. The decreasing energy of the
charge transfer bands responsible for these colours is a reflection of the increasing
polarizability of the anions from F- to I-.
 The MX5 are sublimable giving trigonal bipyramidal structures.
 They are Lewis acids, forming adducts with Lewis bases with diminishing ability from
fluorides to iodides (why?).

MX5 + L MX5L
e.g.
reflux
NbCl5 + 2py NbCl4(py)2
140o C
The tetrahalides of vanadium can be prepared by direct action of the elements but are unstable with VF 5
dispropotionating to VF5 + VF3. VCl4 and VBr4 tend to dissociate to VX3 + ½X2 and so require presence
of excess halogen during preparation. The known tetrahalides of Nb and Ta (except NbI4 which is
prepared by thermal decomposition of NbI5) are generally prepared by reduction of the corresponding
pentahalide and are readily hydrolyzed.

The VX3 are obtained by reduction or thermal decomposition of their pentahalides or action of th
elements under appropriate conditions. They are all crystalline polymeric solids in which the vanadium
is 6-coordinate. They are coloured and have magnetic moments slightly lower than the spin-only value
of 2.83 BM corresponding to two unpaired electrons. Except VF3 which is not very readily oxidized nor
very soluble in water, the trihalides are easily oxidized by air and are very hygroscopic forming
aqueous solutions of [V(H2O)6]3+. The NbX2 and TaX3 are non-stoichiometric.

The dihalides of V have simple structures based on the close packing of halide ions: the rutile structure
for VF2 and the CdI2 structure for the others. They are strongly reducing and hygroscopic, dissolving in
water to give lavender-coloured solutions of [V(H2O)6]2+. By contrast, the Nb and Ta dihalides obtained
by high-temperature reduction of the pentahalides with the metals (or Na or Al) are cluster compounds.
They consist of a series of phases based on [M6X12]n+ units consisting of octahedral clusters of metal
atoms situated above each edge of the octahedral. These may be surrounded by:
a) Four similar units, with each of which a halogen is shared, producing a sheet structure with the
composition [M6X12]X4/2 = M6X14 i.e (MX2.3). The compounds are diamagnetic due to the
metal-metal bonding.
b) Six similar units, with each of which a halogen is shared producing a three-dimensional array
with the composition [M6X12]X6/2 = M6X15 i.e (MX2.5 ). These compounds have magnetic
moments corresponding to one unpaired electron per hexamer and so indicate the same metal-
metal bonding within the cluster.

These cluster compounds are may be regarded as intermediate between the [M6X8]n+ type of Group 6
which generally posses sufficient electrons (26) to allow M-M bonds single bonds on each edge of the
octahedron and the comparatively electron-poor clusters of groups 3 and 4 which generally require the
presence of an interstitial atom to stabilize them.

47
Read more on their reactions

Oxohalides
Table 22.7 shows the known oxohalides of group 5 elements. It is worth noting that whereas the V 5+
halides are not known except the fluoride, the oxohalides VOCl 3, VOBr3, VO2Cl and VO2Br are known
(Explain why?). These may be obtained from the reaction of the oxides with the halogen in the presence
of carbon or the oxide and a halogenated solvent under appropriate temperatures e.g.

300oC
V2O5 + Cl2 + C VOCl3, or VO2Cl
red heat

V2O5 + CCl4 VOCl3, VO2Cl (sometimes VCl2 or VCl3 may form)

They are limited almost entirely to the oxidation states of +4 and +5. Those in oxidation state of +4 are
relatively stable but those in +5 are notably hygroscopic and hydrolyze vigorously to the hydrous
pentoxides.

Question: The compounds VOCl and VOBr where V is in oxidation state +3 are known but not NbOCl
and TaOCl. Explain why this could be so.

Answer: TaCl3 are cluster compounds whereas VCl3 is a simple compound (mononuclear) where two
chlorides may be replaced by an oxygen to give VOCl. On the other hand the formation of NbOX or
TaOX would require breaking of M-M bonds to make MOX.

48
49
50
51
Tables from Greenwood and Earnshaw

52
Compounds with oxoanions are not well characterized. The +5 oxidation state is too high to allow the
formation o simple ionic salts even for Nb and Ta. In the lower oxidation states, the higher sublimation
energies of the heavier metals, coupled with their ease of oxidation militates against the formation of
simple salts of the oxoacids. The only simple oxanion salts are the sulfates of V 3+ and V2+ which can be
crystallized from aqueous solutions as hydrates and are both strongly reducing. Examples include the
blue-violet alums MV(SO4)2.12H2O and the reddish-violet tutton’s salts M2V(SO4)2.6H2O, the
ammonium analogues of which are more air-stable when dry.

Complexes
These elements form complexes mainly in the high oxidation states.
Oxidation state +5

Vanadium forms complexes in this state that contain the VO2+ group. Species such as cis-[VO2Cl4]3-,
cis-[VO2EDTA]3- and cis-[VO2(C2O4)2]3-. The cis arrangement of the dioxo compounds of metals
without d electrons is preferred over the trans-arrangement found in some other metal dioxo systems,
e.g. RuO22+ because the strongly π-donating O ligands then have the exclusive share of one dπ orbital
each (dxz, dyz) and share a third one (dxy), whereas in the trans-configuration they would have to share
two dπ orbitals and leave one unused. Under non-aqueous conditions the complexes formed are largely
derived from the Lewis acid behaviour of VF5 and the oxohalides. For example, addition of KF to VF5
gives KVF6- which is hydrolyzed by water. Others include VOCl3(Net3)2, VOCl3(MeCN)2, VOF4- and
VOCl4- and alkoxides such as VO(OR)2Cl.

Most complexes of Nb and Ta are derived from the pentahalides. For example NbF 5 and TaF5 dissolve
in aqueous solutions of HF to give [MOF5]2- and if the HF concentration is high [MF6]- are formed.
Even in more concentrated solutions [MF7]2- and [MF8]3- are formed. Other complexes resulting from
Lewis acidity include MX5L with O, S, N, P and As donor ligands.

Oxidation state +4 Complexes

For V4+ perhaps the most important and widely studied are the vanadyl (VO2+) complexes. They are the
usual products of hydrolysis of other vanadium (IV) complexes. The VO2+ cation behaves as a class-a
cation forming stable compounds with F (especially), Cl, O and N donor ligands. They are usually blue
to green , cationic, anioinic or neutral and 5-coordinate with geometry being invariably square
pyramidal. Examples include [VO(acac)2] in which the V=O bond length is about 157-168 pm (about
50 pm shorter than the four equatorial V-O bonds). Another example is the trigonal bipyramidal
[VOCl2(NMe3)2]

O
H3C C O V CH3
O
C
HC
O O
C CH
C
CH3 H3 C

The vanadyl acac complex

The tetrahalides are Lewis acids forming 6-coordinate adducts. Examples include
 [VF4L] (L = NH3, py) – insoluble in common organic solvents, and have magnetic moments of

53
 about 1.8 BM. They could be halogen- bridged polymers.
 [VCl4L2] (L = py, MeCN, aldehydes etc.). Also [VCl4(L-L)] (L-L = bipy, Phen, diars, etc).
These are brown paramagnetic, readily hydrolyzed compounds thought be 6-coordinate
monomers. Similar Nb and Ta complexes are known and are paramagnetic suggesting they too
are 6-coordinate monomers without metel-metal bonds.
 [MX6]2-, (M = V, X = F, Cl; M = Nb, Ta, C = Cl, Br.

Read other oxidation states

Biochemistry of Vanadium
 [V(η5-C5H5)2Cl2] has anti-tumor activity
 A number of nitrogen fixing bacteria contain vanadium. For example, Azotobacter contains
three distinct nitrogenase systems based in turn on Mo, V and Fe, each of which has an
underlying functional and structural similarity. Models are being sought that can convert N 2 to
NH3 at ambient conditions. To this end complexes such as [Na(thf)] +[V(N2)2(dppe)2 (dppe =
Ph2PCH2CH2PPh2) have been prepared from VCl3 and shown to liberate NH3 on acidification.

Read the organometallic chemistry of the elements

54
 UNIT 6
Group Six Elements

Table 15: The elements of Group 6

24 42 74
Property Cr Mo W (wolfram)
No of Natural 4 7 5
isotopes
Electron [Ar]3d54s1 [Kr]4d55s1 [Xe]4f145d46s2
configuration
Electronegativity 1.6 1.8 1.7
Atomic radius 128 139 139
(pm)
Density (20o C)/g 7.14 10.28 19.3
cm3
MP/oC 1900 1620 3422
BP/oC 2690 4650 (5500)
Chromite, FeCr2O4, Crocoite, Molybdenite, MoS2, Wulfenite, Scheelite, CaWO4,
Common ores PbCrO4 and Chrome ocre, PbMoO4 and Powellite, Ca(Mo, wolframite, (Fe,
Cr2O3 W)O4 Mn)WO4
NB: The number naturally occurring isotopes imposes limits on the precision with which their atomic weights
have been determined, especially Mo and W. The most important ores are given in bold.

Introduction
The oxide of Cr was discovered by Frenchman L.N Vauquelin in 1797 in a Siberian mineral 4 PbCrO4. It
was isolated by charcoal reduction the following year and named chromium (after the Greek word
Chroma, colour) because of the variety f colours found in its compounds.

Molybdenum is from the Greek word for lead (molybdos) due t the colour of its oxide being black like
lead which was already known at the time. It was isolated by charcoal reduction from its oxide about
1782 by P,J. Hjelm. The oxide was discovered by Swedish chemist C.W. Scheele from the mineral
MoS2.

In 1781 Scheele and T. Bergman Isolated the oxide of W from the mineral scheelite (CaWO4) which
was then called tungsten (Swedish tung sten, heavy stone). Two years later the Spanish brothers J.J. and
F. d’Elhuyar showed that the same oxide was a constituent of the mineral wolframite and reduced to the
metal by heating with charcoal. The name wolfram from which the symbol of the element is derived is
still in use in German literature and is recommended by IUPAC while in the English literature the name
tungsten is used.

