Inorganic Chemistry

CHIC 411

Transition and Inner transition

Elements
(Part A)
Occurrence
Occurrence
1. Abundances tend to decrease going down each family.

2. The lighter elements are normally bonded to oxygen in

their natural deposits. The heavier, softer metals
generally prefer sulfur.
OR
The more electropositive "hard' metals occur as oxides
and are extracted by reduction. Chemically soft members
of the block occur as sulfide minerals and are partially
oxidized to obtain the metal.

3. The oxidation state preferences are reflected in the

ores and minerals of these metals.
Going across the first transition series, the relative
natural abundances follow the order
Sc << Ti>> V« Cr < Mn << Fe >> Co < Ni> CuZn
The 4d and 5d elements are rare, with the exception of
zirconium (about 160 ppm in the lithosphere, roughly
the same as vanadium). The most abundant element of
each family is the lightest one.
Several elements, including silver, gold, and platinum,
have such positive M"/M reduction potentials that they
occur as native metals.
The remaining free elements are obtained by chemical
reduction.
The elements on the left of the 3d series occur in nature primarily
as metal oxides or as cations in combination with oxoanions. Of
these elements, titanium the most difficult to reduce, and the
element is widely produced by heating TiO2 with Cl2 and C to
produce TiCl4, which is then reduced by molten magnesium at at
1000°C in an inert-gas atmosphere.

The oxides of Cr, Mn, and Fe are reduced with C, a much cheaper
reagent.

To the right of Fe in the 3d series, Co, Ni, Cu, Zn occur mainly as

sulfides and arsenides, which is consistent with the increasingly
soft Lewis acid character of their dipositive ions.
Sulfide ores are usually roasted in air to the metal directly (for
example, Ni) or to an oxide that is subsequently reduced.

Copper used in large quantities for electrical conductors;

electrolysis is used to refine crude copper to achieve the high
purity needed for high electrical conductivity.
The difficulty of reducing the early 4d and 5d metals Mo and W is
apparent from Table. It reflects the tendency of these elements to
have stable high oxidation state.

The platinum metals (Ru and Os, Rh and I, and Pd and Pt), which
are found at the lower right of the d block, occur as sulfide and
arsenide ores, usually in association with larger quantities of Cu,
Ni, and Co.

They are collected from the sludge that forms during the
electrolytic refinement of copper and nickel.

Gold (and to some extent silver)is found in its elemental form.

The general characteristics of d-block elements are:
1. Nearly all the transition elements have typical metallic properties
such have high tensile strength, ductility, malleability, high
thermal and electrical conductivity and metallic lustre.

2. Except mercury which is liquid at room temperature, other

transition elements have typical metallic structures.

3. They have high melting and boiling points and have higher heats of
vaporisation than non-transition elements.

4. The transition elements have very high densities as compared to

the metals of groups I and II (s-block).

5. The first ionisation energies of d-block elements are higher than

those of s-block elements but are lesser than those of p-block
elements.
6. They are electropositive in nature.

7. Most of them form coloured compounds.

8. They have good tendency to form complexes.

9. They exhibit several oxidation states.

10. Their compounds are generally paramagnetic in nature.

11. They form alloys with other metals.

12. They form interstitial compounds with elements such as hydrogen,

boron, carbon, nitrogen, etc.

13. Most of the transition metals such as Mn, Ni, Co, Cr, V, Pt, etc. and
their compounds have been used as good catalysts.
Properties Common to the Transition Elements

1. The free elements conform to the metallic bonding model. Thus,

their lattices are typically either close-packed or body-centered
cubic. They generally have high thermal and electrical
conductivities, and they are malleable and ductile.

2 Nearly all have more than one positive oxidation state. (zinc and
cadmium are two exceptions.)

3 Nearly all have one or more unpaired electrons in their atomic

ground states, and form paramagnetic compounds and ions. (Zinc is
again an exception.) Because of this, studies of magnetic properties
using experimental tools such as NMR, ESR (clectron spin
resonance), and magnetic susceptibility are often employed in this
area of chemistry.
4. Low-energy electron transitions are observed for the free
elements and their compounds and complexes. The transitions may
fall into the infrared, visible, or ultraviolet region; for the visible
cases, and colored species are the result.

