2021

TRANSITION METALS
A LEVEL CHEMISTRY

SIR LAYAN
EXTRATERRESTRIAL
CONTENT
COMPILED AND EDITED BY MR MAGABA 0774 372 589
TRANSITION ELEMENTS I
• A transition element is a d-block element that forms one or more stable ions with an incomplete d
subshell.
• We do not define Sc and Zn as transition elements.
• Scandium forms only one ion (Sc3+) and this has no electrons in its 3d subshell – the electronic
configuration of Sc3+is (Ar) 3d04s0.
• Zinc forms only one ion (Zn2+and this has a complete 3d subshell –the electronic configuration of
Zn2+is (Ar) 3d104s0.

Electronic configurations

The d Orbitals
• The 3d subshell has got 5 degenerate orbitals, designated dxy, dxz, dzy, dz2 and dx2- y2
• Each orbital carries a maximum of two electrons, so the d sub shell has a maximum capacity of
10 electrons. This maximum occupancy is found at copper and zinc.
• The first three orbitals (dxy, dxz, dzy) each have four lobes that are aligned between the axis, for
example, the dxy has lobes oriented between the x and y axis.

• The remaining two d orbitals form their own set (in terms of geometry) in that they have lobes
that are directed along the axis, as shown below.

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 The dz² and dx2 – y2 orbitals respectively have lobes that are directed along the axes

Physical Properties of the Transition Elements

a) Generally small atomic radii.
b) High Melting and Boiling Points
c) High Electrical Conductivities
d) High Densities
e) they are hard and rigid, and so are useful as construction materials

Generally small atomic radii

• The large number of protons in the nucleus results in shells being attracted strongly towards the
nucleus. This causes the atoms to shrink.

Poor shielding effect of the d orbitals

• Because of their shape, the d orbitals poorly shield the outer 4s shell from the nucleus. As a
result, the outer shell feels a strong attraction by the nucleus, to which it is attracted, resulting in
shrinking of size.

Trend in atomic radii across the first-row transition elements

• The decrease in atomic radii does occur but not as rapidly as happens in the non-transition periods
such as Period 3.
• This slow and gradual decrease in atomic size is due to the fact that across the row, electrons
enter a penultimate (underlying) 3d shell, thus shielding the outer 4s sub shell from feeling the
full attractive influence of the nucleus.

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High Densities
• Density is given by mass/Volume.
• The high densities of the transition metals are a direct consequence of the small atomic radii and
heavy nucleus (large number of protons and neutrons) i.e. the atoms have large masses and yet
their size is small.
• The atoms of transition elements are quite small compared to their mass. The effect of small
atomic radii (volume) and large mass is to increase density, that is, each atom has a large mass
packed in a small volume.

Melting and Boiling Points

• Melting or boiling a metal requires the breaking of metallic bonds. The melting point or boiling
point of a metal is therefore a measure of the strength of these bonds.
• Transition metals have high melting points and boiling points compared to s-block elements due
to stronger metallic bonds compared to those in s-block metals.
The strength of these bonds can be explained in terms of:
a) The large charge that remains on the metal atoms after they have contributed their 4s and 3d
electrons into the pool of delocalization.
b) the large number of delocalized electrons in the metal lattice. Remember that these electrons
come from both the 4s and the 3d sub shells of the atoms.
These two factors result in very strong electrostatic attractions between the positive metal atoms and the
sea of delocalized electrons.

• The large nuclear charge of the atoms and the protons in the nucleus also have an attraction for
the delocalized electrons. This attraction is strong in the transition metals due to the large number
of protons in their nuclei.
• We expect melting and boiling points of the transition elements to increase across the period in
response to increasing nuclear charge and decreasing atomic radii. A clear trend in melting points
is not observed because the metals tend to have different crystal structures.
• When melting and boiling points are plotted against proton number, both graphs have two
maxima, with an immediate minimum at manganese. The minima suggest that the half-filled
subshell of 3d electrons is not available for metallic bonding.

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Transition elements are excellent conductors of electricity
• Conductivity in a metal is a result of delocalized electrons.
• The greater the number of electrons in the delocalized sea, the greater the conductivity.
• In transition elements, the 4s and the 3d shells, being very close in energy, act as if they are one
shell.
• Electrons are thus lost from both the 4s and the 3d sub shells and contributed to a common pool.
There are therefore a large number of electrons in the delocalized sea to conduct electric current.
• On the other hand, even though a transition metal has a large number of delocalized electrons,
mobility of these electrons is restricted by attraction to the large positive charge on the metal
atoms and the large number of protons in the nucleus of the atom.

Ionisation Energy
• Ionization energy measures how strongly valence electrons are held to the atom. In transition
elements, the outermost electrons are firmly held for two reasons.
1. The atoms are small, so the valence electrons are close to the nucleus and they feel a
powerful attraction by protons.
2. The charge density in transition metal atoms is high. The large number of protons in the
nucleus attracts the valence electrons strongly.
• Transition elements have relatively high ionization energies which change only gradually across
the period due to the increase attraction for the valence electrons.
• The first ionisation energy of transition metals is almost constant as we move across the first row
of the transition elements.
• This is because the electrons are being removed from the same subshell i.e. 4s subshell, therefore
almost the same amount of energy will be required to the electrons.

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Chemical Properties of Transition Metals
a) They exhibit variable oxidation states in their compounds.
b) They tend to form complex compounds.
c) They tend to form coloured compounds.
d) Their compounds show catalytic activity.

Variable Oxidation States

• Transition metals have a variable oxidation states due to the close proximity of the 3d and 4s
subshell.
• As a result, there is a very small difference in energy level between the 3d and 4s subshell.
• Thus, the amount of energy required to remove electrons from these subshells is almost the same.
• Different oxidation states would be formed corresponding to the total number of electrons lost
from the 4s and 3d sub-shells.
• In all transition compounds, except copper, the +1 state is very unstable. To form the +1 state,
one electron would have to be lost from the 4s subshell. This would leave a single electron in the
valence shell. Such a configuration is very unstable.
• Electrons are always lost first from the 4s subshell, because it is the valence shell.
• Only unpaired d-electrons may be lost during reactions because paired electrons are more stable.
• The range of possible oxidation states therefore decreases when one or more d orbitals contain
paired electrons.

• The lower oxidation states form aqua complexes with water, for example, the species usually
abbreviated as Cu²⁺(aq) is in fact the hexaaqua complex, [Cu (H2O)6]2+
• The higher oxidation states, from the +4 and upwards, cannot exist as hexaaqua complexes. These
ions would have a charge density so high that they would immediately polarize water molecules,
releasing hydrogen ions and bonding with oxygen to form anions.

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Transition Metals Complex
• A complex compound is one which is made up of electron rich species known as ligands that are
bonded to a central metal cation through dative bonds.
• A ligand is a specie with at least a lone pair of electrons which can be used to form dative bonds
with a transition metal.
• An example of a complex ion is [Co(NH3)6]3+, in which ammonia ligands form dative covalent
bonds to a central Co3+ ion.

• Transition metals have partially filled 3d subshells which can accommodate the lone pair of
electrons from ligands.
• When the ligands surround the transition element a dative bond is then formed resulting in the
formation of a complex.
Transition metals form stable complex ions because:
1. Their ions are small and they have a high charge density.
2. They have 3d orbitals of low energy that accommodate electrons donated by ligands.
• A few non-transition metals can also form complex ions
• The prerequisite for complex ion formation is availability of vacancies to accommodate extra
electron density, or simply the ability to attract and form stable compounds with ligands.

Ligands
• A ligand is an electron rich species, either neutral or negatively charged, and carrying one or
more lone pairs of electrons which can be used to form one or more dative bonds to a central
metal cation.

Classification of Ligands
• Ligands can be classified in terms of the number of dative bonds they can form, per molecule of
the ligand, to the central metal cation.

Different Types of Ligands

1. Monodentate
2. Bidentate
3. Tridentate
4. Polydentate

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Monodentate Ligand
• These are species which form one dative bond with a transition element e.g. H2O, Cl-, NH3, OH-,
F-, CO, CN-.
• Examples of complexes that contain such ligands are [CuCl4]2- yellow, [Co(NH3)6]3+ golden
brown ,[ Fe(H2O)6]2+ light green.

Bidentate Ligand
• Bidentate literally means ‘two toothed’.
• These are species which form two dative bonds with a transition element.
• Bidentate ligands form more stable complexes than monodentate ligands because of their
chelating effect.
• A chelating agent is a ligand which forms a complex which is so stable that further substitution of
the ligand by monodentate ligands is unlikely.
Examples of Bidentate

Tridentate Ligand
• These are species which form three dative bonds with a transition element.
• Tridentate ligands form more stable complexes than bidentate ligands because of their chelating
effect e.g. diethylenetriamine

Polydentate Ligand
• A polydentate ligand can form more than two dative bonds with the central metal ion.
Examples of Polydentate Ligands

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 • The coordination number of EDTA is 6 and the overall charge is -4.
• Polydentate ligands form more stable complexes than mono, bi and tridentate ligands because of
their chelating effect.
• ETDA is a very strong ligand and it can easily displace other ligands.

Charge on the complexes

• Complexes can be positively charged, negatively charged, or they can be neutral.
• The net charge on the complex depends on the charge on the ligands and the metal cation.

Consider the hexa-aqua complex [Cu(H₂O)6] ²⁺

• It contains a +2-metal cation and 6 neutral water ligands.
• The net charge on the complex is equal to charge on the metal ion, since the ligands do not
neutralize the positive charge carried by the cation.

Consider the complex CuCl4x

• The net charge x on the complex is determined by adding the total negative charge from the
ligands to the positive charge on the metal cation.

• The complex therefore has the formula CuCl42-

• Neutral complexes are usually insoluble in water.

The co-ordination number of a complex

• The co-ordination number of a complex refers to the total number of dative bonds around the
central metal ion.
• The smallest possible co-ordination number in a complex is 2, and this gives rise to linear
complexes, for example the diamine silver (I) ion, [Ag (NH3)2]2+.
• The number of dative bonds (bond pairs) around the central metal ion determines the shape of the
complex.
• This is a direct application of the VSEPR method for the determination of molecular geometries.
• In the diamine silver (I) complex shown below, there are two bond pairs around the central Ag+
ion. These bond pairs must be spaced out at 1800 relative to each other.
• The complex is therefore linear.