Terrestrial abundance is as follows: Cr 122 ppm of the earth’s crustal rocks, Mo and W are both quite
rare with 1.2 ppm abundance. It is important to note however that for commercial exploitation
availability in large concentrated deposits is more important than abundance which may see a mineral

4
The naturally occurring compounds in the earth’s crust are known as minerals. Those which can be exploited as
a source of commercial materials are termed ores. Metals with electrode potentials greater than hydrogen are
rarely found in the free state whereas those with values below those of hydrogen often occur in the native
condition, e.g. Ag, Au, Cu and Hg. The metallic compounds found in the earth’s crust (within 10 - 50 km) usually
have a low solubility in water. The more soluble naturally occurring compounds are found either in sea water or in
large salt-bed deposits formed by the evaporation of inland seas.

55
very abundant but uniformly distributed.

Chromium

Extraction
Chromite, FeCr2O4, found mainly in southern Africa (96% of world reserves), is the most commercially
useful ore, and is extensively used for extraction of chromium. Chromium is produced in two forms:
(Chemistry of the Elements, Greenwood and Earnshaw, Chapter 23).

(a) Ferrochrome by the reduction of chromite with coke in an electric arc furnace. A low-carbon
ferrochrome can be produced by using ferrosilicon instead of coke as the reductant. This iron/chromium
alloy is used directly as an additive to produce chromium-steels which are "stainless", hard and
corrosion resistant.

FeCr2O4 + 4C Fe + 2Cr + 4CO

Ferochrome is 70% Cr and 30% Fe

(b) Chromium metal by the reduction of Cr2O3. This is obtained by aerial oxidation of chromite in
molten alkali to give sodium chromate, Na2CrO4, which is leached out with water, precipitated and then
reduced to the Cr(III) oxide by carbon.

Fuse
FeCr2O4 + 8Na2CO3 + 7O2 8Na2CrO4 + Fe2O3 + 8CO2

Extract residue with minimum H2O, evaporate and cool to

deposit Na2CrO4.10H 2O (or K2CrO4 if K2CO3 was used
instead of Na2CO3).

Na2CrO4.10H2O (yellow)

Acidify with H2SO4

Reduce with carbon

Cr2O3 Na2Cr2O7.2H2O (orange)

The oxide can be reduced by aluminium (aluminothermic process) or silicon:

Cr2O3 + 2Al 2Cr + Al2O3

2Cr2O3 + 3Si 4Cr + 3SiO2

Uses of Chromium
 The main use of the chromium metal so produced is in the production of nonferrous alloys. The
use of pure chromium is limited because of its low ductility at ordinary temperatures.

 The Cr2O3 is dissolved in sulphuric acid to give the electrolyte used to produce the ubiquitous
chromium-plating which is at once both protective and decorative.
 The sodium chromate produced in the isolation of chromium is itself the basis for the
manufacture of all industrially important chromium chemicals.

56
Properties of Chromium
An excellent site for finding the properties of the elements, including chromium is at
www.webelements.com

All the group 6 elements have metallic bcc structures and in massive state they are lustrous, silvery and
fairly soft when pure. The most obvious characteristic for Mo and W is their refractive nature, and W
has the highest melting point of all the elements except carbon in diamond allotrope. The refractory
behaviour and indeed relative stabilities of different oxidation states can be explained by the role of the
(n-1)d electrons. Cr has lower melting and boiling point as well as enthalpy of atomization than
vanadium which implies that at Cr the 3d electrons are now just beginning to enter the inert electron
core of the atom and so are less readily delocalized by the formation of metal bonds. Again this is
noticed from the fact that the most stable oxidation state has now dropped to +3 while Cr 4+ is strongly
oxidizing.

½Cr2O72- +7H+ +3e- Cr3+ + 3.5H2O Eo = 1.33V

For the heavier congeners, for example, tungsten, in the group oxidation state is much more stable to
reduction. It is apparently the last element in the third transition series in which all the 5d electrons
participate in metal bonding.

Chemical reactivity and Trends

All the elements resist atmospheric attack and this is why Cr is used to protect other reactive metals like
iron. At high temperatures they react with most non-metals to give mostly interstitial and non-
stoichiometric products.

The reactivity of Cr with acids depends on its purity, but it is generally more reactive than both Mo and
W. It dissolves readily in HCl, (Eo Cr2+/Cr = -0.91V) but if pure it resists dilute H2SO4. HNO3 whether
dilute or concentrated as well as aqua regia (30% HCl in HNO3) render it passive. Conc

The metals are readily attacked by oxidizing agents such as KNO3, or KClO3 and alkali melts to give
MO42-. They form compounds in all oxidation states from +6 to -2. In oxidation state +6 Cr tends to
form poly oxoanions, but their diversity is a pale shadow of that of the polymolybdates and the
polytungstates.

Oxidation states +5 and +4 occur in Cr as unstable intermediates and +3 is its most stable state leading
to a coordination chemistry, the fecundity of which is exceeded only by that of Co(III). Cr(II) is
strongly reducing but still with an extensive aqueous chemistry. The chemistry of Mo and W in states
+5 to +2 is dominated by clusters and multiple-bonded species.

Molybdenum has been of great interest also because of its role in biological processes and catalytically
in the hydrodesulfurization (HDS) processes for removing sulphur compounds from petroleum
feedstocks.

For an article that reviews simple chemistry see

www.chemguide.co.uk/inorganic/transition/chromium.html

Chromium Compounds
Most compounds of chromium are coloured (why is Cr(CO)6 white?). The most important are the
chromates and dichromates of sodium and potassium and the potassium and ammonium chrome alums.
The dichromates are used as oxidizing agents in quantitative analysis, also in tanning leather. Other

57
compounds are of industrial value; lead chromate is chrome yellow, a valued pigment. Chromium
compounds are used in the textile industry as mordants5, and by the aircraft and other industries for
anodizing aluminium.

Halides of Group 6 elements

Table 16 shows all the known halides of the group 6 elements. It is worth noting the following:

 Cr only forms the halides CrF6, CrF5 in the high oxidation states. These halides are unstable and
strongly oxidizing.
 MoF6, and WF6 are monomeric, colourless liquids with the former strongly oxidizing.
 Only W is known for certain to form other hexahalides WCl6 and WBr6, the latter being
susceptible to reduction.
 Cr only forms the pentafluoride, a strongly oxidizing bright red, volatile solid. Prepared from
the elements under more severe conditions than CrF6. Even Mo does not form the
pentabromides and pentaiodides.
 The most stable tetra halide of Cr is the CrF4 which is an unreactive solid. The existence of
CrX4, (X = Cl, Br, I) as well as both Mo and W tetraiodides is doubtful. The tetrahalides of Mo
and W are readily oxidized and form adducts of the form MX 4L2.
 The trihalides show major differences between the metals:

o For Cr this is the most stable oxidation state and so all the four halides are known. They
are prepared by direct reaction between the halogens and the metal. CrF3 is however
better obtained by reacting HF with CrCl3 a 500o C. It forms layer structure in which
the metal is octahedrallly surrounded by chlorides (Fig 13). stable hydrated CrCl 3 can
also be readily obtained from aq solutions. CrCl3.6H2O is a well known example of a
complex that shows hydrate isomerism; [Cr(H2O)4Cl2]+Cl-.2H2O (deep green),
[Cr(H2O)5Cl]2+2Cl-.H2O (pale green) and [Cr(H2O)6]3+3Cl- (violet). In aqueous solution
all the chloride is precipitated by silver nitrate on the violet chloride. two thirds of the
chloride is precipitated from the ale green compound and one third from the deep green
chloride.

Cl Cl Cl
Cl Cl
Cr Cr
Cl Cl Cl
Cl Cl Cl Cl
Cr Cr
Cl Cl Cl Cl
Cl Cl Cl
Cr Cr
Cl Cl Cl
Cl Cl

Figure 13: Structure of solid CrCl3 (Cl in cold face are below the plane of the paper)

o The violet anhydrous CrCl3 is not very soluble in water but dissolves rapidly in the
presence of tin(II) chloride or CrCl2 to give a green solution.
o CrCl3 is a Lewis acid forming adducts with donor ligands such as THF, NH3, pyridine, etc.

5
A mordant is a substance used to set dyes on fabrics or tissue sections by forming a coordination complex with
the dye which then attaches to the fabric or tissue. It is always a polyvalent metal ion.

58
 e.g. [Cr(NH3)5Cl]2+ , [Cr(THF)3Cl3], etc.

Table 16: The halides of Group 6 elements (mp/oC)

Oxidation state Fluorides Chlorides Bromides Iodides

CrF6
yellow (d > -100°)
MoF6 , colourless (MoCl6)
+6 (17.4°) bp 34° black
WF6 , colourless WCl6 dark blue WBr6
(1.9°) bp 17.1° (275oC) bp 346° dark blue (309°)
CrF5 red (34°)
bp 117°
MoF5, yellow (67°) MoCl5 , black (194°)
+5 bp 213° bp 268°
WCl6, dark green WBr5
WF5, yellow
(242°), bp 286° black
CrF4 CrCl4, (d > 600°, gas
CrBr4? CrI4
violet -amethyst(a) phase)
+4 MoCl4 MoBr4
MoF4, pale green MoI4?
black black
WF4, red-brown WCl4, black WBr4, black WI4?

