!

"# "%&'( )&''( *

HSC St udy Buddy
! Exclusive band 6 and state ranking level notes
! Interactive online tutorials with State Ranking students
! HSC videos providing tips and breaking down the syllabus
! All resources sourced exclusively from band 6 and state ranking
students.





















!!!"#$%$&'()*'(()"%+,"-'
/01+2#$%$&'()*'(()"%+,"-'




"#$%&' ( )*+ ,*+-%.$/0 &1 2/$
3#-4&56 7 8 9/:,50&$ ;#6+':#+'& </$&+6)

Sources of Pigments in Early History

Colour Pigments
Black Charcoal burnt wood, animal bones, soot
White Gypsum CaSO4.2H2O
Chalk - CaCO3
Kaolin - Al2Si2O5(OH)4
Red Ochre crushed rocks
Cinnabar HgS
Yellow/Brown Orpiment As2S3
Limonite FeO(OH)H2O
Green Malachite Cu2(CO3)(OH)2
Grey Galena PbS
Cerussite PbCO3

In early history, the pigments used were the minerals readily available in coloured earth and soft
rocks.

Insolubility of Pigments
Pigments need to be insoluble in most substances for several reasons:
1. To ensure that the pigment particles remain on the painting after the medium has dried
2. To ensure that the pigments are not easily removed from the surface of the painting when
exposed to rain
3. To ensure pigments used in cosmetics do not get washed away by perspiration

Prehistoric Use of Pigments Self Decoration
Aborigines:
" Body art used red and yellow ochres, white clay and charcoal as pigments
" Pigments were applied with fingers or brushed to produce symbols representing history and
myths
" Mainly used for ceremonial purposes

Egyptians:
" Accentuated the eye as the main facial feature (symbol of the sun god Ra)
" Cosmetics used include: kohl as eyeliner, green malachite as eye shadow, white lead to
whiten the skin, red ochres on lips and cheeks and dyes as nail polish
" Raw pigments were prepared by grinding on a stone slab and applied in powder form
" Some cosmetics contained metallic poisons e.g. lead, mercury and antimony

Ancient Greeks:
" White lead was used to whiten faces and red lead was used as blush on cheeks

Prehistoric Use of Pigments Preparation of the Dead for Burial
The Egyptians had a reverence for the passage of the dead into the afterlife and therefore used
pigments for the dead in much the same way as they did for the living.
" The main colours used included white, black, red, yellow and ultramarine blue and due to
the lack of sunlight in the tombs, the colours remained vivid for long periods of time
!"# "%&'( )&''( +


" Egyptian tombs (sarcophagi) were pained inside and out with representations of the dead
and the life they lived
" Mummified bodies were also decorated with geometric designers to ensure the continued
survival of the owner
" Cosmetic boxes of pigments were often buried with the dead in tombs to be used in the
afterlife e.g. powdered gypsum, orpiment and haematite

Prehistoric Use of Pigments Cave Drawings
The Aboriginal cave drawings are considered to be amongst the earliest known paintings.
" Few pigments were available, with the main ones being: chalk, ash, charcoal, limonite,
kaolin and red, yellow and brown ochres
" Binders used included egg yolk, tree resin, blood, urine and saliva
" Traditional techniques were used to apply paints e.g. use of sticks and barks as well as
body parts such as fingers and spraying with the mouth
" Cave paintings were used to tell stories and pass on information e.g. tales of the
Dreamtime

Health Risks of Heavy Metal Pigments
Ancient cultures including the Egyptians and the Romans often used heavy metals in the
preparation of cosmetic products.
" Antimony - Sb2S3 was used as a kohl, mascara or eye shadow. It is known to be
carcinogenic and can cause nausea and vomiting in the short term
" Copper - used in eye make-up in the form of malachite or as a kohl in black copper oxide
form. It can cause anaemia, liver and kidney damage and intestinal irritation
" Lead - Galena (PbS) was crushed up and used in black eye makeup. White lead (PbCO3)
was also used as a face powder. Use may result in damage to the nervous system, mental
retardation and even death
" Mercury - often used in cinnabar (HgS) for lipsticks due to its vibrant red colour. Mercury
poisoning can result in numbness, tunnel vision and brain damage

Structure of Paintings
Wood and canvas (the support) are normally unsuitable to paint on directly as they are too rough
and absorbent and will therefore be prepared through layers of ground or by priming. Gypsum or
chalk would be applied as a warm liquid and then later scrapped off as a white layer. On the
ground, paint layers were added, which consisted of pigments mixed with a binding medium or
oil. Paint layers were then protected by a cover of varnish.