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Coordination number 4
• A co-ordination number of four gives rise to tetrahedral or square planar complexes e.g.
[Pt(NH3)2Cl2] and [CuCl4]2-

Tetrahedral
• In tetrahedral molecular geometry, a central atom is located at the centre of 4 substituents, which
forms an angle of 109.50

• Tetrahedral geometry is common for complexes where the metal has 3d0 or 3d10 subshells.
• Tetrahedral complexes have dx2-y2 and dz2 orbitals are equally low in energy because they are
between the ligand axis and experience little repulsion.

Square Planar
• In square planar molecular geometry, a central atom is surrounded by constituent atoms, which
forms the corners of a square on the same plane and an angle of 900.

• Note that [Pt(NH3)2Cl2] is a mixed ligand complex. There are two NH3 ligands and two Cl-
ligands.
• The square planar is prevalent for transition metals with 3d8 subshell.

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 • Square planar complexes can be derived from octahedral complexes yet the dx2-y2 level is the
most destabilised and is left unfilled.

Coordination number 6
• This gives rise to an octahedral geometry (bond angle, 900). Examples of such complexes include
[Cu(EDTA)]2-, [Pt(C2O4)3]3-and [Cu(en)3]2+ where en = ethanediamine.
• Note that each ligand in the complex is bidentate so there is a total of 6 dative bonds around the
central metal ion.

• In octahedral complexes, the splitting results in the dxy, dxz and dzy occupying the lower energy
level, whilst the dz2 and the dx2- y2 occupies the higher energy level.

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Magnetism in complexes of transition elements
Different types of magnetism
1. Ferromagnetism
2. Paramagnetism
3. Diamagnetism

Ferromagnetism
• This property is exhibited by transition elements which form permanent magnets.
• Ferro magnetic compounds are strongly attracted in the magnetic field e.g. Iron, cobalt and
Nickel

Paramagnetism
• Paramagnetism is the observation that some metals are weakly attracted in a magnetic field.
• The opposite of paramagnetism is diamagnetism, in which a substance is slightly repelled by the
magnetic field of a magnet.
• Paramagnetism in transition metals is a result of unpaired electrons in the d orbitals.
• This explains why copper and zinc are diamagnetic. Their d-electrons are all paired.

Diamagnetism
• Diamagnetic complexes are weakly repelled in magnetic field.
• This is exhibited by complexes with paired electrons or no electrons at all in 3d orbital.
• This explains why copper and zinc are diamagnetic. Their d-electrons are all paired.
• Non-transition metals such as magnesium tend to be diamagnetic.

Predicting Magnetic properties of a complex

• When a transition metal forms a compound, the 3d orbitals split in energy
• Most bidentate and polydentate ligands are strong ligands which results in a large separation
between the lower and the higher d orbital sets and electrons enter only the lower set of the d
orbitals because a large amount of energy would be required to place an electron in the higher
orbital set. This situation allows for the least number of unpaired electrons and is known as low
spin.
• If the ligands are weak, the energy difference between the two energy levels is small. Electrons
therefore first enter singly in all the orbitals (both lower and higher), thereafter pairing may take
place, starting with the lower set of orbitals. This situation allows for the greatest number of
unpaired electrons and is known as high spin.

Steps to predict the magnetic properties of complex compounds

i. First determine the oxidation number (charge) on the central metal ion, as this tells us how many
electrons were lost by the metal in forming the complex.
ii. Consider the strength of ligand. Ligands are classified as strong field or weak fields ligands based
on the spectrochemical series.

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Strength of the Ammonia Ligand

• It depends on the central atom, coordination number and oxidation state.

• If the coordination is 6 (Octahedral) and an oxidation state of +2, ammonia acts as a weak field
ligand
• If the coordination number is 4 (Tetrahedral) ammonia acts as a weak field ligand.
• If the coordination number is 6 and the oxidation state is +3 then ammonia acts as a strong field
ligand.
Question
Work out the number of unpaired electrons in each of the following complexes. Hence arrange the
complexes in order of increasing paramagnetism and state weather there is low or high spin.
(a) [Mn(C2O4)3]3-
(b) CuCl₄²⁻
(c) [Ni(Cl)4]²-
(d) Co[(NH3)6] 3+
(e) [Ni(NH₃)₆] ²⁺
(f) [Co(NH3)6]2+
(g) [Ni(CN4)]2-

Stability of complexes
• Stability of a complex depends on the strength of the dative bonds which the ligands make to the
central ion.

The strength of these bonds depends on:

a) the nature of the ligand.
b) charge on the ligand.
c) the charge on the central transition metal ion.

Stability constants, Kstab

• Different ligands have different affinities for the central metal cation.
• Stability constants are equilibrium constants that give a measure of the ease with which a
particular ligand can replace water from a specified aqua complex.
• A very large Kstab value indicates that the ligand easily replaces water ligands in the specified
complex, to form a more stable complex.
• Stability constants are often given on a log10 scale. When expressed on a log10 scale, they have
no units.
• Stability constants are true equilibrium constants, so they are affected by temperature. The values
are therefore quoted at 298 K.
[𝑃𝑟𝑜𝑑𝑢𝑐𝑡𝑠]
Kstab = [𝑅𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠]

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Consider the equation below

• Water does not appear in the equilibrium expression because it is in such a large excess that its
concentration is regarded as being constant.
• the units for the stability constant are worked out in the same way as for the units of Kc.
Consider the situation below
Deduce the Kstab expression for the following stepwise reaction below

[Cu(H2O)6]2+(aq) + 2OH- [Cu(OH-)2(H2O)4] (s) + 2H2O

[Cu(OH-)2(H2O)4] (s) + 4NH3 [Cu(NH3)4(H2O)2]2+ + 2OH- + 2H2O
Solution
Kstab = K1 × K2
Kstab = [Cu(OH)2] × [Cu(NH3)4)]2+ [OH-]2
[Cu]2+ [OH-]2 [Cu(OH-)2] [NH3]4
= [Cu(NH3)4)]2+
[Cu]2+ [NH3]4

• Complexes containing CN ligands usually have very large stability constants. In most cases, CN-
ligands act as strong field ligands, that is, they form very strong dative bonds to the central metal
ion. The resulting complexes are very stable.
• Bidentate and hexadentate ligands form complexes that have large stability constants. Such
ligands, for example en and EDTA can easily replace water ligands in a large number of
complexes.

Colour in Complex
• The neutral transition atom has degenerate (same energy) 3d orbitals.
• During compound formation, the d orbitals split in energy, forming a higher set and a lower set of
orbitals. This separation in energy is a result of the electrostatic repulsion which the d orbitals
experience from the approaching ligands.

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 • When light strikes the transition compound, some wavelengths from the visible spectrum are
absorbed.
• The absorbed energy is used to promote electrons from the lower set of orbitals to the higher set.
This is referred to as d-d transitions.
• The colour observed is complimentary to the wavelengths absorbed, for example, red is
complimentary to blue.
• A necessary condition for a complex to be coloured is the presence of vacancies (unpaired
electrons or vacant orbitals) in the higher set of orbitals.
• These vacancies can accommodate electrons that are promoted from the lower set of orbitals by
absorption of light energy.

Charge Transfer
• If the complexes have an empty 3d subshells, as a result when the ligand approaches the
transition element, orbital splitting will not occur. Instead the movement of electrons from the
ligand to the transition element requires energy.
• The energy is absorbed from the visible spectrum and the colour observed is a result of the
compliment of the remaining colours
• If a substance contains bonds which are on the border line between ionic and covalent, it may
change from one type of bonding to another by absorbing visible light.
• This effect is shown by some coloured solids e.g. orange PbO, yellow AgI and black CuO

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Factors that affect colour of complexes
• Identity of the metal cation
• Identity of the Ligand
• The oxidation state of the metal cation
• Geometry of the complex

Identity of the metal cation

Consider [Mn(H2O)]2+ and [Fe(H2O)]3+

• The metal cations are isoelectronic (have the same number of electrons) i.e. [Ar]3d5
• Manganese have 25 protons and iron has 26 protons. An increase in number of protons results in
an increase in the interaction between the approaching ligand and the metal cation hence more
repulsion resulting in a bigger split between the lower set and the higher set.
• Therefore, the energy absorbed by Mn2+ corresponds to a green colour and the complimentary
colour of Mn2+ is pink and the energy absorbed by Fe3+ corresponds to a green colour and the
complimentary colour of Fe3+ is orange

Identity of the Ligand

• The stronger the ligand the stronger the interaction between the ligand and the metal cation
hence more repulsion. This results in a bigger split and more energy is absorbed to promote
an electron from lower energy set to a higher energy set.

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Oxidation State of the metal cation
• The lower the oxidation state the less interaction between the ligand and the metal cation.
This results in a smaller split and less energy is absorbed to promote an electron from lower
energy set to a higher energy set.
• An increase in oxidation state results in stronger interaction between the ligand and the metal
cation. This results in a bigger split and more energy is absorbed to promote an electron from
lower energy set to a higher energy set.

Catalysis by transition elements and their compounds

• Transition metals and their compounds are good catalysts because of the presence of partially
filled d orbitals and the ability of the transition element to change oxidation state during the
catalysis.

Heterogeneous catalysis
• Heterogeneous catalysis is when the catalyst and the reactants are in different phases e.g. when
the catalyst is solid and the reactants are gaseous.
• The partially filled d orbitals in the transition metal are used to temporarily accommodate electron
density from the reactants during the reaction.
• The chemical adsorption (Chemisorption) of reactant molecules onto the surface of the catalyst
weakens their bonds, thus lowering the activation energy of the reaction.
• The adsorption process provides a large surface area and brings the reactants molecules together
so that bonds can form.
• Transition elements such as nickel are particularly good at chemisorbing hydrogen gas.