CrF3 CrCl3, red-violet

CrBr3, very dark CrI3, very dark
green (1404°) (1150°)
green (1130°) green

+3 MoF3 MoCl3, very dark red

MoBr3 MoI3
brown (>600°) (1027o)
green (977o) black (927°)
WBr3, black (d >
WCl3, red WI3
80°)
CrBr2 white CrI2, red-brown
CrF2, green (894°) CrCl2, white (820°)
(842°) (868°)
MoBr2
+2 MoCl2
yellow-red MoI2
yellow (d > 530°)
(d > 900°)
WCl2, yellow WBr2, yellow WI2, brown

(a) It is probable that previously reported green samples were largely CrF3; O. KRAMER and B. G. MULLER, Z.
anorg. allg. Chern. 621, 1969 - 72 (1995).

o The Mo trihalides are obtained by reducing a higher halide with the metal (except MoI3
which is best prepared directly). They are insoluble in water and generally inert. MoCl 3 is
structurally similar to CrCl3 but is distorted so that pairs of Mo atoms lie only 276 pm apart
whixh in view of the low and temperature dependent magnetic moment is evidently close
enough to permit appreciable Mo-Mo interaction.
o WX3 are cluster compounds similar to those of Nb and Ta. WCl 3 and WBr3 are prepared by
halogenation of the dihalides. The structure of WCl3 is based on the [M6X12]n+ cluster unit.
It consists of an octahedron of W atoms with a Cl atom bridging each of the 12 edges .A

59
 further six Cl atoms are situated above the apical W atoms.
o WBr3 has a structure based on the cluster unit [M6X8]n+ (see Fig 14) but since it is formed
by a two electron oxidation of [W6Br8]4+ it does not contain W3+ and is best formulated as
[W6Br8]6+4Br-/2.2Br- where 4Br-/2 represents bridging bromide groups.

Figure 14: [M6X8]4+ clusters with X bridges each face of the octahedron of metal ions.
 Anhydrous dihalides of Cr are conveniently prepared by reduction of the trihalides with H 2 at
300 – 500o C, or by the action of HX (or I2 for the diiodide) on the metal at temperatures of the
order 1000o C. They are all deliquescent and the hydrates can be prepared by reacting pure Cr
with aqueous HX. The all have distorted octahedral structures in the solid state. The distortion
is expected for a metal ion with d4 configuration which are susceptible to Jahn-Teller
distortion6. For example CrF2adopts a distorted rutile structure in which 4 fluoride ions are 200
pm from the Cr atom while the remaining 2 are 243 pm away.

 The strongly reducing properties of Cr(II) halides contracts with the redox stablility of the
molybdenum(II) halides. Even the tungsten(II) halides which admittedly are strong reducing
agents (being oxidised to their trihalides), may by their very existence be thought to depary
from the expected trend. The reason for the enhanced stability of Mo and W dihalides lies in the
prevalence of metal-atom clusters, stabilised by M-M bonding. All 6 of these dihalides (these
elements don’t form difluorides) are isomorphous with a structure based on the [M6X8]4+ shown
above.

Bonding in the [M6X8]4+ cluster unit

In the cluster each metal has a free coordination position. In the dihalides themselves, these positions
are occupied by 6X- ions, 4 of them bridging to other [M6X8]4+ units giving the composition
[M6X8]X2X4/2 = MX2. In each cluster, the 6 metals contribute 6 x 6 = 36 valence electrons of which 4
are transferred to the counter anions, so producing the net charge, and 8 are used in bonding to the
chlorines of the cluster. 24 electrons are left which can provide M-M bonds along each of the 12 edges
of the octahedron of metal atoms accounting for the observed diamagnetism. The 6 Cl - on the M apices
are readily replaced, leaving the [M6X8]4+ core intact throughout a variety of substitutions reactions.

6
The theorem by H.A. Teller and E.Teller (1937) states that a molecule in a degenerate electronic state will be
unstable and will undergo a geometrical distortion that lowers its symmetry and splits the degenerate state.

60
Oxides

Chromium oxides
Formula Colour Oxidation State MP Magnetic Moment
CrO3 deep red Cr6+ 197decomp -
Cr3O8 - intermediate - -
Cr2O5 - intermediate - -
Cr5O12 etc - intermediate - -
CrO2 brown-black Cr4+ 300 decomp Ferromagnetic
Cr2O3 Green Cr3+ 2437 antiferromagnetic < 35 C

Dichromate and chromate equilibrium is pH dependent:

HCrO4- → CrO42- + H+ K=10-5.9

H2CrO4 → HCrO4- + H+ K=10+0.26
2- -
Cr2O7 + H2O → 2HCrO4 K=10-2.2
- 2- +
HCr2O7 → Cr2O7 + H K=10+0.85

Hence the variation found for solutions of CrO3 are:

pH > 8 CrO42- yellow
pH 2-6 HCrO4- and Cr2O72- orange-red
pH < 1 H2Cr2O7

Thus in acidic medium chromate CrO42- is converted to the dichromate Cr2O72- and vice versa i.e.
H+
2CrO42- Cr2O72-
yellow OH- Orange
Polymerization beyond the dichromate ion is apparently limited to the formation of the tri and
tetrachromates (i.e. Cr3O102- and Cr4O132-) which can be crystallized as alkali metal salts from very
strongly acid solutions. They are formed by corner sharing tetrahedra. This is much simpler compared
to the polymerization of V, Mo and W oxoanions probably due to the smallness of the Cr 6+. It limits it
to tetrahedral rather than octahedral coordination with oxygen while simultaneously favouring Cr-O
bonds and so inhibiting the sharing of attached oxygens.

One of the most obvious characteristics of Cr(III) is that it is acidic i.e. it has a tendency to hydrolyze
and form polynuclear complexes containing OH- bridges in a process known as OLATION. This is
thought to occur by the loss of a proton from coordinated water, followed by coordination of the OH - to
a second cation:

H 4+
O
[Cr(H2O)6]3+ [Cr(H2O)5(OH)]2+ (H2O)4Cr Cr(H2O)4 pK = 4 etc
O
H

The ease with which the proton is removed can be judged by the fact that the hexaaquo ion (pKa ~ 4) is
almost as strong as acetic acid. Further deprotonation and polymerization can occur and, as the pH is
raised, the final product is hydrated chromium(III) oxide or "chromic hydroxide".

61
Representative Complexes
The Chromium(III) ion forms many stable complexes and since they are inert are capable of exhibiting
various types of isomerism.

Hydrated chromium chloride, "CrCl3.6H2O", exists as hydrate isomers, including: the violet
[Cr(H2O)6]Cl3, the dark green trans-[CrCl2(H2O)4]Cl.2H2O salt shown above, the pale green
[CrCl(H2O)5]Cl2.H2O, etc.

Anhydrous CrCl3 reacts with pyridine only in the presence of Zinc powder. This allows a small amount
of the Cr(II) ion to be formed, which is very labile but unstable with respect to oxidation back to
Cr(III).

CrCl3 + pyr/Zn [CrCl3(pyr)3]

See the laboratory manual for this course for a range of other Cr(III) complexes for which you should
know the structure.

[Cr2(OAc)4].2H2O is an example of a Cr(II) complex which is reasonably stable in air once isolated.
Each Cr(II) ion has 4 d electrons but the complex is found to be diamagnetic which is explained by the
formation of a quadruple bond between the two metal ions. The Cr-Cr bond distance in a range of these
quadruply bonded species has been found to vary between 195-255 pm.

Overlapping of atomic orbitals to give quadruple bond in Cr2(OAc)4

62
 Metal-metal bonding in Cr(II) acetate complex.

A recent report describes the structure of a Cr complex with a quintuple bond between two Cr(I) ions.

Cr(I) - Cr(I) quintuple bonded structure.

The compound Ar'CrCrAr' (R = isopropyl) was very air and moisture sensitive and crystallized as dark
red crystals. X-ray diffraction revealed a Cr-Cr bond length of about 184 pm and a planar, trans-bent
core geometry. Published in Science by P Power et. al., UCLA Davis, 22 September 2005 [DOI:
10.1126/science.1116789].

Uses of Chromium

63
More than half the production of chromium goes into metallic products, and about another third is used
in refractories. It is an ingredient in several important catalysts. The chief use of chromium is to form
alloys with iron, nickel, or cobalt. The addition of chromium imparts hardness, strength, and corrosion
resistance to the alloy. In the stainless steels, chromium makes up 10 percent or more of the final
composition. Because of its hardness, an alloy of chromium, cobalt, and tungsten is used for high-speed
metal-cutting tools. When deposited electrolytically, chromium provides a hard, corrosion-resistant,
lustrous finish. For this reason it is widely used as body trim on automobiles and other vehicles. The
extensive use of chromite as a refractory is based on its high melting point, its moderate thermal
expansion, and the stability of its crystalline structure.

In chromites and chromic salts, chromium has a valence of +3. Most of these compounds are green, but
some are red or blue. Chromic oxide (Cr2O3) is a green solid. In chromates and dichromates, chromium
has a valence of +6. Potassium dichromate (K2Cr2O7) is a red/orange, water-soluble solid that, mixed
with gelatin, gives a light-sensitive surface useful in photographic processes. The chromates are
generally yellow, the best known being lead chromate (PbCrO4), an insoluble solid widely used as a
pigment called chrome yellow. Chrome green is a mixture of chrome yellow and Prussian blue.
Na2Cr2O7.2H2O yields a wide variety of pigments used in the manufacture of paints, inks, rubber and
ceramics. It is also used to make other chromates used as corrosion inhibitors, fungicides etc. It also
used as an oxidizing agent in organic chemical processes. In acidic medium Cr 2O72- is used as a strong
oxidizing agent in volumetric analysis.

Cr2O72- + 14H+ +6e- 2Cr3+ + 7H2O Eo = 1.33 V

For this purpose K2Cr2O7 is preferred because it is not hygroscopic like the sodium salt and can
therefore be used as a primary standard.

Chromium is used to harden steel, to manufacture stainless steel, and to form many useful alloys. Much
is used in plating to produce a hard, beautiful surface and to prevent corrosion. Chromium gives glass
an emerald green colour and is widely used as a catalyst. The refractory industry has found chromite
useful for forming bricks and shapes, as it has a high melting point, moderate thermal expansion, and
stability of crystalline structure.

