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There are about 50 transition elements and they have interesting chemical properties
such as a variety of different oxidation states in their compounds, their extensive
ability to form complexes, useful and often colourful compounds.
A transition element is a d-block element that forms some compounds containing its
ion with an incomplete d-subshell.
You have to know the electronic configurations of the elements and their ions by
looking at the periodic table.
The 3d block contains ten elements, because the 3d subshell contains five orbitals,
each can accommodate 2 electrons of opposite spins. All these elements involve the
filling of the 3d set of orbitals.
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The 4s orbital is lower in energy than 3d. 4s orbital is filled before 3d orbital.
However, exceptions:
Cr [Ar] 3d5 4s1
Cu [Ar] 3d10 4s1
3d5 - half filled d orbital is preferred.
3d10 full d-orbital
Why? Symmetrical 3d cloud of electrons that screens the nucleus more effectively
than the other configurations.
Before electrons occupy 4s and 3d, 4s is energetically more stable than 3d.
When 3d orbitals are occupied by electrons, they repel the 4s electrons even further
from the nucleus and up to a higher energy level than the 3d orbitals.
Thus, the energy level of the 4s orbital is higher than that of the 3d orbitals.
Properties
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remains
almost constant (increases
slightly)
Chemical properties:
The transition metals and their compounds display chemical behaviour that differ from the
s-block metals and their compounds. The more important common features are:
s-block metals Transition metals
They can form ions and
They form ions and compounds compounds
with with the metal having a variety of
the metal having fixed oxidation oxidation states.
Oxidation states
states. Manganese: (+2) Mn , (+4)
2+
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complex ions.
[Cu(NH3)4]2+, [Fe(CN)6]3,
[Ag(NH3)2]+
They form coloured ions or
They form white solids or compounds.
Formation of coloured ions
colourless dichromate ion: orange,
or compounds
solutions. Iron(III) ion: yellow, MnO4:
purple
Oxidation states : can form often colored ions and compounds with the metal having
different oxidation states.
eg. manganese in its compounds can exhibit a range of oxidation numbers ranging
from +2 to +7.
eg. In the Contact Process (wiki this, this is out of syllabus but came out in exam
before), vanadium (V) oxide is used as a catalyst to convert sulfur dioxide into sulfur
trioxide.
Why do the various transition metal ions have variable oxidation states?
Reason : Close similarity in energy of the 4s and 3d electrons. Hence, once the 4s
electrons are removed, some or all of the 3d electrons may be removed without
requiring much more energy.
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Diagram : Common oxidation states of the transition metal ions
The higher oxidation states tend to involve covalency (eg. TiO2, V2O5, Mn2O7) and
oxo-anions (eg. MnO4-)
Redox reactions:
Generally, ions that have the transition metal in a high oxidation state tend to be
good oxidising agents.
Early transition metals in low oxidation states tend to be good reducing agents. Cr2+,
V2+.
Usually color change when transition metal ions undergo redox reactions.
Ligand exchange
Hydrolysis
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Redox
The oxidation state of the metal is changed by adding or removing one or more
electrons
Catalytic activity
Transition elements, both in the form of elements and in their compounds, are
important catalysts in organic synthesis and in chemical industries.
The catalyst takes part in the reaction but does not undergo any permanent chemical
change after the end of the reaction.
Heterogeneous catalysis:
Haber Process:
Equation :
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Fe 3d partially filled orbitals can accept electron pairs from reactant molecules.
The adsorption process bring reactant molecules closer together and in the correct
orientation.
After reaction, product molecules, ammonia molecules desorb and diffuse away from
catalyst surface so that active sites are exposed for further reaction.
Note:
Forward and reverse reactions are speeded up by catalyst. Products are not formed
more in quantity, but more quickly.
A catalyst provides a different mechanism for the reaction, with a new, lower
activation energy pathway.
A catalyst does not alter the enthalpy change of reaction.
Other catalysts: contact process, hydrogenation of vegetable oils to make margarine
by catalyst nickel.
Homogeneous catalysis:
The ability of transition metals to vary their oxidation state is the key factor in their
efficiency as homogeneous catalysts.
Iron(III) ions as catalyst.
Complex formation:
Transition elements can form complex compounds.
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High charge density of transition metal cations.
The cations have low lying vacant d orbitals that can be used to accommodate the
lone pair of electrons from the ligands, resulting in dative bond formation.
Complexes:
Transition metal cations, the water molecules involved in hydration are held to the
cation by stronger forces, leading to the formation of aqua Complexes general
formula [M(H2O)6]n+.
Ligands in complexes:
The ligands bind to the central metal ion by dative bonds.
L: --> Mn+
Examples of ligands: chloride ion, hydroxide ion, cyanide ion, water, ammonia,
carbon monoxide
Definition:
Ligands can be classified according to the number of dative bonds that it forms with
the central metal ion.
Mondentate ligand: Those that can form only one co-ordinate bond with a central
metal ion (or atom).
Polydentate ligand: Those that bond through electron pairs on more than one donor
atom.
Polydentate ligands are sometimes called chelating agents because of their ability to
hold a metal ion like a claw. (like a crab's claw holding onto its victim [the metal ion]
tightly)
Chelating ligands form stable complex ion with the central metal ion as the pincer-
like grip of these polydentate ligands are able to hold the cation more securely. Eg.
EDTA4-
The nucleophiles from organic chemistry and Lewis bases (electron pair donor)
from general inorganic chemistry fulfil the same role.
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Complexes :
A complex is formed by a central ion ( or atom) dative-bonded by surrounding ions or
molecules (known as ligands)
L --> M <-- L
A complex can be neutral, cationic or anionic.
In order to maintain charge neutrality in the compound, the complex ion is typically
associated with other ion, called counter ions.
Co-ordination number indicates the total number of dative bonds around the central
atom or ion. The most common values are 2, 4 and 6.
Silver diamine compounds. [Ag(NH3)2]+ ions (coordination number : 2) are used in
carbonyl chemistry to oxidise aldehydes to ions with the formation of a silver mirror
or a silver precipitate.
IMPORTANT!
Why are transition metal complexes often coloured?
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Transition metal compounds are frequently coloured. This is due to the absorption of
light in the visible region of the electromagnetic spectrum.
Nature of ligands
Different ligands have different effects on the splitting of the d-orbitals. The larger the
splitting of energy levels, the shorter the wavelengths absorbed and the longer
wavelength light is thus observed.
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You need to know the Common transition metal compounds and their colours.
IMPORTANT!
The variety of color among transition metal complexes has long fascinated the
chemists.
For example, aqueous solutions of [Fe(H2O)6]3+ are red, [Co(H2O)6]2+ are pink,
[Ni(H2O)6]2+ are green, [Cu(H2O)6]2+ are blue and [Zn(H2O)6]2+
are colorless. Although the octahedral [Co(H2O)6]2+
are pink, those of tetrahedral [CoCl4]2- are blue. The green
color of [Ni(H2O)6]2+
turns blue when ammonia is added to give [Ni(NH3)6]2+.
Haemoglobin:
Haem binds with O2 molecule , O2 forms a dative bond with the iron to form a
species called oxyhaemoglobin.
CO ligand forms a very stable complex with hame
To form carboxyhaemoglobin which is very stable and displaces oxygen from the
cells of the body. Harmful effects on body are observed.
Review question:
Is the formation of a complex a reaction between a Lewis acid and a Lewis base?
Shapes of complexes: You can use VSEPR model to predict the shape of the
complexes (with limitations). Common shapes are linear, tetrahedral, square planar
and octahedral.
COMPLEMENTARY COLORS
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