Iron in the Haber process

• The reaction is catalysed by iron. The catalyst works by allowing hydrogen and nitrogen
molecules to come close together on the surface of the iron.
Adsorption

The reactant molecules are chemically adsorbed onto the surface of the iron. The bonds formed between
the reactant molecules and the iron are:
i. strong enough to weaken the covalent bonds within the nitrogen and hydrogen molecules so the
atoms can react with each other
ii. weak enough to break and allow the products to leave the surface.

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Reaction

• the adsorbed nitrogen and hydrogen atoms react on the surface of the iron to form ammonia.
Desorption

• the bonds between the ammonia and the surface of the iron weaken and are eventually broken.
Diffusion

• ammonia diffuses away from the surface of the iron.

Homogenous Catalysis
• It occurs when the catalyst is in the same phase as the reaction mixture.
• Homogeneous catalysis often involves changes in oxidation number of the ions involved in
catalysis.
• Transition elements have the ability to change oxidation state during the catalysis.

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The iodine–peroxodisulphate reaction
• Peroxodisulfate (persulfate) ions, S2O82–, oxidise iodide ions to iodine. This reaction is very slow.

• The peroxodisulfate and iodide ions both have a negative charge. In order to collide and react,
these ions need considerable energy to overcome the repulsive forces when like charges approach
each other.
• Fe3+(aq) ions catalyse this reaction. The catalysis involves two redox reactions.
Reaction 1

• reduction of Fe3+ ions to Fe2+ ions by I– ions.

Reaction 2

• oxidation of Fe2+ ions back to Fe3+ by S2O82– ions

• In both reactions 1 and 2, positively charged iron ions react with negatively charged ions.

Isomerism in Transition Elements

Transition metals exhibit different types of isomerism and these include:
a) Structural
b) Conformational
c) Geometrical
d) Optical
e) Ionisation

Structural - Positional
• This exists in complexes with two or more different ligands.
• In this type of isomerism ligands are molecules will be occupying different positions in the
isomers.

Structural - Ionisation isomerism

• Ionisation isomers occur when a ligand that is bound to the metal center exchanges places with
the anion or neutral molecule that was originally outside the coordination complex
• The geometry of the central metal ion and the identity of other ligands are identical.

[Co(NH3)5Cl]Br- and [Co(NH3)5Br]Cl-

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Structural - Hydrated Isomerism
• It is a specific kind of ionisation isomerism which occurs when a hydrated salt can exist in
different forms. typical example is exhibited by the salt CrCl3. 6H2O(s).
• There are three different solid forms that share this molecular formula and it is possible to
distinguish between the three solid isomers by dissolving them separately in water and then
determine the amount of free chloride ions in each solution by adding AgNO3 (aq)
• The isomers differ in how many chloride ions are directly bonded to the central metal (acting as
ligands). The chloride ions that are bonded to the metal ion via covalent dative bonds are said to
be part of the co-ordination sphere.
• Chloride ions outside the co-ordination sphere act as counter - ions to neutralize the positive
charge on the co-ordination complex. In solution, these ions are dispersed in water and so can be
precipitated as AgCl when aqueous AgNO3 is added.
Isomer Colour in Effect of Remarks
solution adding
AgNO3(aq)
[Cr (H2O)6]3+ .3CI- Blue-Violet All chloride The three chloride ions are outside
ions are the coordination sphere i.e. they
precipitated as are not covalently bonded to the
AgCl central metal ion. The ions are
therefore free in solution and can
be precipitated by Ag+ ions
[Cr (H2O)5CI]2+ .2Cl-. (H2O) Green Only 2/3 of Two of the three chloride ions are
the chloride outside the coordination sphere i.e.
ions are they are not covalently bonded to
precipitated the central metal ion. The ions are
therefore free in solution and can
be precipitated by Ag+ ions
[Cr (H2O)4CI2]1+. Cl- .2(H2O) Darker Only 1/3 of One of the three chloride ions is
Green the chloride outside the coordination sphere i.e.
ions are it is not covalently bonded to the
precipitated central metal ion. The ion is
therefore free in solution and can
be precipitated by Ag+ ions

Practice Question on Ionisation isomerism

A and B are compounds of formula CrCl3. 6H2O. In an aqueous solution containing 0.02moles of A
required 25cm3 of 0.08moldm-3 of AgNO3. 0.02moles of B required 50cm3 of 0.08moldm-3 AgNO3
a) Suggest the structural formula of A and B.
b) Draw the diagrams to show isomers of A.
Solution
Number of moles A = 0.02moles
Number of moles (Ag+) = 0.025dm3 × 0.08mol/dm3 = 0.02moles

Ag+ + Cl- AgCl

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Using the equation, the number of moles of Ag+ = n(Cl-). Therefore, the actual number of A is 0.02moles
and 1 mole of Cl- was obtained from the compound.
A = [CrCl2 (H2O)4 ] Cl-.2H2O
Two of the chloride ions are directly attached to the metal cation with strong covalent dative bonds. These
ions are not available in solution to react with Ag+
Considering Compound B
Number of moles (Ag+) = 0.05dm3 × 0.08mol/dm3 = 0.04moles

Ag+ + Cl- AgCl

Using the equation, the number of moles of Ag+ = n(Cl-)
The number of moles Cl- = 0.04moles
The number of moles of B = 0.02moles
Ratio
B : Cl- = 1: 2
Therefore, 2 moles of Cl- was obtained from compound B
B= [CrCl(H2O)5 ] 2Cl-.H2O
A and B are ionisation/hydrate isomers

Structural - Linkage Isomerism

• It occurs with ambidentate ligands.
• These are ligands which are capable of coordinating in more than one way.

[Co(ONO)(NH3)5]Cl- and [Co(NO2)(NH3)5]Cl-

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Conformational
• This exist in some complexes with only 4 ligands resulting in the formation of a tetrahedral shape
and square planar.
• Thus the complex NiCl2(R3P)2 (where R3P is Trialkyl phosphine) can exists not only in a green,
paramagnetic tetrahedral form ,but also in a brown ,diamagnetic square planar form.

R3P: :Cl R3P:

Ni Ni

Cl: :R3P R3P: :Cl

:Cl

Geometric Isomerism
• This occurs in octahedral complexes of the general formula MA4B2 or MX2Y2 where
❖ M is the central metal
❖ A, B are monodentate ligands
❖ X are bidentate ligands and Y are monodentate ligands
• The complex [Cr (NH3)4Cl2]1+ can be used to illustrate geometric isomerism in an octahedral
complex.

• The complex Ni(en)2(H2O)2 can be used to illustrate geometric isomerism in an octahedral

complex.

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 • It also occurs in square planar complexes of the general formula MA2B2.

• In the trans isomer, similar ligands occupy positions which are on opposite sides of the central
metal ion.
• In the cis isomer, similar ligands are on the same side of the central metal ion.
Properties of Geometric isomers
▪ Cis-trans isomers usually have different colours.
• The isomers also differ in polarity. The trans isomer is non - polar because it has equal dipole
moments that operate in opposite directions.
• The dipole moments therefore cancel out, so that the molecule is overally non - polar. The cis
isomer is polar.

Optical isomerism
• This occurs in octahedral complexes which contain at least two bidentate ligands.
• Optical isomers lack a centre of symmetry and so their mirror images are non-superimposable.
Consider the octahedral complex formed between Ni2+ and ethanediamine

• The three ethanediamine ions can bond to the metal ion in two different ways, giving rise to two
stereoisomers that are mirror images of each other, as shown in Figure below

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Consider the octahedral complex formed between Co+, ethanediamine Br-

Questions on Transition Elements 1

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INDIVIDUAL TRANSITION ELEMENTS II
Major Objectives when studying individual transition metals
1. The Common oxidation states
2. Common oxidation states associated with given oxidation states
3. Colour of the complexes
4. Most stable oxidation state
5. The unique chemistry of a transition element
6. Reactions of an element with bases (NaOH and NH3), acids
7. Uses of Transition metals.

Vanadium Chemistry
Atomic number: Z= 23
Configuration: [Ar] 3d³4s²
Possible oxidation states in compounds: +2, +3, +4 and +5
Most stable oxidation state: + 4
Magnetism: all oxidation states except +5 are paramagnetic
Common Oxidation States Common Complexes Colour of Complexes
+2 V2+ / [V (H2O)6 ]2+ Violet

+3 V3+ / [V (H2O)6]3+ Green

+4 VO2+ / [VO (H2O)5]2+ Blue

+5 VO2+ / [VO2 (H2O)5] + Yellow

VO3- / [VO3(H2O)3]-

Unique Chemistry of Vanadium

Reduction Reaction
• Vanadium complexes with higher with higher oxidation states e.g. +5 oxidation state can undergo
a stepwise reduction process in the presence of a suitable reducing agent.
• During the reduction reaction, the reduction occurs in steps i.e. from +5 oxidation state to the +4-
oxidation state, from the +4 oxidation state to +3 oxidation state, from +3 oxidation state to +2
state.’
Question
1. Using the data booklet explain what is going to happen when a salt of NH4VO3 is dissolved in
acidic solution and shaken with excess granulated zinc.

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Solution
Reduction from +5 to +4 oxidation state

VO3- +4H+ + e VO2+ + 2H2O (+1.00)

Zn Zn2+ + 2e (+0.76)
2VO3- + Zn + 8H+ 2VO2+ + Zn2+ + 4H2O (+1.76)
• As the reaction progresses, an immediate lime green colour is observed which is a mixture of
VO3- and VO2+.
• Colour changes from yellow to blue
Reduction from +4 to +3 oxidation state

VO2+ +2H+ + e V3+ + H2O (+0.34)

Zn Zn2+ + 2e (+0.76)
2VO2+ + Zn + 4H+ 2V3+ + Zn2+ + 4H2O (+1.10)
▪ Colour changes from blue to green
Reduction from the +3 to +2

V3+ + e- V2+ (-0.26)

Zn Zn2+ + 2e (+0.76)
2V3+ + Zn 2V2+ + Zn2+ (+0.50)
• Colour changes from green to violet
• As the reactions above are occurring colour changes are due to changes in oxidation states
i.e.VO3- to VO2+
• The vanadic ion, VO₂⁺, can be prepared from solid ammonium metavanadate, NH₄VO₃.
• In water, this solid dissolve to give the vanadate ion, VO₃⁻, in which vanadium has the +5
oxidation state.
• Upon addition of an acid, the vanadate ion is converted to the vanadic ion.