Health

Chromium is an essential trace element in mammalian metabolism. In addition to insulin, it is

responsible for reducing blood glucose levels, and is used to control certain cases of diabetes. It has also
been found to reduce blood cholesterol levels by diminishing the concentration of (bad) low density
lipoproteins "LDLs" in the blood. It is supplied in a variety of foods such as Brewer's yeast, liver,
cheese, whole grain breads and cereals, and broccoli. It is claimed to aid in muscle development, and as
such dietary supplements containing chromium picolinate (its most soluble form), is very popular with
body builders.

Ammonium Reineckate, NH4(Cr(NH3)2(SCN)4).H2O, is used to test for the presence of

dihydromorphinone and other substances generally found in persons involved in substance abuse.

Q: Draw the structure of a mer- isomer of Cr(III) picolinate complex.

References:
1. "Inorganic Chemistry", 3rd Edition, Catherine Housecroft, Alan G. Sharpe, Publisher: Prentice
Hall
2. "Complexes and First-Row Transition Elements", D. Nicholls

64
3. "Basic Inorganic Chemistry", F.A. Cotton, G. Wilkinson and P.L. Gauss
4. "Advanced Inorganic Chemistry", F.A. Cotton, G. Wilkinson, C. A. Murillo, and M. Bochmann
5. "Chemistry of the Elements", N.N. Greenwood and A. Earnshaw
6. "Hydrolysis of Cations", Baes and Messmer

65
 UNIT 7
MANGANESE GROUP

Table 17: The elements of Group 7

25 43 75
Property Mn Tc Re
No of Natural 1 None 2
isotopes
Electron [Ar]3d54s2 [Kr]4d55s2 [Xe]4f145d56s2
configuration
Electronegativity 1.5 1.9 1.9
Atomic radius (pm) 127 136 137
Density (20o C)/g 7.43 11.5 21.0
cm3
MP/oC 1244 2200 3180
BP/oC 2060 4567 (5650)
Terrestrial 1060pp 0.0007 ppm
abundance
Pyrolusite, MnO2
Common ores Hausmannite, Mn3O4
rhodochrosite, MnCO3

 MnO2 has been known since the time of Pharaohs. The mineral pyrolusite has been used in glass.
Being a class -a metal it occurs in primary deposits as the silicate. Generally it occurs in over 300
different and widely distributed minerals of which about 12 are commercially important.
 Tc is the first new element to be produced artificially and placed in the position reserved for eka –
manganese (Z = 43)in Mendeleev’s periodic table
 Re is the last naturally occurring element to be discovered. This filled the other gap left in the
Mendeleyev periodic table dvi-manganese (Z = 75)

Mn
First isolated by C.W. Scheele in 1774 the recognized that pyrolusite (MnO2) contained a new element.

Tc (artificial)
 Detected in a sample of Mo which had been bombarded with electrons in the cyclotron of E.O
Lawrence – C. Perrier and E. Segré.
 Present as β emitters 95Tc, and 97Tc, with half lives 61 and 90 days, respectively.
 Naturally occurring traces 99Tc (½ life 2.11 x 105yrs due to spontaneous fission of uranium).

Re
 Discovered in a sample of gadolinite (a basic silicate of beryllium, iron and lanthanides) by O.
Berg, W. Noddack, and I. Tacke in 1925 and named after the river Rhine.
 Later found independently by F.H. Loring and J.F.G Druce in manganese compounds.
 Now usually recovered from the flue dusts produced in the smelting of Cu-Mo ores.

Manganese
Main ores
(i) Pyrolusite – MnO2
(ii) Braunite – Mn2O3

66
 (iii) Manganese Blende MnS

Extraction
heat
3MnO2 Mn3O4 + O2
strongly

Mn3O4 + 4C 3Mn + 4CO

Purer product can be obtained by reducing the trimanganic tetroxide with aluminium in the
Aluminothermic process:

3Mn3O4 + 8Al 9Mn + 4Al2O3 kJ

Electrolytic manganese of high purity can be obtained by the electrolysis of MnSO4 solutions

Uses
 Alloys with Fe such as ferromanganese used in making steel. This is extremely hard and is used for
the saws of rock crushers, railway points and heavy machinery.
 Manganin – a Cu-Mn-Ni alloy. Shows little change in resistance with change in temperature and is
used in certain electrical measuring instruments.

Properties
 Hard white metal, stable in dry air, slowly attacked by H2O

Mn + 2H2O →Mn(OH)2(s) + H2

 Attack by water is speeded up by addition of NH4Cl which dissolves the hydroxide.

 Slowly attacked by dilute mineral acids giving pink solutions of Mn(II) salts containing maybe
[Mn(H2O)6]2+
 Electron configuration of [Ar]3d54S2 imples that max oxidation state = +7 which occurs in
MnO4- and Mn2O7.. These are strongly oxidizing going to Mn2+ with electron configuration
[Ar]3d5 as the most stable state.

Other rxns are summarized in the figure below.

Oxides
The following oxides are known for the group seven elements

Oxidation state +7 +6 +5 +4 +3 +2
Mn Mn2O7 MnO2 Mn2O3, Mn3O4 MnO
Tc Tc2O7 TcO3? TcO2
Re Re2O7 ReO3 Re2O5 ReO2

67
 Mn(OH)2 MnS

H2O
S
O2 or air Mn3O4
[Mn(H2O)6]2+ dil acid
Mn
Cl2

C
MnCl2
Mn3N2
Mn3C

Reactions of manganese

MnO
 Green solid with rock salt structure
 Basic dissolving in acids to give pure solutions of Mn(II) salts.

Mn2O3
 Brown solid
 Basic, dissolving in acids to give Mn(III) salts. E.g

Mn2O3 + 3H2SO4 →Mn2(SO4)3 + 3H2O

Mn3O4
 Red solid
 Mixture of MnII and MnIII oxides and is therefore basic

MnII(MnIIIO2)2 + 4H2SO4 → MnSO4 + Mn2(SO4)3 + 4H2O

Conc

MnO2
Occurs naturally and can be used to make all the lower oxides

300oC
MnO2 + H2 MnO + O2 Mn2O3
manganese dioxide manganese(II) oxide manganese sesquioxide
Go = -466 Go = -363 Go = -893

o
1000 C

Mn3O4 = MnII(MnIIIO2)2
trimanganic tetroxide
Go = -1280

68
 Thus Mn3O4 is the final compound when all others are heated.

 Most important of the Mn oxides

 Possesses an non-stoichiometric rutile lattice structure whose composition approximates MnO 1.95
 Insoluble in dilute acids
 It reacts with cold concentrated HCl to give the complex [MnCl6]2- which on warming gives MnCl2
and free chlorine:

MnO2+6HCl → [MnCl6]2- + 2H2O

[MnCl6]2- → Mn2+ + 4Cl- + Cl2

 Concentration H2SO4 reacts to give violet solutions of Mn2III(SO4)3.

 Mn(SO4)2 is produced by action of H2SO4 and KMnO4 on MnSO4. However, this is unstable being
hydrolyzed by H2O to MnO2

Mn2O7
 Obtained by adding KMnO4 powder to cold conc. H2SO4. This forms a dark green solution.
Dilution with ice-cold water causes drops of Mn2O7 to separate.

2MnO4- + 2H+ → H2O + Mn2O7

 Liable to explode violently to give MnO2 and O2

2Mn2O7 →2H+ → H2O+ Mn2O7

 It is covalent, acidic, and yields permanganic acid in H2O

Mn2O7 + H2O →2HMnO4

 The structure consists of two tetrahedral sharing a corner.

 

Mn Mn
 
 

Figure 15: Mn2O7

Uses of MnO2
 Decolorization of glass (glass is usually green due to presence of Fe). MnO2 is added to molten
glass producing red-brown MnIII thus equalizing the absorption across the visible spectrum.
 Production of dry cell batteries where it acts as depolarizer to prevent the undesirable
production of H2 gas on the carbon probably through the reaction

MnO2 + H+ + e-→MnO(OH)

 In the brick industry – providing arrange of red to brown or grey tints.

69
  Oxidation of aniline for the preparation of hydroquinone an important material as a
photographic developer and also in the production of dyes and paints.
 In electronics MnO2 is used to make the ceramic ferrites (MIIFe2O4) MII = Mn, Zn which are
used on the sweep transformer and deflection yoke of a TV set due to its higher electrical
resistivity and low cost.

Zinc-carbon battery
A zinc-carbon dry cell is described as a primary cell because as the cell is discharged, it is not intended
to be recharged and must be discarded. A zinc-carbon dry cell or battery is packaged in a zinc can that
serves as both a container and negative terminal. The positive terminal is usually a carbon rod or
graphite rod surrounded by a mixture of manganese dioxide and carbon powder. The electrolyte used is
a paste of zinc chloride and ammonium chloride dissolved in water. Zinc chloride cells are an improved
version from the original ammonium chloride variety

Chemical Reactions

The container of the zinc-carbon dry cell is a zinc can. This contains a layer of NH4Cl with ZnCl2
aqueous paste separated by a paper layer from a mixture of powdered carbon & manganese (IV) oxide
(MnO2) which is packed around a carbon rod.

Cross-section of a zinc-carbon battery.

In a dry cell, the outer zinc container is the negative terminal. The zinc is oxidized according to the
following half-equation.

Zn(s) → Zn2+(aq) + 2 e-

A graphite rod surrounded by a powder containing manganese(IV) oxide is the positive terminal. The
manganese dioxide is mixed with carbon powder to increase the electrical conductivity. The reaction is
as follows:

2MnO2(s) + H2(g)→ Mn2O3(s) + H2O(l)

70
The H2 comes from the NH4+(aq):

2NH4+(aq) + 2e- → H2(g) + 2NH3(aq)

and the NH3 combines with the Zn2+.

In this half-reaction, the manganese is reduced from an oxidation state of (+4) to (+3) preventing the
formation of hydrogen at the anode of the battery.

