TOPIC 13: THE PERIODIC TABLE – The transition metals

13. 1 First-row d-block elements

Electronic configuration

The first-row d-block contains 10 elements because the 3d sub-level has 5 orbitals each accommodating two
electrons. These 10 elements, although they are in the same row and therefore in different groups, show a lot
of similarities but also some changes. However, as you move across the row these changes are only very
gradual (=transitional) as opposed to the more pronounced changes when you go across periods 2 and 3.

The reasons why these elements share properties so closely must be found in their electronic structures and
the relative energy levels within their atoms.

The following are characteristic properties of transition elements:

variable complex ion coloured catalytic magnetic

oxidation states formation compounds properties properties

To be able to explain these properties, we need to know the electronic configuration of these first row
transition metals. Complete the electronic configurations below using the Aufbau rules of the first 10 transition
elements.

3d 4s
Sc [Ar]

Ti [Ar]

V [Ar]

Cr [Ar]

Mn [Ar]

Fe [Ar]

Co [Ar]

Ni [Ar]

Cu [Ar]

Zn [Ar]

Exceptions to the general patterns in the electron arrangement are:

* Cr: [Ar] 3d5 4s1 instead of [Ar] 3d4 4s2 as the first is the preferred arrangement and appears to be more
stable in terms of energy; the 3d sub-level is half-filled (a half-filled or filled or empty orbital has greater
stability than a partially filled orbital although this does not always apply) which gives a lower total
energy; because the 3d and 4s are so close together they can be considered as degenerate orbitals.
This 3d54s1 only happens in the electronic configuration of Cr atoms.

* Cu: [Ar] 3d10 4s1 instead of [Ar] 3d9 4s2 because filling up of 3d is a more stable arrangement.

Electronic configuration of transition metal ions

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You recall that when filling up orbitals, the 4s orbital is filled before the 3d orbitals. This is because in the
empty atom, the 4s orbital has a lower energy than 3d orbitals. However, once the electrons are actually in
the 4s orbitals, the energy order changes; the 4s electrons repel each other and this increases the 4s energy
level beyond the 3d energy level. When the 3d sublevel is being filled it is at an energy level below 4s.
As a result in all the chemistry of the transition elements, the 4s orbital behaves as the outermost, highest
energy orbital when it has electrons in it. So the reversed order of the 3d and 4s orbitals only applies to
building the atom up in the first place. In all other respects, you treat the 4s electrons as being the outer
electrons.
As the 3d electrons are on a slightly lower energy level than the 4s electrons when the transition metal atoms
ionise, it are the 4s electrons (they are also shielded from the nuclear charge by the 3d electrons) which are
removed first before the 3d electrons.

Complete the table below

species electronic configuration species electronic configuration

Sc3+ Fe2+
Ti4+ Fe3+
V5+ Co2+
Cr3+ Ni2+
Cr6+ Cu+
Mn2+ Cu2+
Mn3+ Zn2+

Variable oxidation states (except zinc). Why? Similar successive ionization energies of 3d and 4s
electrons

● Oxidation state of a transition element in a compound or molecular ion = number of electrons

released/sharing in either covalent (sometimes the bonds formed have a greater covalent character) or
ionic bonds.
● When writing an oxidation state we write the sign first then the number e.g. +3 unlike an ionic charge
which as number first and then the sign e.g. 3+.
● All transition elements, except Sc (+3 only) and Zn (+2 only), have more than one stable oxidation
state.
● Common oxidation state: as first and second ionization energies are very similar in all transition
elements, all first row d-block elements have + 2 as an oxidation state which corresponds with the loss of
the 4s electrons. Exceptions are Cr and Cu that lose the single 4s electron and one 3d electron to have
+2 as their oxidation state. Similar trends occur in other rows of transition metals.
● You should be familiar with the following oxidation states (in brackets are their configurations):

Cu +1 (=[Ar] 3d10 ) +2 (=[Ar] 3d 9)

Cr +3 (=[Ar] 3d3 ) +6 (=[Ar] )
Mn +4 (=[Ar] 3d3 ) +7 (=[Ar] )
Fe +3 (=[Ar] 3d5 ) +2 (=[Ar] 3d6)

● Transition metals have variable oxidation states because the 3d and 4s electrons have similar
successive ionization energies (only a gradual increase) because the five inner d orbitals are at a
similar energy level as the single 4s orbital.
● The only gradual increase in successive ionization energies is because there is less repulsion every time
an electron is removed so electrons are attracted more strongly by the nucleus. However, the decrease in
repulsion is also only gradual.
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One first row d-block element is not considered a transition element

The definition below is a recent development as the part about an atom has been added which now means
that scandium is considered a transition element with its [Ar] 4s23d1 which it was not before this change in the
definition.