VO3- (aq) + 2H+ (aq) VO2+ (aq) + H2O (l)

Reaction with acids

• Vanadium metal is prone to attack by dilute acids, forming the purple (II) salt.
• The +2 salt undergoes further oxidation by the acid to form the +3 salt.
• This shows that the +3 state is more stable than the +2 state.

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Use the Data Booklet to verify the following outcomes

i. V(s) + 2H+ (aq) V2+ (aq) + H2 (g) Eθ cell = +1.20

ii. V(s) + 2H+ (aq) V (aq) + H2 (g) Eθ cell = +0.26
3+

iii. V2+(aq) + 2H+(aq) V3+ (aq) + H2 (g) Eθ cell = +0.26

• Vanadium can also be attacked by a mixture of oxygen and water to form vanadium (II) in the
form of V(OH)2 (s), which undergoes further oxidation in air to form V(OH)3.

2V(s) + O2 (g) + 2H2O (l) 2V2+ (aq) + 4OH- (aq)

• Reactions of Vanadium metal might not be observed in practice because of the presence of a
tough and impermeable surface layer of vanadium (III) oxide, V2O3, which protects the metal
from chemical agents.
• Vanadium is therefore rendered kinetically stable by the superficial oxide layer.
• It is resistant to attack by oxygen, water and dilute acids.

Uses of vanadium and its compounds

• Vanadium is added to steel to make a very strong alloy which is also resistant to corrosion.
• Vanadium improves the strength of steels by reacting with carbon present in the steel, forming
vanadium carbide, which is a very strong substance
• Vanadium pentoxide is used as a catalyst in the contact process for the manufacture of sulphuric
acid.

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Chromium
Atomic number: 24
Configuration: [Ar] 3d54s1
Possible oxidation states in compounds: +2, +3, +4, and +6
Stable oxidation states: +3 and +6
Most Stable Oxidation State: +3
Paramagnetism: all oxidation states are paramagnetic except Cr(VI)

The complexes of chromium are usually octahedral

Common Oxidation States Common Complexes Colour of Complex
+2 Cr2+ or [Cr(H2 O)]2+ Blue
+3 Cr3+ or [Cr(H2O)]3+ Violet
+6 CrO42- Yellow
+6 Cr2O72- Orange

The Unique Chemistry of Chromium

Higher Oxidation states of chromium (+4 and +6)
• The dichromate and chromate ions are well known species in which chromium has an oxidation
state of +6.
• In the lab, these ions can be obtained from the crystalline salts potassium dichromate (orange) and
sodium chromate (yellow)
• High oxidation states of a transition metal (+4 and higher) cannot exist as simple (aqua) ions in
solution. Having a high charge density, such ions would easily undergo hydrolysis and extract the
oxygen atoms from water, forming ions that contain oxygen (oxo anions).

Interconversion of the +6 oxidation state

• In aqueous solution, the oxo anions can be interconverted by changing pH.

Effect of basic environment

• CrO42- is more stable in basic environment.
• Cr2O72- is unstable in a basic environment.
• The dichromate ion (Cr2O72-) is orange in neutral aqueous solution. Upon addition of a strong
alkali such as OH-, the solution turns yellow due to the conversion of dichromate to chromate
ions.
Cr2O72- (aq) + 2OH- (aq) 2CrO42- (aq) + H2O (l)

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Effect of acidic environment
• Cr2O72- is more stable in an acidic environment.
• CrO42- is unstable in acidic environment.
• Therefore, the yellow chromate can be converted back to the orange dichromate by adding a
strong acid.
2CrO42- (aq) + 2H+ (aq) Cr2O72- (aq) + H2O (l)
• Note that reactions above are neutralization reactions not redox i.e. dichromate acts as an acid and
chromate acts as a base.

Oxidising ability of Higher Oxidation States

• The Cr2O72- and CrO42- are highly oxidising.
• Transition metals with higher oxidation states have a tendency of accepting electrons forming
more stable complexes with lower oxidation states.
• High oxidising abilities of complexes with high oxidation states is shown by large positive Eθ
value.

Cr2O72-+ 14H++ 6e- 2Cr3+ + 7H2O (Eθ = +1.33V)

• Use relevant equations from the Data Booklet to construct a balanced equation for the reaction
between potassium dichromate and FeSO4. Calculate the cell potential of the reaction.
Consider Half Equation of Cr2O72- and Fe2+

Cr2O72-+ 14H++ 6e- 2Cr3+ + 7H2O (Eθ = +1.33V) …………1

Fe3+ + e- Fe2+ (Eθ = +0.77V) ………....2

Net Overall equation

Cr2O72- + 6Fe2+ +14H+ 2Cr3+ + 6Fe3+ + 7H2O + (Eθ = +0.56V)

Reduction of Higher oxidation states

• Dichromate ions can also be reduced to Cr3+ by acidified hydrogen peroxide.
When you choose the relevant half equations from the data booklet, make sure that:
i. the half equation involving hydrogen peroxide has an Eθ value which is less than that of
dichromate (+1.33V). This allows dichromate to act as an oxidizing agent (more positive Eθ) and
hydrogen peroxide to act as a reducing agent.
ii. the half equation you select for hydrogen peroxide contains hydrogen ions. This is because
hydrogen peroxide is a reducing agent in an acidic medium (In an alkaline medium it is an
oxidising agent).

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 Cr2O72-+ 14H++ 6e- 2Cr3+ + 7H2O (Eθ = +1.33V) …………1

O2 + 2H+ + 2e H2O2 (Eθ =+0.68) …………....2

Net Overall equation:

Cr2O72- (aq) + 8H+ (aq) + 3H2O2 (aq) 2Cr3+(aq) + 7H2O (l) + 3O2 (g) (Eθ cell = +0.65V)
Observations

• the orange colour of dichromate changes to the green colour of Cr3+.

• bubbles of oxygen gas are liberated.

The +3 oxidation state

• The +2 and +3 oxidation states of a transition metal ions exist as simple aqua ions in water.
• However, due to their high charge density, the +3 ions undergo hydrolysis, resulting in the
formation of an acidic solution.

Acidic Nature of +3 oxidation state

• Dative covalent bonds are established between water molecules (ligands) and Cr3+ ions, resulting
in the formation of an octahedral hexa-aqua complex, [Cr(H2O)6]3+.
• Due to the large density of the Cr3+ ion, a water ligand undergoes hydrolysis, releasing H+ and
OH- ions. The hydroxide ion, being a strong ligand, immediately forms a covalent dative bond to
the metal ion.

[Cr(H2O)6]3+(aq) [Cr[(H2O)5(OH)]2+(aq) + H+(aq)

Redox Reaction of Cr3+

Colour of Cr3+

• The green colour of Cr3+ is usually observed when the ion is formed in a chemical reaction.
• When the salt is dissolved in water, the violet complex [Cr(H2O)6]3+ is formed.
• During chemical reactions water ligands are replaced by negative ions from the salt and this
results in a change of colour from violet to green.

Oxidation of Cr3+ to (CrO42- / Cr2O72-)

• Lower oxidation states of the transition metals tend to act as reducing agents, that is, in redox
reactions, they tend to lose electrons and are thus oxidized to higher oxidation states.
Consider Cr3+ and H2O2 in Acidic Condition

Cr2O72-+ 14H++ 6e- 2Cr3+ + 7H2O (Eθ = +1.33V) …………1

H2O2 + 2H+ + 2e– 2H2O (Eθ = +1.77V) …………2

Net Overall Equation

2Cr3+(aq) + 3H2O2 (aq) + H2O (l) Cr2O72- (aq) + 8H+ (aq) (Eθ = +0.44V)

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Reaction of the most stable state (Cr3+) with bases
Precipitation by NaOH (aq) and NH3 (aq)
• When dilute NaOH (aq) is added gradually to Cr3+ (aq), a green precipitate is formed which
dissolves in excess NaOH to form a colourless solution.
• There are two types of reactions involved.
• First, precipitation occurs, forming Cr(OH)3(s), which is green in colour.

Cr[(H2O)6]3+ + 3OH- Cr[(H2O)3(OH)3](s)

(Violet) (Green ppt)

• When an excess of NaOH is added, complexation occurs, causing the precipitate to dissolve.

Cr[(H2O)3(OH)3](s) + 3OH- [Cr(OH)6 ]3- + 3H2O

(Green ppt) (Pale Green Solution)

• The reaction above is characterised by a ligand displacement caused by the increase in

concentration of OH- ions.

Reaction of the most stable (Cr3+) oxidation state with ammonia

• When dilute NH3 is added to Cr3+(aq), a green precipitate of [Cr(H2O)3(OH)3] is formed, which is
insoluble in excess of the dilute NH3.
• In aqueous state NH3 partially dissociate to create the equilibrium below

NH3 (aq) + H2O (l) NH4+ (aq) + OH- (aq)

• Cr3+ then reacts dropwise with OH-

Cr[(H2O)6]3+ + 3OH- Cr[(H2O)3(OH)3](s)

(Violet) (Green ppt)
• However, if concentrated ammonia is used, the precipitate does dissolve, forming the violet
complex [Cr(NH3)6]3+.

Cr[(H2O)3(OH)3](s) + (excess) 6NH3 [Cr(NH3)6]3+.+ 3OH-

(Green ppt) (Violet)

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Relative stabilities of the +2 and the +3 oxidation states
• The +2 oxidation state is less stable than the +3 oxidation state.
• The sky blue Cr2+ (aq) can be prepared by dissolving chromium metal in an acid.
• However, the blue Cr2+ solution formed immediately turns green as it is oxidized to Cr3+ by
oxygen in air.