There are other possible side-reactions, but the overall reaction in a zinc-carbon cell can be represented
as:

Zn(s) + 2MnO2(s) + 2NH4+(aq) → Mn2O3(s) + Zn(NH3)22+(aq) + H2O(l)

The battery has an e.m.f. of about 1.5 V. The approximate nature of the e.m.f is related to the
complexity of the cathode reaction. The anode (zinc) reaction is comparatively simple with a known
potential. Side reactions and depletion of the active chemicals increases the internal resistance of the
battery, and this causes the e.m.f. to drop.

Leakage of dry cell batteries

When the dry cell has been used for a certain time, the zinc container becomes thinner because zinc
metal is oxidized to zinc ions. When the zinc case thins enough, zinc chloride begins to leak out of the
battery. The old dry cell is not leakproof. It becomes very sticky as the paste leaks through the holes in
the zinc case. The service life of the battery is short, with a shelf life of around 1.5 years.

Furthermore, the zinc casing in the dry cell gets thinner slowly, even when the cell is not being used. It
is because the ammonium chloride inside the battery is acidic, reacting with the zinc.

The Zinc Chloride Cell

The zinc chloride cell is an improvement on the original zinc-carbon cell, using purer chemicals and
giving a longer life and steadier voltage output as it is used. These cells are often marketed as "Heavy
Duty" cells, to differentiate them from "General Purpose" carbon-zinc cells. This has been a source of
consumer confusion after the introduction of alkaline cells, which last longer than the zinc-chloride
"Heavy Duty" cell. Instead of an electrolyte mixture containing much NH4Cl, it is largely only ZnCl2
paste. The cathode reaction is thus a little different:

MnO2(s) + H2O(l) + e- → MnO(OH)(s) + OH-(aq)

as is the overall reaction:

Zn(s) + 2 MnO2(s) + ZnCl2(aq) + 2 H2O(l) → 2 MnO(OH)(s) + 2 Zn(OH)Cl(aq)

In the alkaline version or "alkaline battery", the ammonium chloride is replaced by KOH or NaOH
and the half-cell reactions are:

Zn + 2OH- → ZnO + H2O + 2e-

2MnO2 + 2e- + H2O → Mn2O3 + 2 OH-

71
The alkaline dry cell lasts much longer as the zinc anode corrodes less rapidly under basic conditions
than under acidic conditions.

Other types of dry cell batteries are the silver battery in which silver metal serves as an inert cathode to
support the reduction of silver oxide (Ag2O) and the oxidation of zinc (anode) in a basic medium. The
type of battery commonly used for calculators is the mercury cell. In this type of battery, HgO serves
as the oxidizing agent (cathode) in a basic medium, while zinc metal serves as the anode. Another type
of battery is the nickel/cadmium battery, in which cadmium metal serves as the anode and nickel oxide
serves as the cathode in an alkaline medium. Unlike the other types of dry cells described above, the
nickel/cadmium cell can be recharged like the lead-acid battery.

Note
The words anode and cathode can be very confusing. In electrolytic cells, the anode is referred as the
positive terminal since all the anions (negative ions) will migrate to the anode to be selectively
discharged while the cathode is the negative terminal because the cations (positive ions) will move to
the cathode to be selectively discharged. Meanwhile, for voltaic cells, the anode and cathode are
opposite to each other. This means that the anode is the negative terminal, while the cathode is the
positive terminal. This is due to the theory which states that all anodes are terminals that undergo
oxidation or release of electrons, and all cathodes are terminals which undergo reduction

Rechargeable batteries

These are known as secondary cells because their electrochemical reactions are electrically
reversible. Rechargeable batteries come in many different shapes and sizes, ranging anything
from a button cell to megawatt systems connected to stabilize an electrical distribution
network. Several different combinations of chemicals are commonly used, including: lead-acid,
nickel cadmium (NiCd), nickel metal hydride (NiMH), lithium ion (Li-ion), and lithium ion
polymer (Li-ion polymer).

Rechargeable batteries have lower total cost of use and environmental impact than disposable
batteries. Some rechargeable battery types are available in the same sizes as disposable types.
Rechargeable batteries have higher initial cost, but can be recharged very cheaply and used
many times.

The Nickel-metal hydride cell

A nickel-metal hydride cell, abbreviated NiMH, is a type of rechargeable battery similar to the
nickel-cadmium cell. The NiMH battery uses a hydrogen-absorbing alloy for the negative
electrode instead of cadmium. As in NiCd cells, the positive electrode is nickel oxyhydroxide
(NiOOH). A NiMH battery can have two to three times the capacity of an equivalent size
nickel-cadmium battery. Compared to the lithium-ion cell, the volumetric energy density is
similar but self-discharge is higher.

The negative electrode reaction occurring in a NiMH cell is

The charge reaction is read left-to-right and the discharge reaction is read right-to-left.

72
On the positive electrode, nickel oxyhydroxide (NiOOH) is formed,

The "metal" M in the negative electrode of a NiMH cell is actually an intermetallic compound.
Many different compounds have been developed for this application, but those in current use
fall into two classes:

i) The most common is AB5, where A is a rare earth mixture of lanthanum, cerium,
neodymium, praseodymium and B is nickel, cobalt, manganese, and/or aluminium.
ii) Very few cells use higher-capacity negative material electrodes based on AB2
compounds, where A is titanium and/or vanadium and B is zirconium or nickel,
modified with chromium, cobalt, iron, and/or manganese, due to the reduced life
performances.

Any of these compounds serve the same role, reversibly forming a mixture of metal hydride
compounds.

When overcharged at low rates, oxygen produced at the positive electrode passes through the
separator and recombines at the surface of the negative. Hydrogen evolution is suppressed and
the charging energy is converted to heat. This process allows NiMH cells to remain sealed in
normal operation and to be maintenance-free.

NiMH cells have an alkaline electrolyte, usually potassium hydroxide. For separation of the
electrodes, hydrophilic polyolefin nonwovens are used.

The Hydroxides of Manganese

Mn(OH)2 is the only true hydroxide

Mn2+ + 2OH- →Mn(OH)2

White ppt
Mn(OH)2 readily undergoes atmospheric oxidation to brown hydrated Mn (III) oxide.

4Mn (OH)2 + O2 →2Mn2O3 H2O + 2H2 O

The Halides of Manganese

Table 3 shows all known halides of Group 7 elements

 ReF7 is the only thermally stable heptahalide of a transition element. TcF6 is next.
 Mn only forms MnF4 as the highest halide (cf Cr which forms CrF6 and CrF5). Others are MnF3 and
MnX2 (X = F - I). Even then MnF3 decomposes above room temperature.
 No Mn(III) bromides or iodides are known and MnX2 (X = F - I) even then it decomposes above
room temperature.
 No Mn(III) bromides or iodides are known and the chloride is only stable below -35 oC
 MnF2 hydrolyses rapidly in H2O. It is prepared by fluorinating any Mn(II) halide.

73
 MnX2 are the only simple dihalides of this group. Pale pink in colour and obtained by dissolving
the metal or its carbonate in aqueous HX.
 MnF2 is insoluble in H2O and forms no hydrates whiile the others form soluble hydrates with
tetrahydrates being the most common.
 ReCl3 is the most interesting among the low oxidation state halides. It exists as trimetric dusters
which persist throughout the chemistry of ReIII

Cl
Cl
Cl
Cl Re
Cl
Re Re
Cl Cl
Cl Cl
Figure 16: Idealized structure of Re3Cl9
 In crystalline ReCl3 the trimeric units are linked into planar hexagonal networks through chloride
bridges. The coordination sites occupied by Cl from adjoining clusters can steadily be occupied by
other ligands (various ligands) instead.

 TcCl4 is the only thermally stable chloride of Tc prepared from the elements just like MnF4.

Note
The nature of cluster formed by the 2nd and 3rd transition series elements are getting smaller across the
series as the number of electrons available for M-M bonding reduce and d electrons become more core.
Thus Re forms three-atom cluster while the earlier group elements such as Nb , Ta, Mo and W form 6-
atom clusters.

Manganates and Permanganates

Managates MnO42- contain Mn+6 (only compound of Mn in + 6 oxidation state)

K2MnO4 → 2K+ + MnO2-4

Green solution.

Produced by fusing MnO2 with NaOH/KOH and a little KClO4 with free access of air;
fuse
MnO2 + 4OH- + O2 2MnO42- + 2H2O
dark green mass
cool, dissolve in a little water
and evaporate in vacuum

K2MnO4 or Na2MnO2.10H2O
Alternative Method:
Boil permanganate with strong alkali.

4MnO4- + 4OH- 4MnO42- + 2H2O + O2

Purple green

74
MnO42- is only stable in excess alkali. Dilution, acidification or passage of chlorine produces MnO 4-

3MnO42-+ 2H2O → 2MnO4- + MnO2 + 4OH-

3MnO42- + 4H+ → 2MnO4- + MnO2 + 2H2O

2MnO42- + Cl2 → 2MnO4- + 2Cl-

Evaporation of these solutions → NaMnO4 3H2O or KMnO4 (deep purple)

Purple HMnO4 can be obtained by oxidizing Mn(II) salts in HNO3 and sodium bismuthate. This also
acts as a qualitative test for Mn:

2Mn2+ + 5BiO3- + 16H+ → 2HMnO4 + 7H2O+ 5Bi3+

 A pure solution of HMnO4 can be made by treating barium permanganate with dilute sulphuric acid
and filtering off the ppted BaSO4. Concentration of the solution at -73oC with high vacuum
produces a distillate of pure HMnO4 2H2O and a residue of HMnO4 containing a little MnO2
 Both HMnO4 2H2O and HMnO4 are strong oxidizing agents, the latter explosively.
 MnO4- are strong oxidizing agents both in acidic and basic media.