Medieval Painting
An example of a medieval painting is Madonna and Child with Saints Jerome, John the Baptist,
Bernardino and Bartholomew. The painter was Sano Di Pietro and it is estimated that the art work
was completed in Sienna, Italy 550 years ago.



In this painting, a layer of linen was glued to the wood. Next, a layer of gesso grosso (CaSO4) was
mixed in with animal glue, followed by finer layers of gesso sottile. Finer layers are highly polished
to a smooth surface and fine black powder is added to fill in any holes.

Charcoal was used in the underdrawing. The gold leaf was adhered to the surface of the pain
through oil, varnish or garlic juice. Mordant gilding was used in order to apply it over the paint.
Pigments used included vermilion (red), ultramarine (blue), gypsum (white), Naples yellow and
orpiment (yellow) and malachite (green).

Obtaining Colour
For paintings, colours are obtained through spreading several layers of paint and superimposing
them, allowing the creation of complex colour effects. Pigments themselves are rarely mixed.

The same pigments were also used in the production of coloured glass. The oxides were finely
powdered and added to the class mixture before melting e.g. cobalt oxide produces blue and
manganese oxide produces a purple, both in accordance to temperature and pressure. Flashing
involves coating clear glass with a thin layer of coloured glass to produce a lighter colour. Staining
involves painting glass with silver nitrate before firing it in an oven. According to the number of
times the glass is stained, a range of tones can be achieved.

Structure of Paints
Paint is formed through the colouring matter (the pigment) and a liquid (medium) which carries
the pigment, allowing it to be spread over a surface.

" A pigment is a substance in particulate form which is substantially insoluble in a medium,
but which can be dispersed in this medium to modify its colour
" The binder is the material used in paint that causes pigment particles to adhere to one
another to the support. This provides a protective film, improving hardness and resistance to
water

Examples of binders include:
" Egg tempera - formed when egg yolk is mixed with a pigment to form a long lasting paint,
used since the 14th century
" Linseed oil - mixed with pigments in varying proportions to form oil paints, goes brownish
yellow with age and is generally acidic
" Acrylics - these are used in the majority of synthetic paints used today as they are durable,
flexible and suitable for use on paper, panels and canvas

The Egyptians were advanced in using dyes, which are different to pigments in that the colouring
matter is dissolved in solution. This provided new pigments for painting e.g. vegetable dyes were
dissolved in water and fixed onto an insoluble white powder, which could be dried and extracted.

Lake pigments are manufactured by precipitating a dye with an inert binder. The binder used
must be inert and insoluble and must be white or very neutral. Madder lake is a natural pink-red
dyestuff formed form the root of the madder plant rubia tinctorium. Lakes are fugitive in that they
will lighten in a relatively short time when exposed to light because the dyes are unstable.

Increasing Range of Pigments
The very first Aboriginal cave paintings only used red, yellow and black pigments as these were
easily obtained in the forms of ochres and charcoal. As time progresses, new minerals are
available due to improvement in extraction methods e.g. terra verte (green earth) was the first
green pigment used and was only used after the iron silicate and clay mixture could be
extracted.

!"# "%&'( )&''( ,


The Egyptians and the Romans had better extraction technologies and therefore had a wider
array of pigments available. Better purification techniques mean pigments are more easily
isolated from ores.

More recently, there has been a shift from natural to synthetic pigments due to further
advancements in technology. More and more organic pigments (carbon based) are being used.

Colours and the Periodic Table


Metals are present in each pigment and most of the metals involved are transition metals. The
metals present in the pigment often have the same colour or colour range.



3#-4&56 = 8 >&6'%&'65 +1 &#5 ?&+, -0( 3+@+'6$

Flame Colours
A flame test reveals that many metallic elements emit light of a distinctive colour when their
compounds are heated in a flame or when their vapours are exposed to electrical discharge.