Reduction half equation Eθ/V

1 Cr2+ + 2e- Cr -0.91
2 Cr3+ + 3e- Cr -0.74
3 Cr3+ + e- Cr2+ -0.41
4 O2 +4H++ 4e- 2H2O +1.23
5 2H+ + 2e- H2 0.00

Combining equations (1) and (5)

Cr + 2H+ Cr2+ + H2 Eθ/V = +0.91V

• This shows that chromium metal can be oxidized by an acid to Cr2+.
Combining equations (3) and (5)

Cr2+ + 2H+ Cr3+ + H2 Eθ/V = +0.41V

• This shows that Cr2+ is further oxidized by the acid to Cr3+. In other words, Cr3+ is more stable
than Cr2+
Combining equations (3) and (4)

4Cr2++ 4H+ + O2 4Cr3++ 2H2O Eθ/V = +1.67V

• It can therefore be concluded that Cr2+ is a powerful reducing agent since it is readily oxidized to
Cr3+

Uses of chromium metal

• In chrome plating i.e. chrome plated objects, for example, car bumpers, are strong, resistant to
corrosion and attractive.
• Manufacture of stainless steel i.e. The presence of chromium hardens (strengthens) steel and
increases resistance to corrosion. This is because it forms a tough and impermeable surface layer
of chromium (III) oxide is formed, protecting the rest of the metal from attack by oxygen and
water. This oxide layer helps to protect steel from corrosion.

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Manganese Chemistry
Atomic number: 25
Configuration: [Ar] 4s23d5
Possible oxidation states: +2, +3, +4, +5, +6, +7
Most stable oxidation state: +2
Paramagnetism: all oxidation states except +7 are paramagnetic
Common Oxidation States Common Complexes Colour of Complex
+2 Mn2+ or [Mn(H2O)]2+ Pale Pink
+3 Mn3+ or [Mn(H2O)]3+ Red
+4 MnO2 Brown
+5 MnO43- Bright blue
+6 MnO42- Green
+7 MnO4- Purple

Unique Chemistry of Manganese

Oxidising Abilities of Higher Oxidation states of chromium (+4, +6 and +7)
• The MnO2, MnO42- and MnO4- are highly oxidising.
• Transition metals with higher oxidation states have a tendency of accepting electrons forming
more stable complexes with lower oxidation states.
• High oxidising abilities of complexes with high oxidation states is shown by large positive Eθ
value.

MnO4- +8H+ + 5e Mn2+ + 4H2O Eθ/V = +1.52V

• It can oxidize Cl- ions (in concentrated HCl) to chlorine gas. This is a good method for preparing
chlorine in the lab.
• It can oxidize the light green Fe2+(aq) to the yellow brown Fe3+(aq).
• It oxidizes ethanedioate ions (C2O42- = oxalate) to carbon dioxide

Disproportionation of (+6 oxidation state) MnO42-

• In an acidic medium MnO42- is unstable and readily disproportionates to MnO4-and MnO2.
• In neutral solution, the disproportionation occurs slightly and slowly. MnO42- is therefore more
stable in aqueous solution than in an acidic environment.
• The disproportionation of MnO42- does not take place when the solution is made strongly
alkaline.

Disproportionation of (+6 oxidation state) MnO42- in an acidic environment

MnO42- MnO4- + e Eθ/V = -0.56V

MnO42- + 4H+ + 2e MnO2 + 2H2O Eθ/V = +1.26V

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 • Combining the two equations gives the net equation for the disproportionation of MnO42- in
acidic medium.

3MnO42-(aq) + 4H+(aq) 2MnO4-(aq) + MnO2(s) + 2H2O(aq)

Eθ cell = -0.56V + 1.26V = 1.70V
• In this reaction, the green MnO42- is simultaneously oxidized to the deep purple MnO4- and
reduced to the black solid MnO2.

MnO42- MnO4- + e- Eθ/V = -0.56V

MnO4- +8H+ + 5e- Mn2+ + 4H2O Eθ/V = +1.52V

MnO42- + 8H+ 4MnO4- + Mn2+ + 4H2O Eθ/V = +0.96V

Disproportionation of (+6 oxidation state) MnO42- in aqueous environment
• Disproportionation of MnO42- can still take place in aqueous solution, but the reaction is
somewhat energetically unfavourable and is slow, as indicated by the very small value of the cell
potential.

2MnO42- 2MnO4- + 2e- Eθ/V = -0.56V

MnO4- + 2H2O + 3e- MnO2 + 4OH- Eθ/V = 0.60V

Net Overall Equation

2MnO42- + 2H2O MnO4- + MnO2 + 4OH- Eθ/V = +0.04V

• The disproportionation of MnO42- does not take place when the solution is made strongly
alkaline. This is because an increase in concentration of OH- ions on the right-hand side of
equation causes the equilibrium to shift to the left-hand side (Le Chatelier’s principle).

Preparation of +6 oxidation state (Reverse Disproportionation)

• A mixture of MnO4-, MnO2 and a strong concentrated alkali such as NaOH is heated. Formation
of MnO42- occurs according to the reverse of reaction.

MnO4- + MnO2 + 4OH- 3MnO42- + 2H2O Eθ cell = -0.04V

• The reaction occurs despite the fact that it has a negative cell potential. This is because the
conditions employed are not standard conditions (concentrated alkali and heat) and the redox
potential is a small negative number.

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Relative stabilities of the +2 and the +3 oxidation states of manganese
• The +2 state is very stable in acidic or neutral solution with respect to oxidation to the +3
oxidation state, as shown by the large and negative electrode potential for the oxidation reaction.

Mn2+ Mn3++ e Eθ = -1.49V

• However, in alkaline solution, Mn (II) is easily oxidized in air to Mn (III)

Reaction of Mn2+ with bases

Reaction with NaOH
• Add dilute NaOH or NH3 gradually until in excess. An off white (buff) precipitate is formed
which is insoluble in excess NaOH or NH3,
• It is possible to miss this observation because the precipitate immediately turns to brown in air.
Dropwise Addition

Mn[(H2O)6]2+(aq) + OH- Mn(OH)2 (s)

Faint Pink Off White
In excess

• An off white (buff) precipitate formed insoluble in excess NaOH.

• The precipitate immediately turns to brown in air.

Mn(OH)2(s) O2 (g) Mn(OH)3

Off White Brown

Reaction with NH3

• Dropwise Addition of ammonia an off white ppt that does not dissolve in excess NH3 but the
white ppt is immediately oxidised to brown ppt Mn (III) by atmospheric oxygen.
• In aqueous state NH3 partially dissociate to create the equilibrium below

NH3 (aq) + H2O (l) NH4+ (aq) + OH- (aq)

Mn[(H2O)6]2+(aq) + OH- Mn(OH)2 (s)
Faint Pink Off White

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MnO2 (black powder)
• Add cold dilute hydrogen peroxide. There is brisk effervescence and the reaction mixture
becomes warm. The gas produced relights a glowing splint.
• During the reaction, no visible change occurs to the MnO2.Manganese dioxide catalyzes the
decomposition of hydrogen peroxide to oxygen and water.

Uses of Manganese Complexes

• MnO2 is used as a polariser in battery cells e.g. in dry cells.
• Manganese is used as a rubber additive.
• Manganese is used in the production of stainless steel.

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Iron Chemistry
Atomic number: 26
Configuration: [Ar] 4s23d6
Main oxidation states: +2, + 3and +6
Most stable oxidation states: +2, +3
Paramagnetism: +2 and +3 states are paramagnetic, except some low spin complexes of iron
(II)
Common Oxidation Common Complexes Colour
States
+2 Fe2+ or [Fe(H2O)6]2+ Green
+4 Fe3+ or [Fe(H2O)6]3+ Brown
+6 FeO42-

The Most Stable State

• In normal aqueous solution, the +3 oxidation state is more stable than the +2 oxidation state. This
is because Fe3+ has a half filled 3d subshell which is stable.
• The stability of Fe ions is also affected by the conditions under which the ions will be existing in.

Conditions which affect the stability of Fe ions

1. Type of Ligand
2. PH

Type of Ligand
• The ligand attached to an Fe ion will determine the oxidation state in which it will be stable.
Consider the CN- and H2O ligand

[Fe(H2O)6]3+ + e- [Fe(H2O)6]2+ Eθ/V = +0.77V

[Fe(CN)6]3- + e - [Fe(CN)6]4- Eθ/V = +0.36V

• If we are to reduce the +3 complexes into +2 complexes using the iodide ions.
Consider Water as a Ligand

[Fe(H2O)6]3+ + 2I- [Fe(H2O)6]2+ + I2 Eθ/V = +0.23V

brown green

• The Eθ value is positive and it implies that the reaction is feasible and the I- can easily reduce the
Fe3+ to Fe2+ when water is a ligand.
• This shows that the Fe3+ is less stable the Fe2+ when water is a ligand.

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Consider water as a ligand

[Fe(CN)6]3- + 2I- [Fe(CN)6]4- + I2 Eθ/V = -0.18V

• The Eθ value is negative, this shows that the reaction is not feasible thus the iodide ions cannot
reduce Fe3+ to Fe2+ with CN- as a ligand.
• Therefore, Fe3+ is more stable than Fe2+ when CN- is a ligand.

PH
Under Acidic Conditions

Fe3+ + e- Fe2+ Eθ/V = +0.77V

Under Basic Conditions

Fe(OH)3 + e- Fe(OH)2 Eθ/V = -0.56V

Reversing the above equations

Fe2+ Fe3+ + e- Eθ/V = -0.77V

Fe(OH)2 Fe(OH)3 + e- Eθ/V = +0.56V
• It would require a strong oxidising agent with an Eθ value greater or equal to +0.77 to oxidise Fe2+
to Fe3+. Therefore, it shows that Fe2+ is more stable in acidic conditions compared to Fe3+.
• Any substance with an Eθ value of less than -0.56 can easily oxidise Fe2+ to Fe3+ under basic
conditions.
• This clearly shows that Fe2+ is not stable under basic conditions therefore it is easily oxidised to
the stable Fe3+.

Complexes of FeO42-
• Iron has only one oxo anion, FeO42-, which is very unstable and is easily reduced by many
reducing agents to Fe3+.

FeO42- + 8H+ + 3e- Fe3+ + 4H2O Eθ/V = +2.20V

Complexes of Fe2+
• Most of the complexes are octahedral.
• Fe(II) forms a reasonably stable complex, [Fe(NH3)6]2+ with concentrated ammonia. The complex
is not formed when dilute ammonia is used.
• Fe(III) does not form a complex with ammonia.