In acidic media

MnO4- + 8H+ + 5e → Mn2+ + 4H2O Eo = 1.52V

This will oxidize

5C2O42- → 10CO2 + 10e-

5Fe2+ →5Fe3+ + 5e-

2I- → I2 + e-

5NO2- + 5H2O → 5NO3- + 10H+ + 10e-

In basic media

MnO4- + 2H2O + 3e-→ MnO2 + 4OH – E0 = +1.23v

It will oxidize iodide to iodate, I- + 3H2O → IO-3 + 6H+ + 6e-

75
 UNIT 8
GROUP 8 ELEMENTS
Group 8 contains the three elements Fe, Ru, and Os. However in the Mendeleev’s periodic table the
elements of group 8, 9, and 10 are grouped together into one large group called group 8. These are:

Group 8 Group 9 Group 10

26 27 28
Fe Co Ni
44 45 46
Ru Rh Pd
70 77 78
Os Ir Pt

Because of marked ‘horizontal’ similarity as opposed to the expected horizontal similarity, the elements
are separated into two sets, one containing Fe, Co, and Ni and the other containing the platinum group
metals (Ru, Os, Rh, Ir, Pd and Pt)-forming two horizontal groups.

Note
The effect of lanthanide contraction is less pronounced in this part of the periodic table. This means that
the similarities between the 2nd and 3rd now acts are not so pronounced as in the early groups.The close
horizontal similarities in the ferrous metals and in the Pt metals are largely due to the similarity of their
atoms and ions in size (eg Fe2+ = 0.6140 Co2+ = 0.6540 and Ni2+ 0.6940)

Probably the oldest known and most abundant of these elements is iron – known since before the
prehistoric times. No other metal has played a more important role in man’s material progress as iron
has. Biologically iron plays crucial roles in the transport and storage of oxygen and also in the electron
transport. It is safe to say that, with only a few possible exceptions in the bacterial world, there would
be no life as we know it today without iron.

Occurrence
 6.2% i.e. 62000 ppm in the earth’s crustal rrocks.
 4th most abundant element after O2, Si and Al.
 2nd most abundant metal, in fact Fe + Ni make up earth’s core

Ores
 Haematite, Fe2O3
 Magnetite, Fe3O4
 Lemonite, 2Fe2O3.3H2O or FeO(OH)
 Siderite, FeCO3
 Iron pyrite, FeS2 (‘fool’s gold) – commonly not used as a source of iron due to difficulty in
eliminating the sulfur.

Extraction
May be done in small scale or large scale.

Small scale
a) Pure Fe: Reduction of pure oxide or hydroxide with hydrogen. Carbonyl process in which iron is
heated with CO under pressure and the Fe(CO)5 so formed is decomposed at 250o C to give
powdered metal.

b) Steel

76
  This is the most important use of iron > 700 metric tones produced worldwide annually.
 Done in blast furnace in first state.
 The furnace is charged with a mixture of the ore (usually haematite), coke and limestone, then a
blast of hot air with fuel oil is blown in at the bottom.
 The coke burns producing such intense heat that temperatures approaching 2000o C are reached
near the base of the furnace and perhaps 200 - 500oC at the top.
 The net result is that the ore is reduced to iron, and silicaceous gangue forms a slag (mainly
CaSiO3) with the lime stone. The overall process for the extraction of Fe is:

2Fe2O3 + 3C → 4Fe + 3CO2

SiO2 + CaCO3 → CaSiO3 + CO2

The molten iron and the molten slag which floats on the iron collect at the bottom of the furnace
and are tapped off separately. As the charge moves down, the furnance is recharged at the top,
making the process continuous. Main reactions are as shown below (from
http://wwwchem.uwimona.edu.jm/courses/blast.html)

At 500 °C
3Fe2O3 +CO → 2Fe3O4 + CO2
Fe2O3 +CO → 2FeO + CO2

At 850 °C
Fe3O4 +CO → 3FeO + CO2

At 1000 °C
FeO +CO → Fe + CO2

At 1300 °C
CO2 + C → 2CO

At 1900 °C
C+ O2 → CO2
FeO +C → Fe + CO

Blast Furnace diagram 40 m high x 15 metres diameter produces 10,000 tones of pig iron /day. The main
reduction occurs at the top as the hot rising gases meet the descending charge. Here too the limestone is converted
to CaO.

The molten iron tapped off at the base of the furnance is known as pig iron or cast iron. It is very brittle
and contains up to 5% impurities, namely 3 - 4%C, phosphorus, sulphur, silicon and manganese. Some
of the carbon is found in it the form of iron carbide, or cementide (Fe3C). This is collected in moulds
make of sand and allowed to solidify into ingots called ‘pigs’. Once cold, pig iron is hard and very
brittle. The molten iron (Pig or cast iron) can be cast into a variety of shapes in moulds; it is used for
fire grates, gutter piping, railings, machine beddings, etc. Slag is used to make building materials like

77
breeze blocks or cements.

General properties of Fe
 Silvery in colour
 Not very hard
 Quite reactive
 Fairly divided metal in pyrophoric
 Little affected by dry air
 Most air quickly oxidizes the metal to hydrous ferric oxide (rust). This forms a non coherent
layers which flakes off and exposes more metal to attack.
 Dissolves in cold dil. non-oxidizing acids to give Fe3+ as well as Fe2+
 Oxidizing acids give only Fe3+
 Strong oxidizing agents like conc. HNO3 or K2Cr2O7 passivate the metal because of the
formation of a protective coat of oxide. If scratched the layer exposes more metal.
 Slightly amphoteric. Not affected by dilute NaOH but is attacked by conc. NaOH.

Wrought iron – much purer iron

 Also called malleable iron.
 The purest form of commercial iron
 Made by oxidizing the impurities in a reverbatory furnace lined with haematite. The haematite
oxidizing carbon to CO.

Fe2O3 + 3C → 2Fe + 3CO

Limestone is added as a flux and sulfur, Si, and P are oxidized and pass into the slag. The metal is
removed and freed from the slag by passing through rollers.

Properties
 Fibrous structure due to the thin films of slag trapped between the layers of pure irons.
 Contains about 0.5% of impurities, ½ of which in carbon.
 MP = 1400o C but can be welded at 1000oC. MP of pure Fe = 1535oC
 Tough, malleable, and ductile and can be used for making chains, bolts, frameworks etc.
 For structural purposes it has been replaced by mild steel.
 Nowadays the bulk of pig iron is converted to steel.

Steel - Iron alloys

 All Fe/C alloys containing < 2% C
 Broadly classified as follows:
a) Mild steel – 0.1 – 0.3% C. (Cheaper than wrought Fe and stronger or more workable)
than cast Fe
b) Medium carbon steel – 0.3 – 0.6% C
c) High carbon steel & tool steel – 0.6 – 1.3% C

 Steel may also contain other metals such as Ni, W, etc. Such is known as alloy steel and is
prepared by addition of appropriate alloying metals.
o Ductile and can be rolled or machined into shape. Hardness and strength increase with
C content.

78
Processes of Making steel (Modern)

a) Basic oxygen process (BOP)

 A set of pure O2 is blown through retractable water cooled steel ‘lances’ into or over the
surface of molten pig-iron mixed with lime which is contained in a basic lined furnace. O 2
penetrates molten metal & oxidizes impurities rapidly. Heat generated keeps the metal
molten. Impurities form a slag which is usually removed by tilting the converter.

 Impurities are oxidized eg C, Si and P. Addition of lime slags off CaSiO3 and calcium
phosphates. The furnace is eventually tipped and molten steel poured either into moulds to
give steel castings or into ingots which in turn may be passed to rolling mills.

Advantages of using O2 rather than air

1. There is faster conversion, so a given plant can produce more per day.
2. Larger quantities can be handled (eg a 300 tn charge can be converted in 40 minutes compared with
6 tonnes in 20 minutes for Reserve process).
3. It gives a purer product, and the surface is free from nitrides.

Composition of various steels

%C Name
0.15 – 0.3 Mildsteel
0.3 – 0.6 Medium steel
0.6 – 0.8 High Carbon Steel
0.8 – 1.4 Tool steel

Steels may also contain other metals such as manganese, nickel, tungsten, etc.

b) Electric arc process

 This uses an electric arc through the metal (direct arc) or an arc just above the metal
(indirect arc) as a means of heating. Widely used in the manufacture of high quality alloy
steels such stainless steel, heat resistant steel, and high speed cutting steel which contains
18%W, and 5% Cr for cutting edges on lathes. Stainless steel contains 12-15% Ni, for
cutlery contains 20% Cr and 10% Ni.

c) Older methods of making steel.

(i) Bessemer process – used pear shaped furnance lined with silica. Compressed air was blasted
through pig iron to oxidize impurities.
(ii) Open hearth process
(iii) Puddling process

All platinum group metals are isolated from platinum concentrates which are commonly obtained either
from ‘anode slimes’ in the electrolytic refining of nickel and copper or as ‘converter matte’ from the
smelting of sulphide ores.

Classical methods of separation, refining on selective precipitation, are still widely used or employed
but solvent extraction and ions exchange techniques are increasingly being introduced to effect primary
separations. They offer superior efficiency.

79
The Chemistry of Iron
Common oxidation states are Fe2+ (ferrous) and Fe3+ (ferric). In absence of air, it reacts with mineral
acids to give iron(II) salts

Fe(s) + 2HCl → FeCl2(aq) + H2 (g) or

Fe(s) + 2H+ → [Fe (H2O) 6]2+ + H2 (g) Eo = 0.45V

HCl – is non oxidizing unlike HNO3 and H2SO4

Fe2+ (aq) → Fe3+ (aq) + e- Eo = -0.77V.

The negative Eo means that oxidation stops at Fe2+.

In air Fe2+ is slowly oxidized to Fe3+ or [Fe(H2O)6]3+ by atmospheric oxygen.

4Fe2+(aq) + O2(g) + 4H+ → 4Fe3+(aq) + 2H2O(l) Eo = 0.46V

With oxidizing acids like HNO3 iron is oxidized directly to Fe3+. E.g

Fe + NO3 + 4H+ → Fe3+ + NO(g) + 2H2O(l) Eo = 1.00V

Addition of base to Fe3+ precipitates Fe(OH)3(s).