Name of Element Cation Flame Colour
Sodium Na
+
Yellow
Potassium K
+
Lilac
Calcium Ca
2+
Orange-red
Barium Ba
2+
Apple-green
Strontium Sr
2+
Red
Copper Cu
2+
Green-blue

Excitation of Electrons
According to the Bohr Model, electrons can move between energy levels by absorbing or
emitting photons. A photon is an energy packet of electromagnetic radiation and its energy will
equal the difference in energy between two orbits or energy levels.

Electrons are promoted or excited into higher energy levels when it is exposed to energy (e.g.
heat). As the electron drops down to lower energy levels, it emits photons characteristic of the
element and thus produces the colour we see.

The energy of an atom is not continuous but quantitised i.e. it exists only in fixed amounts. The
photon frequencies absorbed or emitted by an atom are fixed by the differences between
energy levels of the orbit of electrons. Any photon that has a frequency that lies between two
orbits is unable to excite the electron.

Line Spectra
Atoms give off visible light and other forms of electromagnetic radiation when heated or
otherwise energetically excited. However, this is not a continuous distribution of wavelengths (i.e.
the whole spectrum of visible light) but only consists of a few. Spectral lines are the discrete lines
which represent the frequencies of light emitted when a gaseous sample of an element is
dissociated and the atoms are excited.

The absorption spectrum is produced when atoms of a cool gas absorb photons of certain
wavelengths from white light and become excited from lower to higher energy levels. When
photons from the light pass through the gas, some of them can interact with the atoms and bump
an electron to a higher energy level (provided that they have just the right frequency). Photons at
those frequencies are thus absorbed by the gas and the rest pass through the sample. It therefore
appears as black lines against a bright background.

The emission spectrum is formed when atoms that have been excited to higher energy levels emit
photons characteristic of the element as they return to lower energy levels. In the visible part of
the electromagnetic spectrum, it is seen as coloured lines on a black background. Emission and
absorption spectra for the same substance have lines at identical positions.



!"# "%&'( )&''( -




The reflectance spectrum is formed when atoms and molecules absorb and reflect energy at
wavelengths related to their atomic structures. When a substance absorbs certain wavelengths of
light in the visible region, the colour of the substance is determined by the wavelengths of visible
light that remain. The substance exhibits the colour complementary to those absorbed.

Bohr Model of the Hydrogen Atom
In 1913, Bohr attempted to explain the hydrogen spectrum and proposed that in a hydrogen
atom, the electron moves around the nucleus in a circular orbit without radiating energy. He also
put forward the idea that only by emitting or absorbing a photon can an electron move from one
electron shell to another. Part of his proposal was the belief that the hydrogen atom had only
certain allowable energy levels or stationary states. Each state was associated with a fixed
circular orbit (electron shell).

In his work, Bohr used Rutherford's model of the atom, which involved electrons orbiting the
nucleus, as well as Max Planck's theory that energy is quantised i.e. it exists as photons.

The Principal Quantum Number
Bohr calculated a set of allowed energies, with each value corresponding to a circular path of
different radii. Each energy level corresponds to a principal quantum number (n), they will have
the values 1, 2, 3, 4 etc. The term shell can also be used to describe the energy levels. The energy
level closest to the nucleus is denoted as n = 1 and so on. The lower the quantum number, the
smaller is the radius of the orbit and the lower is the energy of the atom.

Energy Levels and Colours
Every line in the hydrogen spectrum represents a transition from one energy level to another.
When an electron jumps from one energy level to a lower energy level, a photon of radiation is
emitted. The energy of this photon is exactly equal to the difference in energy between the two
levels of this atom. For some of these emissions, the energy released is in the visible spectrum
region and so can be seen on the visible line spectrum.

When the electron is in a higher level, the atom is said to be in an excited state. When the
electron is in its lowest energy state, the atom is said to be in its ground state. Elements other than
hydrogen also show atomic line emission spectra when energetically excited electrons fall from
higher energy levels to lower ones.

