Topic 13: The periodic table—the transition metals
13.1 First-row d-block elements
Transition elements have variable oxidation numbers, form complex ions with ligands, have coloured compounds,
and display catalytic and magnetic properties.
Physical properties: The transition elements are all metals with the following general physical properties:
high electrical and thermal conductivity
high melting point
malleable – they are easily beaten into shape
high tensile strength – they can hold large loads without breaking
ductile – they can be easily drawn into wires
iron, cobalt, and nickel are ferromagnetic.
These properties can be explained in terms of the strong metallic bonding found in the elements.
As the 3d electrons and 4s electrons are close in energy, they are all involved in bonding, and form part of the
delocalized sea of electrons which holds the metal lattice together (Topic 4). This large number of delocalized electrons
accounts for the strength of the metallic bond and the high electrical conductivity. The smaller atomic radii of the d-
block metals compared to their s-block neighbors also account, in part, for their higher densities.
Chemical properties
form compounds with more than one oxidation number
form a variety of complex ions
form coloured compounds
act as catalysts when either elements or compounds
Zn is not considered to be a transition element as it does not form ions with incomplete d orbitals.
Transition metals are element whose atoms have an incomplete d sub-shell, or which can give rise to cations with an
incomplete d sub-shell.
Zinc is not a transition metal!!
Zinc compounds do not generally form coloured solutions.
it shows only the +2 oxidation state in its compounds.
Because of the electronic configuration of its atom and the Zn2+ ion – the d sub-level is complete in both species
Sc3+ (aq) is also colourless in aqueous solution as it has no d electrons, but it is a transition metal as its atom has an
incomplete d sub-shell.
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Transition elements show an oxidation number of +2 when the s electrons are removed.
Explanation of the ability of transition metals to form variable oxidation states from successive ionization energies.
The Ca3+ ion is energetically unstable because there is a large jump in ionization energy as the third electron is removed
from the inner 3p orbital.
The increase in successive energies for titanium is more gradual as the 3d and 4s orbitals are close in energy.
Titanium shows the +2, +3, and +4 oxidation states. A large jump occurs between the fourth and fifth ionization energies, as
the inner 3p electron is removed, so titanium does not form the +5 state.
Common oxidation numbers of the transition metal ions are listed in the IB Data booklet in sections 9 and 14.
The more common oxidation states are highlighted in blue.
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• Oxidation states above +3 generally show covalent character. Ions of higher charge have such a large charge
density that they polarize negative ions and increase the covalent character of the compound.
• Compounds with higher oxidation states tend to be oxidizing agents. The use of
potassium dichromate(VI) (K2Cr2O7), for example, in the oxidation of alcohols is discussed in Topic 10.
Explanation of the nature of the coordinate bond within a complex ion.
Transition metal ions in solution have a high charge density and attract water molecules which form coordinate bonds
with the positive ions to form a complex ion.
The complex ion [Fe(H2O)6]3+
The water molecules are ligands as they form coordinate bonds to the
central ion.
More generally a complex is formed when a central ion is surrounded by molecules or ions which possess a lone pair
of electrons. These surrounding species (ligands), are attached via a coordinate bond.
All ligands have at least one atom with a lone pair of electrons which is used to form a coordinate bond with the
central metal ion.
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The number of coordinate bonds from the ligands to the central ion is called the coordination number.
The shapes of some complex ions and their coordination numbers are shown.
In aqueous solution, water molecules generally act as ligands but these can be replaced in a process known as ligand
exchange. As complexes often have distinctive colours they can be used in qualitative analysis
Deduction of the total charge given the formula of the ion and ligands present.
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Transition metals and their ions are important catalysts
Catalysts: substances that speed up chemical reaction by lowering the activation energy without being used up in the
reaction
Transition metals are effective catalysts because:
• their ability to form complexes allows them to bind then release reagents during a chemical reaction
• their variable oxidation states allow them to interact with the reagents in chemical reactions to facilitate the transfer of
electrons
Explanation of the magnetic properties in transition metals in terms of unpaired electrons.
Substances can be distinguished by their response to externally applied magnetic fields
Materials are classified as diamagnetic, paramagnetic, or ferromagnetic based on their behavior when placed
in an external magnetic field.
Diamagnetism is a property of all materials and produces a very weak opposition to an applied magnetic field. A
diamagnetic material is repelled by a magnetic field.