5. The cations of these elements (and often the neutral atoms as

well) behave as Lewis acids, and there is a strong tendency to form
complexes. Complexes having 2-6 bases (ligands) are common, and
species with as many as 14 ligands about a single metal are known.
The commercial uses of the free metals are dominated by the
steel industry. Steel (of which there are many classifications) can
be loosely defined as an alloy for which iron is the major
component.

The addition of other metals is useful for improving certain

desirable properties such as strength, hardness, and ductility.

For example, the addition of vanadium or nickel increases

mechanical strength. Vanadium steel is used in automobile springs
and nickel steel is used for armor plating.

Chromium adds luster and general attractiveness (stainless steel).

Zinc coating (galvanization) improves resistance to rust.
Transition Metals and Living Organisms

• Iron – transport & storage of O2

• Molybdenum and Iron - Catalysts in nitrogen fixation

• Zinc – found in more than 150 biomolecules

• Copper and Iron – crucial role in respiratory cycle

• Cobalt – found in vitamin B12

•Cisplatin [PtCl2(NH3)2] square planar Pt(II) coordination number

4 cis-isomer the first of a series of platinum coordination complex-
based anti-cancer drugs (Platinol-AQ)
Physical and Chemical properties

The properties of the d-block metals are largely derived from their
electronic structure.

the lanthanide contraction is responsible for some of the anomalous

behavior of the metals in the 5d series.

The d block of the periodic table contains the metals most important
to modern society. It contains the immensely strong and light
titanium, the major components of most steels (Fe, Cr, Mn, Mo), the
highly electrically conducting copper, the malleable gold and
platinum, and the very dense osmium and iridium.

To a large extent these properties derive from the nature of the

metallic bonding that binds the atoms together.
Electronic configuration
• An inner core of electrons with noble gas configuration ie., ns2 np6.

• (n-1) d orbitals are filled progressively.

• Most of these have electrons in the outermost i.e., ns-subshell. Some

of the elements (e.g., Cr, Cu, Nb, Mo, Tc, Ru, Rh, Ag, Pt, Au, Ag etc.)
have only one electron in ns subshell.

• Pd has no electron in the ns-subshell. Pd (Z 46) : [Kr] 4d10 5s0.

• In the second and third transition series, there are many anomalous
configurations in comparison to those of first transition series.

• These are attributed to factors like nuclear-electron and electron-

electron forces.
1. Atomic Radii
• In a particular series atomic radii decrease with increase in atomic
number but this decrease becomes small after mid way.

• The atomic radius decreases in a period in the beginning because with

increase in atomic number, the nuclear charge goes on increasing and
due to poor shielding effect of d-electrons.

• As the number of d-electrons increases screening effect increases. This

neutralizes the effect of nuclear charge and atomic size remains
almost unchanged after Cr.

• At the end of each period, there is slight increase in atomic radii-

Towards the end, electron-electron repulsion between the added
electron in the same orbital exceeds the nuclear charge. Therefore
electron cloud expands and size increases.

• The atomic radii increases while going down the group- Radii of 4d
and 5d series almost identical due to lanthanoid contraction.
2. Metallic Character and Enthalpy of Atomization

They are solids at room temperature with an exception of Mercury.

They have simple hexagonal close packed (hcp), cubic close packed
(ccp) or body centred cubic (bcc), lattices which are characteristic of
other metals.

The metallic character of transition elements is due to their

relatively low ionisation enthalpies and number of vacant orbitals in
the outermost shell.

The hardness of these metals suggests the presence of strong

bonding due to overlap of unpaired electrons between different
metal atoms. Therefore, these elements exhibit high enthalpies of
atomization.
• In general, the greater number of unpaired d-electrons, greater is
the number of bonds and therefore, greater is strength of these
bonds.

• Cr, Mo and W are very hard metals as they have maximum number
of unpaired electrons and have maximum enthalpies of atomization.

• The Zn, Cd and Hg do not have any unpaired electrons, therefore,

these are not very hard.