Merits and Limitations of the Bohr Model
Merits


1) Bohr's model attempted to explain why electrons did not spiral into the nucleus (principle of
classical mechanics that explained how particles on a curved path emit EMR and so would
eventually lose energy)
2) Attempted to explain how emission and absorption spectra for different elements had a
different and complex energy structure
3) Was able to predict the line spectrum of hydrogen with reasonable precision

Limitations
1) The model does not make it possible to calculate the wavelengths of the spectral lines of
all the other atoms
2) It only works well for atoms with one electron in their outer shell but not for others
3) Does not explain why some spectral line are more intense than others
4) Does not explain hyperfine lines (e.g. Na doublet)
5) Could not account for the Zeeman effect where the emission spectrum shows a splitting of
spectral lines when a gas is excited in a magnetic field
6) The Bohr model is a mixture of classical and quantum physics

The Sodium Doublet
In the case of sodium, the 3p orbital splits into the two different
energy levels of 3p
3/2
and 3p
1/2
due to the magnetic fields caused by
the electrons' spins and their orbits (Zeeman effect). As these two
energy levels have a minute difference, there are two hyperfine lines
on the emission spectra known as the sodium doublet.

The two lines are 0.597 nm apart, with the line at 589.0 nm having
twice the intensity of the line at 589.6 nm due to the energy levels.

Analysis of Pigments
Infrared absorption spectroscopy identifies the presence of organic
functional groups (e.g. in binders and organic pigments) and allows
the molecules to be identified. It is both quantitative and qualitative but it is destructive in that you
have a take a sample and create a solution. The tested material has to be soluble in a solvent.

IR radiation sets up vibrations in the atoms of molecules. The wavelength at which a vibration
occurs is characteristic of the elements forming the bond. These vibrations can then be measured
by passing infrared light through the sample and recording at which wavelengths the absorptions
occur.

Ultraviolet absorption spectroscopy can be used to determine purity or concentration of the
solution of a substance that absorbs UV light as it can cause specific fluorescence in materials
depending on composition and age. The absorbing materials can then be compared to
developed calibration tools to make measurements. It is a quantitative tool.



!"# "%&'( )&''( .


Type of Analysis Source of Radiation Type of Detector
UV-Vis Tungsten lamp or deuterium
discharge tube
A photomultiplier tube which
detects and amplifies light
IR Heated ceramic e.g. a SiC rod A thermocouple

In double beam spectrophotometers, the radiation is split into two beams. One is passed through
the sample while the other is passed through the reference, usually the solvent used to dissolve
the substance being investigated. The detector measures the radiation passing through and a
comparison of the two beams allows the absorption of radiation to be determined.

Infrared reflectography is a non-destructive form of analysis that supplies information about the
whole painting. An IR reflectance lamp is shone on the surface of a painting and the reflected
light is detected. The IR radiation is able to penetrate the pigments and reflect off the white
ground. It is particularly useful for detecting under-drawings in a painting where the artist has used
graphite pencil, charcoal or black inks.

Ultraviolet reflectography uses the fact that higher energy photons in the UV region of the
spectrum are strongly absorbed in these varnishes and binding media. The absorption of UV
photons causes chemical reactions, sometimes resulting in the emission of photons in the visible
region i.e. fluorescence. It can provide additional information in identifying certain pigments and
varnishes.

Reflectance Spectra and the Effect of Infrared and Ultraviolet Light
Reflectance spectra of pigments can be used to determine their presence in different paintings. A
pigment can be studied by shining white light on the surface of the painting and then examining
the spectrum of light that is reflected. As the reflectance spectrum is the compliment of the
absorption spectrum, it can be compared to known spectra for identification.

" Infra-red radiation is known to change the colour of zinc oxide from white when cold to
yellow when hot
" It also changes red CuO2, malachite and verdigras permanently to black copper oxide
" UV light has less of an effect and just causes pigments to fluoresce
" ZnO fluoresces a yellow colour while malachite (containing copper) fluoresces a dirty-
mauve colour

Laser Microspectral Analysis
Laser microspectral analysis involves concentrating a powerful pulsed laser on a small sample of
the pigment to be identified. The material is then vaporised (i.e. it is destructive) and the vapour is
fed through a gap between two electrodes that sparks and excites the atoms and ions,
producing an emission spectrum as electrons are de-excited.