Fe3+ + 3OH- (aq) → Fe(OH)3 aq) ≡ Fe2O3 xH2O

Red-brown gelatinous solid

Fe(OH)3 is very insoluble (Ksp = 2.6 x 10-39). As a result it forms as soon as the pH rises above 2.
Fe(OH)3 is not appreciably amphoteric. It dissolves in acid, but not in excess base (c.f. Cr(OH) 3)

Fe(OH)2 is a true hydroxide which is somewhat amphoteric. It is formed as a pale green precipitate
from Fe2+ solutions upon addition of hydroxide solutions. It is readily oxidized to Fe 2O3.H2O by O2 in
the air (solutions change colour to rusty brown upon standing in air). It dissolves in hot canc. NaOH
forming solutions from which blue Na4[Fe(OH) 6] crystals can be obtained.

The Fe2+ state

 Salts often called ferrous salts
 Well known crystalline compounds
 Mostly coloured pale green and contain the [Fe(H2O)6]2+ ion e.g. FeSO4.7H2O, FeCl2 6H2O and
Fe(ClO4)2.6H2O
 Fe2+ compounds are easily oxidized and so are hard to obtain pure. However, the double salt
FeSO4(NH4)2SO4 6H2O is used as a standard compound in volumetric analysis for titrations with
oxidizing agents such Cr2O72-, MnO4- and Ce4+ solutions. It is also used as a calibration substances
in magnetic measurements.
 FeSO4 and H2O2 are used as Fenton’s reagent for producing hydroxyl radicals and, for example,
oxidizing alcohols to aldehydes.

80
Complexes of Fe2+

 Forms many complexes with haemoglobin being most important biologically.

 Most are Octahedral though a few tetrahedral halide complexes [FeX 4]2- are known.
 Best known is [Fe(CN)6]4-. K4[Fe(CN)6] is a yellow coloured solid made by action of CN- on
Fe2+ salt in solution.
 Potassium ferrocyanide K4[Fe(CN)6] is used to test for iron in solution.

Fe2+ + K4[Fe(CN)6] K2FeII[FeII(CN)6]

White ppt

Fe3+ + K4[Fe(CN)6] KFeIII[FeII(CN)6]

deep blue (Prussina blue)

Fe2+ + K3[Fe(CN)6] K2FeII[FeIII(CN)6]

deep blue (Turnbull's blue)

 KFeIII[FeII(CN)6] and KFeII[FeIII(CN)6] have been used as pigments in ink and paint. They are now
known to be identical. The intense blue colour occurs due to electron transfer between Fe 2+ and Fe3+

[Fe(CN)6]4- + NO3- + 4H+ [Fe(CN)5(NO)]2- + NH4+ + CO2

nitrate
nitrosopentacyanoferrate(II)
(Brown-red crystals)

Na4[Fe(CN)6] + NO2- + H2O Na2[Fe(CN)5(NO)] + 2NaOH + CN-

nitrite
nitrosopentacyanoferrate(II)
or sodium nitroprusside

Nitroprusside is used as a sensitive qualitative test for sulphides.

2[Fe(CN)5(NO)]2- + S2- 2[Fe(CN)5(NOS)]4-

Purple complex

Bright red [FeII(Phen)3]2+ is used for colorimetric determination of iron and also as an indicator i.e. the
redox indicator ‘ferroin’ in titrations. It is easier to oxidize [Fe(H2O)6]2+ to [Fe(H2O)6]3+ than it is to
oxidize [Fe(Phen)3]2+ (red colour) to (Fe(Phen)3)3+ (blue colour). Thus the red colour persists until there
is excess oxidizing agent present. The greater stability of the Fe2+ complex is due to π-bonding between
the metal and low energy π-antibonding orbitals on the ligand.

The brown ring test for nitrates and nitrites depends on forming a brown complex [Fe(H 2O)5(NO)]2+.
Here a freshly prepared solution of FeSO4 is mixed with the solution containing NO2- or NO3- ions in a
test tube. Conc H2SO4 is run down the side of the tube so that the acid forms a layer at the bottom. The
H2SO4 reacts with NO3-, forming NO, which combines with Fe2+ slowly forming the brown complex
[Fe(H2O)5(NO)] 2+ at the interface between the two liquids. If the mixture gets hot or is shaken the
brown colour disappears. NO is evolved and a yellow solution of Fe 2(SO4)3 remains. Nitrites give the
brown colour before H2SO4 is added.

The Fe3+ State

81
 Also called the ferric state
 Ferric salts are obtained by oxidizing corresponding ferrous salts.
 Solutions are frequently yellow – brown coloured. Colour is due to colloidal iron oxide FeO.OH or
Fe2O3
 Fe3+ forms crystalline salts with all common anions except I- and CO32-. Many of the salts exist in
both anhydrous and hydrated forms. Examples include FeCl 3.6H2O, FeF3.4½H2O and Fe2(SO4)3
9H2O- all yellow, FeBr3 6H2O and FeF3 are green, Fe(NO3)3.H2O is colorless while Fe(NO3)3.9H2O
is pale purple

 Several salts contain (Fe(H2O6]3+ ion, the most common being Fe2(SO4)3 which exists in 6 different
hydrates. It’s widely used as a coagulant to clarify drinking H2O and also in the treatment of
industrial effluent and sewage.
 Alums are double salts which crystallize easily. They contain [Fe(H2O)6]3+. Examples include
ammonium ferric alum (NH4)[FeIII(H2O)6][SO4]2.6H2O, potash alum [K(H2O)6][FeIII(H2O)6][SO4)2.
These are used as mordants in the drying industry.

Complexes of Fe3+
Fe3+ prefers liqands which use O donor atoms to those that use N (hard bases). For example, NH 3
complexes are unstable in H2O. Complexes with chelating N ligards such as dipyridyl and 1,10-
phenanthroline are formed, but are less stable than their Fe 2+ counterparts. They cause spin pairing.

The most common complex is [Fe (H2O)] 3+ which is pale purple in strong acid solutions. This tends to
hydrolyze to yellow solutions at pH 2-3. See below.

Halides of Iron
It forms all the FeX2 and FeX3 except FeI3. FeI3 may exist in impure state with FeI2 due to the redox
reaction

Fe3+ + I- Fe2+ + ½I2

The dihalides are prepared by reacting haloacids with the metal. For example,

Fe + HF(aq) FeF2.8H2O (white solid)

Fe + HCl(aq) FeCl2.4H2O (pale green solid)
Fe + HBr(aq) FeF2.4H2O (pale green solid)

Chlorides are used as source material for the synthesis of other iron compounds.

82
 Heat and pass HCl
Fe FeCl2(s) + H2
powder
anhydrous

in THF
FeCl3 + Fe(s) FeCl2(s)

reflux in chrolobenzene
FeCl3 FeCl2(s)
Heat and pass dry Cl2
Fe FeCl3
powder almost black, red-brown crystals

FeCl3 hydrolyses quite readily in moist air. It is soluble in ethers and other polar solvents indicating a
high degree of covalency. In fact, Fe3+ solutions unless strongly acidic, hydrolyze giving yellow
solutions due to formation of hydroxo- species that have charge transfer bands in the UV region trailing
into the visible region. For example,

At pH = 2 - 3
[Fe(H2O)]3+ [Fe(H2O)5(OH)]2+ + H+ K = 10-3.05
[Fe(H2O)5(OH)]2+ [Fe(H2O)4(OH)2]+ K = 10-3.26

At pH = 4 - 5
H
3+ O
2[Fe(H2O)6] (H2O)4Fe Fe(H2O)4 + 2H+ K = 10-2.91
O
H
Oxides of Fe
FeO and Fe2O3 are known. The mixed oxide Fe3O4 (Fe2+ - Fe 3+) is also known.

FeO
Prepared as a black pyrophoric powder by ignition of Fe 2+ oxalate.

Heat in air
Fe(C2O4) FeO + CO2 + CO the quench to prevent dispropotionnation
FeO Fe3O4 + Fe

FeO is usually non-stoichiometric approximating Fe 0.95O implying presence of some Fe3+. It is

completely basic giving Fe2+ salts when reacted with mineral acids.

Fe2O3
o
Heat at 200 C
Fe3+ + OH- Fe2O3.xH2O Fe2O3

o Occurs as mineral hematite

83
 3+
o Has a corundum structure with an hcp (hexagonal close packed) array of O and Fe in
the octahedral interstices.
o Largely basic giving Fe(H2O)63+ with mineral acids.
o Dissolves in conc. NaOH to give [Fe(OH)6]3- which is slightly amphoteric

Fe3O4
 Occurs naturally as magnetite.
 Ignition of Fe2O3 above 14600C yield Fe3O4
 Has the inverse spinel structure.

Test for Fe3+

Mix aqueous solutions containing Fe3+ and SCN- ions. A blood red clolour is produced which is due to
a mixture of [Fe(SCN)(H2O)5)2+ and also some Fe(SN)3 and [Fe(SCN)4]-. The colour may also be used
for the estimation of Fe3+ ions. The colour is destroyed by the addition of F- ions because [FeF6]3-is
formed.

Question: How can one tell if a solution contains Fe3+?

Ferrates
If Cl2 is passed into alkali is solution containing hydrated ferric oxide the solution turns red-purple due
to the formation of the ferrate ion FeO42-. This is a stronger oxidizing agent than KMnO4. This may also
be obtained by oxidizing Fe3+ with aqueous NaOCl of electrolytically.