A transition element is a d-block element that has an atom with a partially filled d-sub-level or
that forms at least one stable cation that has a partially filled d-sub-level.

As Zn does not have neither an atom or a stable ion, Zn2+, with a partially-filled d-sub-level Zn is not
considered a transition metal. Zinc also does not form any coloured compounds, only has one oxidation
state and has no catalytic activity. Many of these properties also fit scandium but this is now considered a
transition metal a it has an atom with a partially-filled d sub-level.

Formation of complexes or complex ions (result of the high charge density of the metal ion)

A complex or complex ion has a metal ion at its centre around which there are a number of other molecules or
negative ions. A complex is a compound that is formed when a ligand, that has been attracted by the charge
of the transition metal ion, donates an electron pair (= dative bond) into an empty low energy orbital (3d, 4s or
4p) of the metal ion.
These complexes/complex ions are usually formed when transition metals are dissolved in water; or become
hydrated. However, these complexes also form in other circumstances.

When the complex is charged it is called a complex ion; the charge on the ion is delocalised over the entire
complex as indicated by the square brackets.

Transition metals can form complexes because their ions have a high charge density:
o they have quite a large nuclear charge but are relatively small;
● the 3d electrons are not so effective (as 2s or 2p electrons) at shielding the effect of the ionic charge
which really comes from the nucleus.

Molecules like water, ammonia and negative molecular ions can all act as ligands as they have at least one
lone pair.

A ligand = a molecule or negative ion which contains a non-bonding electron pair which it
uses to form a dative bond with the central ion in a complex.

Different types of ligands

Ligands can be classified according to their number of atoms that can donate non-bonding pairs and therefore
the number of coordinate bonds that they can form:
o monodentate ligands can only form 1 coordinate bond as they have only one atom that can donate non-
bonding pair/form coordinate bond. Example are water (only oxygen atom can), ammonia and any halide
ion.
o polydentate ligands can form 2 or more coordinate bonds as they have 2 or more atoms that can donate
non-bonding pairs e.g. EDTA, 1,2-ethanediamine as both molecules have 2 nitrogen atoms in them. EDTA
can make 6 coordinate bonds so one EDTA molecule can make a complex ion with an iron (II) or iron (III)
ion.

Co-ordination number

The number of ligands that are attached to such a metal ion is referred to as the co-ordination number.

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Common co-ordination numbers are:

Cu = 4 Fe = 6 Ag = 2

Examples of common complex ions

[Fe(H2O)6]3+ [Fe(CN)6]3- [CuCl4]2- [Cu(NH3)4]2+ [Ag(NH3)2]+

Shapes of complex ions

Complexes also have shapes which we can predict using the VSEPR theory. The shape depends on the
number of ligands:

● if co-ordination number = 6 then shape = octahedral

● if co-ordination number = 4 then shape = tetrahedral (or square planar = less common)

● if co-ordination number = 2 then shape = linear

Examples of octahedral ions.

Q
Magnetic properties

In terms of magnetic properties (attracted or repelled by an external magnetic field) there are 3 types of
materials:

o Paramagnetic materials are magnetic i.e. they are attracted weakly to a magnetic field.
In the case of the transition metals, atoms or ions that contain unpaired d electrons behave like small
magnets. Because of their spin electrons create a magnetic field that can align itself to an external electric
or magnetic field when exposed to it; unpaired electrons can do this because they can spin in any
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 direction – they create a net magnetic moment. As a result atoms with unpaired d-electrons are weakly
attracted to a magnet. The greater the number of unpaired electrons the more paramagnetic the material.
The alignment is only temporary so they are only magnetic for a short period of time.
Examples of paramagnetic materials in the first row d-block:
o atoms: all apart from Zn.
o ions e.g. in compounds and complexes: e.g. Mg2+ has 5 unpaired electrons, Co2+ (3 unpaired
electrons), Ni2+ (2 unpaired electrons), Fe2+ (unpaired electrons).

o Diamagnetic materials only have paired d-electrons and therefore create a magnetic field opposed or not
aligned to an external field that is why they are weakly repelled by that external field. The paired electrons
cancel out each other’s magnetic field so there is no net magnetic moment in the atom or ion.
Examples of diamagnetic materials: Zn and Zn2+.

o Ferromagnetic materials can be made into permanent magnets as their electron alignment caused by an
external magnet can be made permanent e.g. by heating and cooling it in a magnetic field.
Examples of ferromagnetic materials are iron, cobalt and nickel.