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Reactions of Fe2+

Reaction with Observations Notes

NaOH(aq) Green precipitate formed, Fe(OH)2(s) is easily oxidised by air to reddish
insoluble in excess NaOH. brown solid Fe(OH)3(s) i.e. Fe2O3.xH2O
Precipitates turns red brown in
air.

NH3(aq) Green precipitate formed, Fe(OH)2(s) is easily oxidised by air to reddish

insoluble in excess NH3. brown solid Fe(OH)3(s) i.e. Fe2O3.xH2O
Precipitates turns red brown in
air.

CN-(aq) White precipitate formed, Fe2+(aq) + 2CN-(aq) Fe(CN)2(s)

soluble in excess cyanide to white ppt
form a yellow solution.
The precipitate dissolves due to
complexation

Fe(CN)2(s) + 4CN-(aq) [Fe(CN)6]2-(s)

Yellow complex

KMnO4 in KMnO4 is decolourized. Light Fe2+ oxidized to Fe3+ and MnO4- reduced to
acidic medium green colour of Fe2+ changes to Mn2+
yellowish brown .

CO32-(aq) white ppt formed Fe2+(aq) + CO32-(aq) FeCO3(s)

white ppt

[Fe(CN)6]3- A Turnbull’s blue precipitate is An insoluble dye (complex) is formed with a

(complex of Fe3+ Formed blue colour described as Turnbull’s blue.
with cyanide Fe3[Fe(CN)6]2
ligands)
This reaction can be used to distinguish
between Fe2+ and Fe3+

Cl2(g) Light green colour of Cl2 oxidizes Fe2+ to Fe3+

Fe2+changes to yellowish brown

Complexes of Fe3+
• Most of the complexes are octahedral.
• The corresponding aqua complex for Fe(III) does not exist because the high charge density on
the Fe3+ polarizes a water molecule, takes up an OH- ligand and releases H+ in solution.

[Fe(H2O)6]3+(aq) [Fe(H2O)5(OH)]2+(aq) + H+(aq)

• A solution of Fe3+ in water is therefore acidic.

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Reactions of Fe3+

Reaction with Observations Notes

NaOH(aq) Red - brown precipitate Iron (III) hydroxide precipitated
formed, insoluble in excess
NaOH(aq)

NH3(aq) Red - brown precipitate Iron (III) hydroxide precipitated

formed, insoluble in excess
NH3(aq)

CN-(aq) Orange brown solution Hexa cyano complex, [Fe(CN)6]3-(aq),

Formed formed

KI solution turns brown Fe3+ oxidizes colourless I-(aq) to brown

iodine solution. Meanwhile, Fe3+ is
reduced to Fe2+

CO32-(aq) Red - brown precipitate Iron (III) hydroxide is formed, not iron
Formed (III) carbonate.

This is due to the acidic nature of Fe3+(aq)

SCN-(aq) Blood - red solution formed aqua - thiocyanato complex is formed

(thiocyanate
ions) Fe3+ + SCN- [Fe(H2O)5SCN]2+
blood - red complex

This is a good and sensitive test to

distinguish between Fe2+ and Fe3+

[Fe(CN)6]4- Prussian blue precipitate An insoluble dye (complex) is formed,

complex of Fe2+ formed with a blue colour described as Prussian
with cyanide blue. Fe4[Fe(CN)6]

NB Prussian blue and Turnbulls’ blue are

only different in their impure forms. When
purified, they are found to be identical.

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The rusting of iron
• Rusting is the name given to the corrosion (oxidation) of iron by a combination of water and
oxygen.
• It is an electrochemical process, that is, it involves anodic regions where iron is oxidized and
cathodic regions where oxygen and water are reduced.
• Electrical circuits are set on the surface of the metal, which allow electrons to flow through water
from the anodic to the cathodic sites.
• Formation of anodic and cathodic sites is a result of inconsistencies on the surface of the metal,
which cause some sites to become deficient in oxygen (anodic sites) and others to be well aerated
(cathodic sites).
• When water comes into contact with Fe metal, it results in the formation of Fe2+.

• The OH- ions formed at cathodic sites and Fe2+ ions formed at anodic sites attract each other and
combine to form a precipitate of iron (II) hydroxide.

Fe2+(aq) + 4OH-(aq) 2Fe(OH)2(s)

• The iron (II) hydroxide is immediately oxidized in oxygen to form iron (III) hydroxide, which
is a yellowish brown solid. Dehydration of iron (III) hydroxide results in the formation of rust
(hydrated iron (III) oxide).

2Fe(OH)2(s) + O2 2Fe(OH)3(s) Fe2O3.xH2O

Rust Red-Brown

• Rusting of iron can be rapid because a large number of electrochemical cells are simultaneously
formed on the surface of the metal.

Conditions that can accelerate the Rusting of Iron

Salty water (e.g. sea water)
• It rapidly increases the rate of reaction by acting as a good electrolyte for the transfer of electrons
from anodic to cathodic sites.

Differential exposure of iron to air

• It initiates rusting by creating regions that are deficient in oxygen (anodic sites). This results in
the oxidation of Fe2+ to Fe3+.
• The electrons produced at the anodic site then flow to the oxygen rich (cathodic) sites.
• The rusting of iron is therefore faster when one part of the metal is exposed to air and the other is
partially hidden from air.
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Ways of Preventing Rust
Barrier methods
• These methods involve covering the surface of the metal with a tough impermeable substance
which prevents entry of oxygen and air.
• Barrier methods include painting, oiling, greasing and electroplating.

Alloying
• Stainless steel is an alloy of iron whose resistance to corrosion is due to the presence of
chromium.
• Formation of a tough and impermeable layer of Cr2O3 (chromium (III) oxide) on the surface of
the steel object prevents entry of oxygen and water.
• This method is therefore similar to the barrier methods discussed above. The difference is in how
the barrier is introduced onto the surface of the metal.

Sacrificial protection
• In this method, the iron or steel object is brought into contact with a more reactive metal (one
which is higher than iron in the electrochemical series) and the more reactive metal acts as the
anode where the metal is oxidised and loses electrons to form ions protecting the ion which then
serves as the cathode.
• Two commonly used methods of sacrificial protection are galvanizing and cathodic protection.
Iron pipes connected to Magnesium through copper wires

• The magnesium serves as the sacrificial anode so that even if the coating is scratched, the
exposed steel serves as the anode and is still protected by the remaining magnesium.
Galvanisation
Galvanisation protects iron from rusting in the following ways

• It forms a barrier that prevents corrosive substances from reaching the underlying steel or iron
• The zinc serves as the sacrificial anode so that even if the coating is scratched, the exposed steel
serves as the anode and is still protected by the remaining zinc.
Question
1. Explain why tin foods cans can quickly rust when the tin coating gets scratched
This is because iron is more reactive than tin and iron serves as the sacrificial anode and when iron
is exposed to water and air it is oxidised.

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Use of chemical inhibitors
• These are chemicals which stop or slow the anodic or cathodic reactions that take place on the
surface of an iron object.
• Hydrogen carbonate can be used as a cathodic inhibitor.
• It removes OH- ions that are generated in cathodic reactions, resulting in the formation of an
insoluble carbonate.

HCO3-(aq) + OH-(aq) CO32-(aq) + H2O(l)

• Formation of an insoluble layer of metal carbonate prevents further entry of oxygen and water,
and in turn this stops the cathodic reaction.
• Inhibition of the cathodic reaction also stops the anodic reaction. This is because oxygen and
water are not available any more to accept electrons that are produced at the anodic sites.

The biochemical importance of iron

• Iron is one of the major metals found in the human body.
• It is found in the form of Fe(II) in haemoglobin and cytochrome oxidase.

Haemoglobin
• It is found in red blood cells, is responsible for the transportation of oxygen from the lungs to the
rest of the body.
• The basic functional unit in haemoglobin is a molecule known as haem. This is a complex which
contains Fe(II) at its centre.
• It is this iron which bind oxygen ligands at the lungs, allowing them to be carried to the tissues.
• The Fe-O2 dative bond (by making use of a low lying accessible partially filled 3d orbital) is
weak and its formation in is favoured by the high partial pressure of oxygen in the lungs.
• In the tissues, where the concentration of oxygen is low, the bond breaks, thus allowing oxygen to
be delivered to the cells.

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Cytochrome oxidase
• It is an enzyme that is involved in electron transfer during respiration in the mitochondrion.
• Respiration is essentially an oxidation process, involving loss of electrons from the respiratory
intermediates.
• Cytochrome oxidase acts as an electron transfer agent.
• The haem group is also found in cytochrome oxidase, and it is iron (II) at the centre of the haem
group that gives cytochrome oxidase its ability to act as an agent of electron transfer because of
the ability to vary its oxidation state.

CO and CN- poisoning

• Haem has five permanent dative bonds and a sixth co-ordination site which is not selective and it
bind other types of ligands.
• CO and CN- are very strong fields ligands which can form very stable complexes i.e. once they
are formed, they are very difficult to replace.
• If CO and CN- finds its way into the blood stream of living organisms they form very strong
dative bonds with Fe(II) resulting in oxygen not being transferred and as a result asphyxiation
occurs (One will not be able to breathe)
• A person suffering from CO and CN- is treated by being made to breathe pure oxygen.

Uses of iron
• It is used as a catalyst in Haber process.
• It is used as a raw material in the manufacture of steel.

Cobalt Chemistry
Atomic number: Z= 27
Configuration: [Ar]3d74s²
Stable oxidation states: +2 and +3
More stable oxidation state: +2
Common Oxidation Common Complexes Colour
States
+2 Co2+ or [Co(H2O)6]2+ Pink
+3 Co3+ or [Co(H2O)6]3+ Blue

Most Stable Oxidation State

• In aqueous environment the +2 oxidation state is more stable compared to the +3 oxidation state.
• The oxidation state of +2 and +3 oxidation state is affected by the type of ligand present.

Consider water as a Ligand

• The oxidation of Co(II) to Co(III) in aqueous solution. The electrode potential for this
conversion, -1.81V, shows that Co(II) is much more stable in aqueous solution than Co(III).