• The metals of 4d and 5d series have greater enthalpies of

atomization than their corresponding elements of first transition
series.
3. Density

• All these metals have high density.

• Within a period, the densities vary inversely with the atomic radii.
Therefore, the densities increase as the radii decrease.

• The densities of second transition series are higher than those of

first transition series and the densities of third transition series
are still higher.

• Osmium (22.57 g cm3) and iridium (22.61 g cm3) have very high
density among these elements.

• Decrease in atomic radius coupled with increase in atomic mass,

results in general increase in the density of these elements.
4. Melting and Boiling Points
• The transition metals have very high melting and boiling points.
• The melting points of these metals rise to a maximum value and then
decrease with increase in atomic number.
• However, Mn and Tc metals have abnormally low melting points.
• The high melting and boiling points of these metals are due to strong
metallic bonds.
• In general, greater the number of valence electrons, stronger is the
metallic bonding and consequently, melting points are high.
• Therefore, as we move along a particular series, the metallic strength
increases upto the middle with increasing availability of unpaired
electrons upto Cr and then decreases with decreasing availability of
unpaired d-electrons.
• Therefore, the melting points decrease after the middle because of
increase of pairing of electrons.
• Mn have low M.P due to the fact that Mn has stable electronic
configuration (3d5 half filled, 4s2 fully filled). As a result, 3d
electrons are more tightly held by the Mn atomic nucleus and this
reduces delocalization of electrons resulting weaker metallic
bonding. Similar is the case with Tc.

• Zn, Cd and Hg are quite soft with low melting points.

• Hg is a liquid at room temperature and melts at-38°C. These

three elements behave typically because there are no unpaired
electrons available for metallic bonding and, therefore their
melting points are low.
5. Ionization Enthalpy

Ionization Enthalpy
• The I.E of transition elements are generally greater than those of
the s-block elements.

• The ionization energies of the transition metals increase while

moving along the period (due to the increase in atomic number).

• the first ionisation enthalpies of third transition series are higher

than those of first and second transition series.

• In the atoms of third transition series, there are filled orbitals.

The 4f-orbitals have very poor shielding effect. As a result, the
outer electrons have greater effective nuclear charge acting on
the outer valence electrons. Therefore, their ionisation energies
are higher.
6. Oxidation States
• Most of these show variable oxidation states.

• Except Sc, the most common oxidation state of the first row
transition elements is +2 due to loss of two 4s-electrons.

• The elements which show the greatest number of oxidation states

occur in or near the middle of the series.

• In the early elements of the series, Sc (II) is virtually unknown

• Titanium (IV) is more stable than Ti (II) and Ti (I).

• At the other end, the only oxidation state of zinc is +2 in which no

d-electrons are involved.
• In the +2 and +3 oxidation states, the bonds formed are mostly
ionic.

• In the compounds of higher oxidation states (generally formed with

oxygen and fluorine), the bonds are essentially covalent.

• For example, in MnO (Mn in +7) state all the bonds are covalent.

• Within a group, the maximum oxidation state increases with

atomic number. For example, iron shows common oxidation states
of +2 but ruthenium and osmium in the same group form
compounds in the +4, +6 and +8 oxidation states.

• Transition metals also form compounds in low oxidation states such

as and 0 or negative. The common examples are [Ni(CO)4].
[Fe(CO)5].
• The higher oxidation states are more stable in heavier transition
elements.

• For example, Mo (VI) and W (VI) are found to be more stable

than Cr (VI).

• Therefore, Cr (VI) in the form of dichromate in acidic medium is

a strong oxidising agent whereas MoO3 and WO3 are not.

• The transition elements show low oxidation states in some

complexes having ligands such as CO, which not only form sigma
bonds with the metal atoms but also have pi-acceptor
character. For example, nickel in Ni(CO), and iron in FelCO), have
zero oxidation states.
7. Standard Electrode Potentials
• In solutions the stability of the compounds depends upon
electrode potentials.

• In addition to ionization enthalpy, the other factors such as

enthalpy of sublimation, hydration enthalpy, etc. determine the
stability of a particular oxidation state in solution.