The obtained emission spectra consist of lines corresponding to the elements evaporated from the
sample surface. This is useful for determining trace elements in solid and liquid samples. It is
important as it has high sensitivity and requires minimal preparation.

It is particular useful in analysing the elemental composition of pigments used in restoring
paintings. A microscopic amount of a colour of the painting is vaporised using laser energy and
from the analysis, a synthetic substitute for this colour can be prepared. Another use is in the
identification of the validity of an artwork (i.e. whether a painting is from the era it is thought to
have been painted in).








!"# "%&'( )&''( **



3#-4&56 A 8 ;#5 956/+(/% ;-*@5 -0( B@5%&6+0 C/$&6/*'&/+0

Pauli Exclusion Principle
The Pauli exclusion principle states that no two electrons in the same atom can have the same
set of four quantum numbers. Each electron has its own 4 quantum numbers referring to the level
of the shell (n), sublevel or sub-shell (l), orbital (ml) and spin (ms).

Orbits and Orbitals
An orbit refers to the energy level or shell in which an electron can be found. An orbit with
quantum number n can contain up to 2n
2
electrons. An orbital is different and can contain zero,
one or two electrons. If two electrons are present they have opposing spins.

Sub-Shells
Experimental and theoretical evidence suggests that apart from the n=1 shell, each principle shell
consists of a number of energy sublevels or sub-shells with slightly different energies. The number
of sub-shells in any shell is equal to the quantum number of a shell e.g. the n=2 shell has two sub-
shells. More specifically, they are one or more orbitals with the same set of n and e quantum
numbers.

Ground States and Excitation
When an electron is in the orbital closest to the nucleus, it is in its ground state or lowest energy
level. Electrons are only able to move to a higher energy level when they absorb a photon whose
energy equals the difference in energy between the two stationary states.

Hund's Rule
Hund's Rule states that: if two or more orbitals of the same energy are available (same subshell),
then an electron will slot into each orbital until all orbitals are half filled with electrons of the same
spin before any orbital receives a second electron.

This produces a configuration of low energy. If two electrons were placed in the same orbital
when there were empty orbitals available, their mutual repulsion would result in a higher potential
energy.

The S, P, D and F Blocks
Information about energy levels and orbital shells can be
summarised:
" The lowest energy sub-shell within a shell is called a s-
subshell and contains one orbital i.e. an s-orbital. As
there is only one orbital, the maximum number of
electrons the sub-shell can accommodate is two
" The second lowest energy sub-shell within a shell is the
p-subshell, which contains three identical orbitals
called p-orbitals. As there are three orbitals, the
maximum number of electrons accommodated is six
" The third lowest energy subshell within a shell is called a
d-subshell and contains five orbitals called d-orbitals.
As there are five orbitals, the maximum number of
electrons the shell can hold is ten


" The fourth lowest energy subshell is a f-subshell and contains seven orbitals called f-orbitals.
As there are seven orbitals in a f-subshell, the maximum number of electrons held is 14

To determine the order in which sub-shells are filled, place the electrons into orbitals starting with
the lowest energy orbital first. Secondly, place a maximum of two electrons in each orbital but
where more than one orbital of the same energy is available, place one electron in each orbital
before pairing electrons up.

The atomic number of sodium is 11, meaning there are 11 electrons. The first two electrons are
located in the 1s orbital. The next two are located in the 2s orbital and the next six in the three 2p
orbitals in the 2p subshell. The 11th electron is located in the 3s orbital. The electron configuration
of sodium can therefore be written as 1s
2
2s
2
2p
6
3s
1
.

Electron Configuration and the Periodic Table
When elements are listed in order of
increasing atomic number, similar outer
shell or energy level electron
configurations are observed to recur at
regular intervals. In the periodic table,
elements with similar outer shell
electron configurations appear in the
same vertical group.

For example, the group IA elements all
have an s
1
outermost or valence shell
electron configuration.


Electronegativity
Electronegativity is a measure of the ability of an atom in a molecule to attract electrons to itself.
The greater an atom's electronegativity, the greater its ability to attract electrons to itself. It is
expressed on a relative scale with the most electronegative element fluorine assigned a value of
4.0.