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 [Co(H2O)6]3+ + e [Co(H2O)6]2+ Eθ/V = +1.81V

• When the +3 complexes are reduced by iodine the following reactions are observed

[Co(H2O)6]3+ + I- [Co(H2O)6]2+ + I2 Eθ/V = +1.27V

• The iodide ions can easily reduce Co3+ to Co2+.

• Clearly the reaction is very feasible thus this means that the +3 oxidation state is not stable when
water is a ligand.

Consider ammonia as a ligand

[Co(NH3)6]3+ + e- [Co(NH3)6]2+ Eθ/V = +0.10V

• When the +3 complexes are reduced by iodine the following reaction is observed.

[Co(NH3)6]3+ + 2I- [Co(NH3)6]2+ + I2 Eθ/V = -0.44V

• Clearly the reaction is not feasible thus this means that the +3 oxidation state is more stable when
ammonia is a ligand

Unique Chemistry of Cobalt

Reaction with concentrated HCl
• When Co2+ reacts with concentrated HCl, the reaction is characterised by a change in geometry.
• A good illustration is the conversion of the pink hexaaqua [Co(H2O)6]2+ to the blue tetrachloro
[CoCl4]2- complex.

• Increasing concentration of Cl ligands (by heating or by adding concentrated HCl) causes the
solution to change to blue.
• Diluting the blue solution (adding more water ligands) or reducing temperatures reverses the
change and the solution becomes pink once more.

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Reaction of Co2+ with bases
Dropwise Addition

Co(H2O)6]2+ + 2OH- Co(OH)2(s) + 6H2O

Pink Blue
In Excess

Co(OH)2(s) + OH- ppt insoluble in excess

• Instead the blue insoluble ppt undergoes atmospheric oxidation to brown ppt

Co(OH)2 + O2 + H2O Co(OH)3 (brown ppt)

Reaction with ammonia

Dropwise Addition

• Ammonia dissociate as follows in aqueous environment.

NH3 + H2O NH4+ + OH-

Co(H2O)6]2+ + 2OH- Co(OH)2(s) + 6H2O

Excess Ammonia

Co(OH)2(s) + excess 6NH3 Co(NH3)6]2+ (aq) + 2OH-

Blue Golden brown
The golden-brown solution undergoes atmospheric oxidation to dark brown solution

Co(NH3)6]2+ + O2 Co(NH3)6]3+ (aq)

Preparation of Co(III) complexes

• When Co(III) is added to water, its blue colour disappears and is replaced by the pink of Co(II).
• Bubbles of oxygen are also produced and the solution becomes acidic.
• This shows that Co(III) is strongly oxidizing in aqueous solution.

Co(H2O)6]3+ + H2O [Co(H2O)6]2+ + O2 + 4H+

Eθ cell = 1.81 - 1.23 = +0.58V
• The +3 state is stabilized by other ligands such as ammonia and oxalate.

Uses of Cobalt
• It is used to make alloys e.g. Alnico which is used to make permanent magnets
• Anhydrous Co2+ used to test for water
• Cobalt (as Co(III)) is biologically important as it is required for the formation of vitamin B12
• Vitamin B12 helps to make DNA and the genetic material in all cells.
• Vitamin B12 also prevents anaemia.

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Nickel Chemistry
Atomic number: Z = 28
Configuration: [Ar]3d84s²
Stable oxidation state in aqueous solution: +2 (green)
Magnetism: octahedral complexes of Ni2+ are paramagnetic, whereas square planar
complexes are diamagnetic

Extraction
• Nickel occurs in the earth’s crust in the form of sulphide ores.

The stages involved in the extraction of nickel metal from the sulphide ore are;
a) Roasting of the oxide in air
b) Reduction of the metal oxide by carbon
c) Purification of the metal

Roasting of the oxide in air

• This converts the sulphide ore into the metal oxide.

NiS(s) + O2(g) NiO(s) +SO2(g)

Reduction of the metal oxide by carbon

• This results in the formation of impure nickel metal

NiO(s) + C(s) Ni(s) + CO(g)

Purification of the metal

• This can be achieved electrolytically or by the Mond process.

Electrolytic purification
• It involves making the impure nickel metal the anode in an electrolytic cell containing pure nickel
cathodes and an electrolyte of nickel (II) sulphate.
• The anodes dissolve in the process, liberating Ni2+ ions, which then migrate to the cathodes.
• At the cathode, Ni2+ ions are reduced to pure nickel metal, which is deposited on the cathodes

Mond process
• Nickel is heated at 60 0C in the presence of carbon monoxide. This results in the formation of a
volatile neutral complex, tetracarbonyl nickel (0), in which the metal has an oxidation state of 0

Ni(s) + 4CO(g) Ni(CO)4(l)

• Ni(CO)4 is distilled out and then heated at 2000C. This causes it to decompose back to pure nickel
and carbon monoxide. Impurities are lost during the decomposition process, so the nickel formed
is very pure.

Ni(CO)4(l) Ni(s) + 4CO(g)

• The produced CO is recycled back into the system.
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 Common Oxidation Common Complexes Colour
States
+2 Ni2+ Green
+3 Ni3+ Dark Grey / Black

Complexes
• Ni2+ forms both six co-ordinate (octahedral) and four co-ordinate complexes.
• The four co-ordinate complexes usually have a square planar geometry, but a few tetrahedral
complexes are known.
Complex Shape and Bond Angle Colour
[Ni(H2O)6]2+ octahedral, 900 Green
[Ni(NH3)6]2+ octahedral, 900 Blue
[Ni(CN)42- square planar, 900 Yellow
[Ni(Cl)42- tetrahedral, 1090 Blue

The Unique Chemistry of Nickel

The reaction of Ni2+ with HCl
• When Ni2+ reacts with concentrated HCl, the reaction is characterised by a change in geometry.

[Ni(H2O)6]2+ + 4Cl- [Ni(Cl)4]2- + H2O

Green Blue

• Temperature and Type of Ligand affect the geometry of Nickel complexes.

• The colour of the complexes changes due the changes in the type of ligands and change in
geometry as well.

Reaction with CN- Ligand

• When Ni2+ reacts with CN-, the reaction is characterised by a change in geometry.
Consider the following situation
With the aid of an equation, explain the observations made in when Ni2+ (aq) is shaken with KCN in a test
tube.

[Ni(H2O)6]2+ + 4CN- [Ni(CN)4]2- + H2O

Green Yellow

• CN- is a strong field ligand hence it displaces water ligands resulting in a change in geometry and
colour.
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Reaction of Ni2+ with Bases
Reaction with NaOH
Dropwise Addition

Ni(H2O)6]2+ + 2OH- Ni(OH)2(s) + 6H2O

Green Pale Green ppt
In Excess

Ni(OH)2(s) + OH- pale green ppt insoluble in excess

Reaction with ammonia
Dropwise Addition

• Ammonia dissociate as follows in aqueous environment

NH3 + H2O NH4+ + OH-

Ni(H2O)6]2+ + 2OH- Ni(OH)2(s) + 6H2O

Green Pale Green ppt
Excess Ammonia

Ni(OH)2(s) + excess 6NH3 Ni(NH3)6]2+ (aq) + 2OH-

Pale Green ppt Blue

• Due to higher concentration of NH3 the OH- is displaced by NH3 ligands.

Test for Ni2+(aq)

• The most reliable and sensitive test for the presence of Ni2+ involves adding dimethylglyoxime.
• A bright red precipitate indicates the presence of nickel (II).

Uses of Nickel
In alloys
Important alloys that contain nickel include

• Nichrome (60% Ni and 40% Cr), which is used for making high resistance wires.
• ALNICO which is used in the manufacture of powerful permanent magnets. The alloy also
contains aluminium and cobalt.
• Stainless steel. Ni is strong, resistant to corrosion and high temperatures. It imparts these
properties to steel.
• Cupronickel (20% Ni and 80 % Cu) which is used to make silver coins.

Industrial catalyst
• Ni is commonly used in reactions which involve addition of hydrogen to a raw material, for
example, hydrogenation of oils in the manufacture of margarine.

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Copper Chemistry
Atomic number: Z= 29
Configuration:[Ar] 3d104s1
Possible oxidation states in compounds: +1 and +2
Stable oxidation state in aqueous solution: +2
Paramagnetism: Cu(I) compounds are diamagnetic (d10), copper(II) compounds are usually
paramagnetic.

Purification of Copper
• Copper is purified to be used for electrical wiring because 99.99% of purity is required for
efficient transmission of electrical energy. Even small amounts of impurity reduce its
conductivity greatly.

Electrolytic purification of copper is carried out in cells using:

i. an electrolyte of copper (II) sulphate solution acidified with sulfuric acid.
ii. an anode of impure copper.
iii. a cathode of pure copper

At the anode

• The copper anodes dissolve through oxidation, releasing Cu2+ ions, which then migrate to the
cathode.

Cu Cu2+ + 2e
• The anodes therefore get thinner whilst the cathodes gain mass and become thicker. The
impurities in the anode settle down as anode 'sludge'.
• The purification process removes certain impurities, particularly zinc, gold and silver.
• Electrode potentials can be used to explain how these impurities are removed from the impure
copper.

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 • The conversion of zinc metal to Zn2+ has a positive reduction potential (reverse of equation (i)
that is, at the anode, any zinc in the copper easily turns to Zn2+ ions.
• On the other hand, the reduction of Zn2+ ions to zinc metal has a negative reduction potential,
that is, the reduction of Zn2+ ions to zinc metal is not likely in aqueous solution. The ions
therefore stay in solution.
• The reduction potentials of silver and gold are more positive than that of copper (they are more
stable). These two impurities do not easily dissolve at the anode.
• Instead, they remain in their solid metallic state and drop to the bottom of the cell as the impure
copper anode dissolves.

At the Cathode

• At the cathode, Cu2+ ions are reduced, forming copper metal, which sticks onto the cathode.

Cu2+ + 2e- Cu(s)

• Copper ions are transferred from the anode to the cathode. As a result, the cathode gets thicker
and the anode get thinner.
• The concentration of copper (II) sulphate solution does not change because the number of moles
of Cu²⁺ ions formed at the anode is exactly the same as the number of moles of Cu²⁺ions
discharged at the cathode.
Question
Explain why measuring the decrease in mass of the anode would be preferred to measuring the increase in
mass of the cathode.
Answer
The value of current used to discharge mass of copper at the cathode is less than the actual current flow at
the anode because a small percentage of the current is used in dissolving the impurities into the solution
which are not then deposited at the cathode at the anode.