13.2 Coloured complexes

d sub-level splitting

A compound that contains energy levels that are close together could absorb radiation in the visible light
spectrum and therefore display a colour because the colour observed is complementary to the colour
absorbed. This must be the case in d-block metals as their compounds are frequently coloured both in solid
state (hydrated) and in solution.

In the d-block metal ions in complexes in their ground state, the five orbitals in the 3d sub-level have the same
energy (equivalent energy level) but in most of their compounds (usually complexes), these 5 equivalent
orbitals are split in two or three different energy level (non-equivalent energy levels) with some orbitals on
each level.
This splitting of the 3-d sublevel into two or more sets of orbitals is caused by the ligands as the electron
clouds or non-bonding pairs around the ligand repel the electrons in the 3d orbitals of the metal ion. As a
result the ligand electrons push the 3d electrons in the transition metal ion in orbitals closest to them to energy
levels higher than the other orbitals that are not near the ligand. This creates sets of orbitals of different
energy – non-equivalent - and this process is called field-splitting.

d-to-d transition

Although they are different in energy, the two sets of split orbitals are still close together. This allows an
electron in a lower 3d orbital to become excited and absorb radiation (from the visible light spectrum) and be
promoted (=transition) from a lower 3d orbital (low spin) to a higher 3d orbital (high spin). The amount of
energy needed for this d-to-d transition (or the energy difference between the two sets of orbitals)
corresponds to a photon within the visible light spectrum.

The colour shown by the transition metal ion complex is a mixture of the colours or radiation that it transmits
after absorption of the frequencies for transition. The colour observed is a mixture of the colours
complementary to those colours that have been absorbed. You should use a colour wheel to determine
the complementary colour of a colour that has been absorbed.

Therefore for transition metal compounds to form coloured compounds, the transition metals ions must have
partially-filled 3 d orbitals i.e. unpaired electrons.

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The field splitting in a Cu2+ when it forms a complex with water is shown in the diagram below . The symbol
E indicates the difference in energy between the two sets of orbitals. Using Planck’s constant and the
frequencies of the complementary colours you should be able to calculate the amount of energy.

The colour of a transition metal complex

depends on the size of E (or split) in the
diagram to the right which in its turn depends
on:
● The identity of the metal ion as this effects
the nuclear charge which attracts the
ligand; the identity also affects the number
of ligands and the shape of the complex
ions, how strongly ligands are attracted, all
of which affect E. Overall E increases
down a group in the d-block.
● The oxidation state/number of the metal ion
as e.g. the more positive the oxidation
state, the fewer the 3d electrons, the lower
the amount of repulsion caused, the higher
E.

● The identity of the ligand: each ligand has its own effect on the relative energies of the d electrons, e.g.
NH3 has a greater effect than water because nitrogen has a lower electronegativity and therefore
attracts its lone pair less strongly/less closely to the nucleus allowing it to repel more other electrons.
NH3 is considered a stronger ligand than water. The stronger the ligand the more the electrons in the 3d
split sub-level absorb towards the high-energy end of the visible light spectrum. Electronegativity cannot
always be used to explain the difference as Cl- is a stronger ligand than I- as it has a higher charge
density than I- (same ionic charge but greater ionic radius).

Spectrochemical series

The spectrochemical series is a series that ranks various ligands in order of increasing E values (large
splitting). The series is based on experimental evidence. The further up the series the ligand, the more
splitting of it causes, the higher the frequency/lower the wavelength of the radiation needed for a d-to-d
transition.

Example of the effect of a ligand on the colour observed: hexaaquacopper (II) ions have a blue colour. As
ammonia is a stronger ligand it displaces four of the water molecules and converts the complex ions into deep
blue tetraaminediaquacopper (II) ions. This happens because ammonia as a stronger ligand causes greater
repulsion and therefore a greater E. As a result electrons in the tetraaminediaquacopper (II) complex need
to absorb light of a higher energy/frequency to make any d-to-d transitions than in the hexaaquacopper (II)
complex. This means the complementary colours that are observed also have higher frequencies.

Not all d-block compounds are coloured compounds

Compounds containing transition ions with empty d-orbitals (e.g. Sc3+, Ti4+) or full d orbitals (e.g. Zn2+) are
colourless as no transition between split sub-levels or different sets of orbitals can occur (in the case of full
orbitals there are no spaces).

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