• The smaller the value of total energy change for a particular O.S
in aqueous solution, greater will be the stability of that O.S.
8. Formation of coloured compounds

• Most of the compounds of transition metals are coloured in the

solid form or solution Form.

• Due to the presence of incomplete (n - 1) d-subshell and Crystal

field splitting.

• Ti compounds contain one electron in d-subshell. It absorbs green

and yellow portions from the white light and blue and red
portions are emitted. Therefore, Tys ions appear purple.
• Similarly, hydrated cupric compounds absorb radiations
corresponding to red light and the transmitted colour is greenish
blue which is complementary colour to red colour. Thus, cupric
compounds have greenish-blue colour.

• Sc+3, Ti+4, Cu+1 and Zn+2 have completely empty or completely

filled d-orbitals and are colourless.
9. Magnetic properties

The larger the number of unpaired electrons in a substance, the

greater is the paramagnetic character and larger is the magnetic
moment.
10. Catalytic Properties
• Fe, Co, Ni, V, Cr, Mn, Pt, etc. are commonly used.
1. Fe-MO = synthesis of ammonia by Haber's process.
2. Ni = hydrogenation reactions in organic chemistry.
3. V2O5 = oxidation of SO2 to SO3 in the Contact process for the
manufacture of H2SO4.
4. MnO2 = catalyse the decomposition of H2O2 solution.
5. Co salts catalyse the decomposition of bleaching powder.
6. Pt = catalyst in many processes such as contact process for making
H2SO4, in three stage converters for cleaning car exhausts.
7. Pt/Rh is used in Ostwald process during manufacture of HNO3.
8. Pd = hydrogenation reactions in organic chemistry.
It is due to their tendency to form reaction intermediates with
suitable reactants. These intermediates give reaction paths of lower
activation energy and, therefore, increase the rate of the reaction.

In some cases, the transition metal catalysts provide a suitable large

surface area on which the reactants may be adsorbed and, therefore,
come closer to one another for the reaction. This increases the
concentration of the reactants at the catalyst surface and also
weakens the bonds in the reactant molecules. Consequently, the
activation energy gets lowered.
In some cases, the transition metal ions can change their
oxidation states and become more effective as catalysts.
11. Complex formation
• Form a large number of coordination complexes.

• Ex-[Co(NH3)6]2+, [Fe(CN)6]4- etc

• It is due to

1. small size of the atoms and ions of transition metals

2. high nuclear charge.

3. Availability of vacant d-orbitals of suitable energy to accept lone

pairs of electrons donated by ligands.
 12. Interstitial compounds

Transition metals form interstitial

compounds with elements such as
H, B, C and N.

They are generally non-

stoichiometric and are neither
typically ionic nor covalent.

Ex - TiC, MnN, FeH, FeC, TiH etc.

(TiH1.7, VH0.56)

As a result of the filling up of the interstitial spaces, the transition

metals become rigid and hard.
These interstitial compounds have similar chemical properties as the
parent metals but differ significantly in their physical properties
particularly, density, hardness and conductivity.

Ex- Interstitial compounds of steel and cast iron with C are hard.

These spaces are present because of defects in their structures and

existence of variable oxidation states.

The general of these compounds are-

1. They have high melting points which are higher than those of pure
metals.
2. They retain metallic conductivity.
3. They are very hard. Some borides have hardness as that of
diamond.
4. They are chemically inert.
13. Alloy formation
• Alloys are homogeneous solid solutions in which the atoms of one
metal are randomly distributed among the atoms of the other metal.

• The alloys are generally formed by these atoms which have metallic
radii within about 16% of each other.

• Alloys are hard, have high melting points and are more resistant to
corrosion than parent metals.

• Cr, Fe, Mn, V, W, Mo etc. are used to produce variety of steels and
stainless steel.

• Ex- bronze (copper-tin), brass (copper-zinc)

• The transition metals are quite similar in size and, therefore, the
atoms of one metal can substitute the atoms of other metal in its
crystal lattice. Thus, on cooling a mixture solution of two or more
transition metals, solid alloys are formed.
The end