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 Common Oxidation Common Complexes Colour
States
+1 Cu+ White
+2 Cu2+ Blue

Colours of Copper Complex

In ground state copper complexes have the following electronic configurations:
Copper (I) = [Ar]3d10

• Since all of the d - orbitals are fully filled, d-d transitions which are responsible for absorption of
light energy and formation of colour are not possible.
Copper (II) = [Ar]3d94s2

• Cu2+ has a partially filled 3d subshell, therefore d-d transition occurs after orbital splitting
resulting in colour changes.

The most stable oxidation state

• The +2 state is very stable in aqueous solution, in which it has a sky blue colour due to the
hexaaqua complex [Cu(H2O)6]2+

The Cu+ Chemistry

• The +1 state is very unstable in water.
• Cu(I) is unstable in water through disproportionation.
• It rapidly undergoes simultaneous oxidation to Cu2+ and reduction to copper metal.

Disproportion of Cu+

Cu+ + e- Cu Eθ/V = +0.52V

Cu2+ + e- Cu+ Eθ/V = +0.15V

Net Overall Equation

2Cu+(aq) Cu2+ (aq) + Cu (s) Eθ/V = +0.37V

• The disproportion of Cu+ can also be shown by a reaction of Cu2O and H2SO4

Cu2O + H2SO4 CuSO4 (aq) + Cu (s) + H2O (l)

Red Brown Blue Pink

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Conditions which stabilises Cu+ ions
• Cu+ can be stabilised in the presence of the following ligands:
i. I-
ii. CN-
• In the presence of these ligand Cu2+ will not be stable hence they are reduced to stable Cu+ ions.

In the presents of I-
2Cu2+ (aq) + 2I- (aq) 2Cu+ (aq) + I2 (aq) …………(1)
• I- ions reduce Cu2+ ions to copper (I). Meanwhile some of the iodide ions are oxidized to iodine.
• The cell potential for this reaction is negative (0.15 - 0.54 = -0.39V).
• Theoretically we do not expect the reaction to take place since it has a negative cell potential.
• In practice the reaction occurs without any difficulty because as soon as the unstable Cu+(aq) ions
are formed, they are stabilized through precipitation with unreacted iodide ions.

2Cu+(aq) + 2I- (aq) 2CuI(s) (white ppt)………………..(2)

Combing Equation 1 and 2
Net Overall Equation:

2Cu2+ (aq) + 4I- (aq) 2CuI (s) (white ppt) + I2 (aq)

Consider the following example
A 0.250 g sample of a copper-containing alloy was converted into an aqueous solution of Cu2+ ions, and
an excess of I–(aq) ions was added. The iodine liberated required 20.0 cm3 of 0.100 mol dm–3 thiosulphate
to react completely. What is the percentage of copper in the alloy?

In the presents of CN-

2Cu2+ + 4CN- 2CuCN + C2N2
• CN- ions reduce Cu2+ ions to copper (I)
• This shows clearly that Cu2+ ions are not stable in the presence of CN- and I- ligands compared to
Cu+.
❖ The +1 state of copper is also stable in insoluble copper (I) compounds such as Cu2S and Cu2O.

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The Cu2+ Chemistry
The Reaction with HCl
• The reaction is characterised by the change in geometry from octahedral [Cu(H2O)6]2+ and
tetrahedral CuCl42-.
Reaction with dilute HCl followed by warming

• Warming drives out some water and thus increases concentration of Cl- ligands, resulting in the
formation of the yellow complex CuCl42- by ligand exchange.
Heat

[Cu(H2O)6]2++ 4Cl- CuCl42- + 6H2O

Blue Yellow

Reaction with Concentrated HCl

• Ligand exchange occurs and warming is not required.

[Cu(H2O)6]2++ 4Cl- CuCl42- + 6H2O

Observations

• Solution turns from light blue to yellowish- green.

• The greenish-yellow colour is caused by the mixing of colours, the blue of Cu2+(aq) and the
yellow of CuCl42-.

Possible Question
Explain the reaction which occurs when aqueous CuSO4 was mixed with dil HCl

Reaction with Bases

Reaction with NaOH (aq)
Dropwise addition

• Precipitation of Cu2+ by OH- ions.

Cu2+ + 2OH- Cu(OH)2 (s) (Pale blue precipitate)

In excess

Cu(OH)2 (s) + OH- Insoluble in excess

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Observations

• Pale blue precipitate formed, insoluble in excess NaOH.

Reaction with NH3 (aq)

• Ammonia dissociate as follows in aqueous environment

NH3 + H2O NH4+ + OH-

Dropwise addition
The OH- ligand reacts with the Cu2+ ions.
[Cu(H2O)6]2+ + 2OH- [Cu(H2O)4(OH)2] + 2H2O
Pale blue ppt
Excess Ammonia

• The precipitate then reacts further with NH3 molecules in a ligand exchange reaction, to form the
deep blue complex.
[Cu(H2O)4(OH)2] + NH3 [Cu(NH3)4(H2O)2] + 2H2O
Deep blue Complex

The structure of [Cu(NH3)4(H2O)2]

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Reaction with conc HCl followed by conc NH3
Conc HCl

• Solution turns greenish – yellow and CuCl42- is formed.

Followed by Conc NH3

• The greenish - yellow colour is immediately replaced by a deep blue colour.

• Ammonia is a stronger field ligand than chloride. Therefore Cl- ligands in CuCl42- are replaced by
ammonia, resulting in the formation of a more stable complex.
• The new complex formed has a higher stability constant, so its formation is favoured.

Reaction with Conc NH3 followed by EDTA

• EDTA4- is a stronger field ligand than ammonia. EDTA4- ligands therefore replace NH3 in the
complex [Cu(NH3)4(H2O)2]2+, resulting in the formation of the light blue complex
[Cu(EDTA)]2-
• This complex has a very large stability constant which favours its formation.
[Cu(NH3)4] + EDTA [Cu(EDTA)]2- + 4NH3
Observations

• The blue colour changes from deep blue colour [Cu(NH3)4(H2O)2]2+ to pale blue [Cu(EDTA)]2-.

Uses of copper
• Being a relatively cheap metal, which is also resistant to corrosion, it is used in electrical cables.
• Copper is used in car radiators because it is resistant to corrosion and it is also a good conductor
of heat.
• Complexed Cu(II) is used in alkaline solution in the Fehling’s and Benedict’s test for aldehydes,
for example, reducing sugars.
• It is used in the manufacture of alloys, including brass and bronze.
Bronze
Bronze is an alloy of copper and tin. It has greater tensile strength than copper. It can also be cast into
moulds more easily. For this reason, it is used to make sculptures.
Other uses of bronze include:
▪ For electrical connectors (it is a better conductor than most steels)
▪ Boat and ship propellers (It is resistant to corrosion
Brass
Brass is an alloy of copper and zinc. It is harder and stronger than copper. Its colour makes it decorative.
The uses of brass include:
▪ Making musical instruments (brass has excellent acoustic properties)
▪ In ornaments

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PLATINUM GROUP OF METALS
• It consists of 6 noble precious metallic elements.
• These 6 unreactive elements are transition metals and these are:
i. Ruthenium
ii. Rhodium
iii. Palladium
iv. Osmium
v. Iridium
vi. Platinum
• These elements have very similar chemical and physical properties
• They also occur together in mineral deposits

Properties of PGMs
• PGMs and their compounds have inherent properties that make them a significant benefit to the
society and often superior to other materials and often non-substitutable such as:
i. Unique catalytic properties
ii. Resistance to corrosion and oxidation
iii. Mechanical strength
iv. Biocompatibility
v. Electrical conductivity

Platinum
• Platinum is mined together with other metals such as gold, nickel and copper (they exist together
in ores)
• Sperrylite and Cooperite are the most common platinum mineral ores.
• It generally occurs with a wide array of other unusual minerals, including cooperite which include
sulphide ores [(Pt,Pd,Ni)S].

Extraction of Platinum
• The extraction of Platinum consists of a number of stages and these are:
1. Crushing
2. Froth Floatation
3. Drying and Purification
4. Electrolysis

Crushing
• The first process in this process is to crush platinum containing ore to increase the surface area
for the extraction of platinum.

Froth Flotation
• PGMs are usually recovered by flotation as a bulk low-grade sulphide concentrate, followed by
smelting and refining
• Flotation is a selective physico-chemical separation process that utilises the difference in surface
properties of the valuable minerals and the unwanted gangue minerals.
• The basis of separation is mineral affinity for air (aerophilic) and mineral hydrophobicity.

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 • The ore is immersed in the chemical reagents containing water e.g. (collectors, frothers,
regulators and activators)
• During flotation, air is pumped through the water slurry.
• Platinum particles and other minerals chemically attach to the air bubbles and rise to the surface
in a froth that is skimmed off for further refining.

• Fe and Nickel are removed by a magnet due to different magnetic properties to that of platinum.

Drying and Purification

• The froth containing valuable minerals and other impurities is dried.
• The concentrated powder still contains a powder of 1% platinum.
• The powder is heated in an electric furnace at 15000C
• Air is blown so that impurities like Fe and S are removed.
• Electrolytic and chemical techniques are employed to extract Ni, Cu and Co, resulting in a
concentrate of 15% to 20% PGMs.
• Aqua regia (a concoction of nitric acid and hydrochloric acid) is used to dissolve platinum metal
from the mineral concentrate by creating chlorine that attaches to platinum to form chloroplatinic
acid.
• In the final step, ammonium chloride is used to convert the chloroplatinic acid to ammonium
hexachloroplatinate (NH4)2PtCl6, which can be burned to form pure platinum metal.
• The aqua reagia dissolves platinum compound and leaves other metals and other compounds
suspended.

Uses of Platinum
• For jewellery due to high lustre
• In fuel cells
• Catalytic cracking and catalytic reforming as a catalyst
• Making catalytic converters
• To make spark plugs

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COMPILED AND EDITED BY MR MAGABA O774 372 589