Fe3+ + NaOCl → FeO42-

Ferrates contain Fe(IV) and may be precipitated as salts eg Na2FeO4, K2FeO4, BaFeO4. These are purple
coloured and much more strongly oxidizing than KMnO4. The solubility of M(IV) state decreases
across the periodic table CrO42- > FeO42- > > CoO42-. They are only stable in strongly alkaline solution
and decompose in H2O or acid liberating O2

2[FeO4]2- + 5H2O → Fe3+ + 3/2O2

It is tetrahedral like CrO42-. Na and K ferrates are soluble but BaFeO4 is precipitated. Across the
transition series Fe is the 1st element that fails to attain group oxidation state

Bioinorganic chemistry
Biologically Fe is most important transition element involved in several processes:
 O2 carrier in the blood of mammals, birds, and fish (haemoglobin)
 electron carrier in plants animals and bacteria (cytochromes) and for e- transfer in plants and
bacteria (ferredoxins)
 Oxygen storage in flesh tissue (myoglobin)
 Storage and scavenging of Fe in animals (ferretin and transferring)
 Nitrogenase in nitrogen fixing bacteria

Rusting of Iron
 This is a special case of corrosion which is of great practical importance which costs about 1% of
the world’s economy
 Consists of the formation of hydrated oxide, Fe (OH)3 or Fe(OH).
 Its evidently an electrochemical process which requires presence of
a. H2O

84
 b. O2
c. An electrolyte

If one of the conditions is not fulfilled, rusting does not occur to any significant extent. The mechanism
is complex and depends on the prevailing conditions. In air a relative humidity of 50% provides the
necessary amount of water. It can be summarized as follows:

Cathode: 3O2 + 6H2O + 12e- → 12OH-

Anode: 4Fe → 4Fe2+ + 8e-
4Fe2+ → 4Fe3+ + 4e-
Overall: Fe + 3O2 + 6H2O → 4Fe3+ + 12OH- = 4Fe(OH)3 or FeO(OH) + 4H2O

 Electrolyte is required to provide a pathway for the current. In urban places this is provided by
FeSO4 formed as a result of attack by atmospheric SO2. In seaside areas airborne particles of salt
are important.
 It is a complex process which can be simply explained as follows:

Fe atoms are converted to Fe2+ ions and electrons. The electrons move to a more noble metal
which may be present as an impurity in the iron or in contact with it. They discharge H+ ions
present in H2O as H2 gas which reacts with atmospheric oxygen to give water.

Fe → Fe2+ + 2e-
2H + 2e- → 2H
+

2H + ½O2 → H2O

The iron becomes positive and forms the anode and the noble metal serves as the cathode i.e.
small electrochemical cells are formed at the surface. Fe2+ are subsequently oxidized to Fe3+,
either FeO(OH), Fe2O3 or Fe3O4

Because the oxide does not form a coherent protective film, corrosion is continuous.

Prevention of rusting
 Exclusion of O2 H2O and impurities. This is done by
1. Electroplating with a thin tin (Sn) layer
2. Hot dipping Fe in molten Zn
3. Galvanizing (electroplating with Zn)
4. Painting with red lead (Pb3O4, or 2PbO·PbO2)
5. Treatment of Fe with ‘inhibitors’ such as CrO42- or (in the presence of air) phosphate or
hydroxide, all of which produce a coherent protective film of FeO3 etc.
6. Converting outer layer of Fe into iron phosphate. This is done by treating the iron surface
with phosphoric acid or acid solutions of Mn(H2PO4)2 or Zn(H2PO4)2 in the Parkerizing and
Bonderizing processes.
7. Using a sacrificial anode making Fe the cathode

85
 UNIT 9
Platinum group metals
Rare elements, Pt being the commonest with an abundance of about 10-6% whereas the others have
abundances on the order of 10-7%. They occur as metals (elemental form), often as alloys such as
osmiridium, and in arsenide, sulphide and other ores. They are usually associated with one another and
also with Cu, Ag and Au. 98% of the world’s supply of Pt metals comes from former USSR (49%),
South Africa (43%) and Canada (6%).

During extraction, the ore is concentrated by gravitation and flotation, after which it is melted with
lime, coke, and said and is bessemerized in a converter. The resulting Ni-Cu sulfide ‘matte’ is cast into
anodes. On electrolysis in H2SO4 solution Cu is deposited at the cathode, and Ni remains in solution,
from which it is subsequently recovered by electro-deposition. The platinum metals, silver, gold collect
in the anode slimes. These are separated by complicated procedures which earlier involved classical
precipitations or crystallizations and now involve ions exchange and solvent extraction procedures.
Typical solvent extraction process

Pt group metals
concentrates
Disssolve in aqueous HCl
sturated with Cl2
Distill off RuO4 and OsO4
Extract with MIBK
Au, Fe, Te
Boil off HCl
AgCl
Extract with hydroxime
Pd extract
Extract with tributyl phosphate
Pt extract
Strip with aq. HCl or an amine
and NH4Cl
Strip with aq HCl
and ajudt pH to 10
Pd(NH3)2Cl2
H2PtCl6
Ignite Rh, Ir separation
NH4Cl
Boil to remove excess
Pd metal oxidants
(NH4)2PtCl6
(NH4)2IrCl6 (s)
Rh(NH3)5Cl]Cl2 (s) Ignite

2-
Extract with organic amine Pt metal
[IrCl6]

Ignite
Ignite in H2
[Rh(NH3)5Cl]Cl2 Rh metal
Ir metal

Properties and uses of the platinum elements

 Greyish white and are initially obtained as powders by ignition of salts such as (NH 4)2PtCl6

86
  Almost all compounds of these elements give the metal when heated. However, Os is reality
oxidized to the very poisonous volatile OsO4 and Ru gives RuO2. Therefore reduction by H2 is
necessary in order to recover the metals.
 The metals can also be thrown out from acid solution by ‘footing’. Footing involves adding Zn
to the acid solutions especially of Ag and Au.
 Metals are chemically inert especially when massive. Ru and Os are least attacked by fused
alkali.
 Rh and Ir attacked by HCl and NaClO3 at 125 to 150oC
 Pd and Pt are attacked by conc, HCl + Cl2 or aqua regia
 The metals in gauze or foil form and especially on supports such as alumina, or charcoal are
used as catalysts in industry. On the alumina and charcoal supports, the metal salts are absorbed
and then reduced in situ.
 35 – 40% of Pt and about ½ as much Pd is used in the catalytic control of car-exhaust
emissions.
 Pd and Rh compounds are used in homogeneous catalytic syntheses.
 As – 40% of Pt is used for jewelry
 18% Pt in the petroleum & glass industries
 Pt–Re or Pt-Ge on alumina reforming of crude petroleum.
 Catalytic reforming – converts aliphatic compounds to aromatic compounds.
 Catalytic cracking – process of heating the high building material under pressure in the
presence of catalyst (usually finely divided, acid-washed aluminium silicate clay). Under these
conditions large molecules are cracked or broken into smaller fragments and continuous chains
alkanes are isomerizes to branched chain alkanes.

Why do catalytic cracking?

 To increase both quality and quality of gasoline fraction. The gasoline fraction of straight run
distillation is too scanty for the needs of our automobile oriented society. Again straight run
gasoline has poor burning characteristics in automobiles. In automobile engines, continuous
chains hydrocarbons burn eventually and cause knocking (the ticking and malting noise heard
when a car accelerates uphill). To prevent knocking, branched chain alkanes and aromatic
compounds, which burn more evenly than straight chain analogues are added to automobile
fuels.

 To obtain alkanes and aromatic used as starting materials for making plastics and other
synthetic organic compounds. (Fessenden R.J. organic chem. Pg 251.2 F4 1990).

Other uses
 Pt alloys are used in electrical contacts
 Pd and Pt are capable of absorbing large quantities of molecular H2, and Pd is used for the
purification of H2 by diffusion since Pd metal is strongly permeable H2.
 Pd (46%) is used in dentistry
 Over 90% Rh is used in control of car-exhaust emissions.
 In the form of phosphorous complexes it is used in hydrogenation and hydroformylation rxns.
 Ir – coating of anodes in chloralkali plant and as a catalyst in the production of acetic acid.
 Os – in dentistry as a hardening agent in Au alloys
 Ru – as coating of Ti anodes in the electrolytic production of Cl 2 and more recently as catalyst
in production of NH3

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 Table 18: The halides and oxides of Fe, Ru, and Osa (mp/oC)
+2 +3 +4 +5 +6 +7 +8 Others
FeO Fe2O3 RuO2 Fe3O4
Ru2O3h OsO2 (RuO3)h RuO4
(OsO3)h OsO4
FeF2 FeF3
White (d > 1000) pale green (>1000)
FeCl2 FeCl3
pale yellow (674o) brown-black (306o)
FeBr2 FeBr3
yellow-green (d 684o) red-brown (d > 200o)
FeI2 FeI3
grey black
RuF3 RuF4 RuF5 RuF6
dark-brown (d > 650o) yellow dark green (86.5o) dark brown (54o)
RuCl2 RuCl3
brown black (α) dark brown (β)
RuBr2 RuBr3 OsF4 OsF5 OsF6 OsF7
black dark brown (d > 400o) yellow (230o) blue (70o) yellow (33o) yellow

RuI2 RuI3 OsCl4 OsCl5 OsCl3.5

blue black red Black (d > 160o)
OsCl3 OsBr4 OsI
dark grey (d 450o) black (d 350o) metallic grey
OsI2 OsI3
black black
a
unstable one shown in brackets h hydrous oxide

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General properties
Ru and Os
 Are noble
 Very resistant to attack by acids
 Os oxidized to OsO4 by aqua regia

Low Oxidation states of Fe, Ru and Os

-2 is rare but occurs in carbonyl ions (Fe(CO)3]2- and [Ru(CO)4]2-
0 occurs in carbonyls, which may be mononuclear eg Fe(CO)5, Ru(CO)5, and Os(CO)5, dinuclear e.g.
Fe2(CO)9, Os2(CO)9 or trinuclear e.g. Fe3(CO)12, Ru3(CO)12, OS3(CO)12

All these carbonyls are volatile solids except the mononuclear ones. Fe(CO) 5 is available commercially.

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