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Paramagnetism, which only occurs with substances which have unpaired electrons, is stronger than diamagnetism. It
produces magnetization proportional to the applied field and in the same direction.
Ferromagnetism is the largest effect, producing magnetizations sometimes orders of magnitude greater than the
applied field. Fe, Co, Ni
Transition metals and their complexes show paramagnetic properties.
Pair or promote?
The 𝑑-orbital splitting caused by the ligands surrounding a transition metal can cause pairing up of electrons if the
energy required to promote electrons to the higher energy 𝑑-orbitals is greater than the energy required to pair up the
electrons.
The strength of the paramagnetism depends on the number of unpaired electrons and this gives us information on the
bonding structure.
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13.2 Coloured complexes
The d sub-level splits into two sets of orbitals of different energy in a complex ion.
𝑑-orbitals are split into two sets of different energy due to the electric field of the surrounding ligands
the 𝑑-orbitals are not completely filled with electrons allowing electrons to move between the two sets of orbitals
electron transitions between the 𝑑-orbitals of different energy absorb energy in the visible part of the spectrum
Complexes of d-block elements are coloured, as light is absorbed when an electron is excited between the d orbitals.
The colour absorbed is complementary to the colour observed.
The relation between the colour observed and absorbed is illustrated by the colour wheel in the IB Data booklet in section 17.
The colour of transition metal ions can be related to the presence of partially filled d orbitals.
The ion Sc3+ is colourless because the 3d sub-level is empty; Zn2+ is colourless because the 3d sub-level is full.
If the d-orbital is full or empty, no electronic promotion can take place, so the complex appears white or colourless
since no coloured light will be absorbed.
White light is composed of all the colours of the visible spectrum. Transition metal compounds appear coloured
because their ions absorb some of these colours. [Fe(H2O)6]3+ , for example, appears yellow because it absorbs light in
the blue region of the spectrum.
Transition metals absorb light because the d orbitals split into two sub-levels
The electric field produced by the ligand’s lone pair of electrons, cause the splitinhg of the d orbitals into two sublevels.
Example, the octahedral complex [Ti(H2O)6]3+. When light passes through a solution of [Ti(H2O)6]3+, one 3d electron is
excited from the lower to the higher energy sub-level. A photon of green light is absorbed and light of the
complementary colour (purple) is transmitted, which accounts for the purple colour of a solution of [Ti(H2O)6]3+.
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The spectrochemical series is given in the IB data booklet in section 15.
Explanation of the effect of the identity of the metal ion, the oxidation number of the metal, and the identity of the
ligand on the colour of transition metal ion complexes.
nuclear charge and identity of the central metal ion
Ligands interact more effectively with the d orbitals of ions with a higher nuclear charge.
[Mn(H2O)6]2+ [Fe(H2O)6]3+
Both are isoelectric (same number of electrons for Mn and Fe)
Oxidation state of Mn is +2 and Oxidation state of Fe is +3
However; Fe has a greater nuclear charge than Mn; so has a stronger interaction with the water ligands;
greater splitting of the d orbitals
Manganese(II) compounds are pale pink in aqueous solution as the ions absorb in the green region of the
visible spectrum of light, whereas iron(III) compounds are yellow/brown as they absorb higher energy light in
the blue region of the spectrum
Increasing the nuclear charge, increases the size of the d-orbital splitting.
the identity of the ligand
Some ligands create a stronger electrostatic field than others and consequently cause a greater degree of 𝑑-orbital
splitting and absorption of light as higher frequencies.
The stronger electric fields absorb at higher, bluer, frequency (shorter wavelength).
Students are not expected to recall the colour of specific complex ions.
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Explanation of the effect of different ligands on the splitting of the d orbitals in transition metal complexes and
colour observed using the spectrochemical series.
the oxidation number of the metal
Only the splitting of the 3-d orbitals in an octahedral crystal field is required.
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A list of polydentate ligands is given in the data booklet in section 16.
Some ligands are molecules with multiple lone pairs positioned to form coordinate bonds with a metal ion.
They are called chelating agents because they can cage a metal ion in a claw like grip.
EDTA (ethylene diamine tetraacetic acid) is a hexadentate ligand which can form an octahedral complex on its own.
Students are not expected to know the different splitting patterns and their relation to the coordination number.
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