Electronegativity depends on several factors:
" The number of protons in the nucleus
" The distance from the nucleus
" The amount of screening by inner electrons

Electronegativity increases across periods from left to right i.e. from metals to non metals. This is
because there is an increase in nuclear charge across the periods. Although an extra electron is
added for each element, this does not fully shield the effect of the increased number of protons.

Electronegativity decreases going down groups of the periodic table. This occurs because in
moving down a group, the size of the atom is increased and the attractive force of the shielded
nucleus is therefore reduced.

Ionisation Energy
Ionisation energy is the amount of energy required to remove the outermost electron from a mole
of gaseous atoms or ions. The first ionisation energy is the energy required to remove the first
electron from a neutral atom. Strength of ionisation energy will be determined by the same
factors affecting electronegativity.

The elements that show the highest ionisation energies are helium, neon and argon. As these are
the noble gases, this indicates that the electron configurations of these elements are very stable.
!"# "%&'( )&''( *+


On the other hand, the alkali metals (e.g. lithium, sodium and potassium) have very low ionisation
energies. This is because these elements have only one electron in their valence or outer shell.
Overall, this means that ionisation energy increases moving from left to right across a period.

There is a gradual decrease in ionisation energy going down a group. This occurs because the
outer electrons are further from the nucleus as atomic number increases. Although the charge on
the nucleus increases, the number of electrons shielding the outer electrons from the nuclear
charge also increases.



Successive Ionisation Energies
When successive electrons are removed from an atom, they are removed from their orbitals in the
reverse order to which they were filled. The second ionisation energy (l2) is the energy required to
remove the second electron and so forth. Successive ionisation energies of atoms have larger
values because the electrons are being removed from progressively larger positive charges.

The greater the charge on the ion from which the electron is removed, the greater the energy
required to remove the electron. Another factor that can contribute to an increase in ionisation
energy is the removal of an electron from a shell or energy level closer to the nucleus.





3#-4&56 D 8 ;6-0$/&/+0 E5&-@$

The Transition Elements
A transition metal is one which forms one or more stable ions which have incompletely filled d-
orbitals. Transition elements occupy the d-block of the periodic table. They occur in the fourth, fifth
and sixth rows of the periodic table and result from the filling of the d-subshell of the third, fourth
and fifth shells. Each d-subshell contains five orbitals and as a result, each transition series consists
of 10 elements.

Zinc has the electron structure [Ar] 3d
10
4s
2
. When it forms ions, it always loses the two 4s electrons
to give a 2
+
ion with the electronic structure [Ar] 3d
10
. The zinc ion has full d levels and therefore is
not a transition metal. When d-block elements form ions, the 4s electrons are lost first.

Oxidation States of Transition Elements
Oxidation states refers to the number
of electrons gained or lost by an atom
or ion. Transition metals differ from
most main-group metals in that they
exhibit a variety of oxidation states.
This is because they can lose
electrons from both the 3d and 4s
sub-shells, which have similar
energies.

The +2 oxidation state, which occurs
commonly for nearly all transition
metals, is due to the loss of two 4s
electrons. Oxidation states above +2
result from the additional loss of 3d
electrons. Maximum oxidation states
are equal to the total number of 4s
and 3d electrons in the atom. E.g.
from scandium through to
manganese, the maximum OS
increases from +3 to +7.

Oxidation States and Colour Changes
The colour of transition metal compounds are due to the absorption of photons of light by
electrons. The small energy differences between the d-orbitals are similar to the energies of
photons of visible light. Thus the absorption of photons of appropriate frequency can result in an
electron being excited from a lower to a higher energy orbital.

Transition metals in different oxidation states often exhibit different colours e.g. when yellow VO2
+
is
combined with zinc in dilute HCl, it is reduced to blue VO
2+
, then green VO
3+
and finally violet V
2+
.
The colour of transition metal compounds will often give a clue to the transition metal involved
e.g. most copper(II) compounds are blue while nickel compounds are usually green.

Species of Transition Metals as Oxidising Agents
Transition metal elements in their highest oxidation state will combine with highly electronegative
oxygen and fluorine e.g. chromium forms the chromate and dichromate ions. Complex ions such
as CrO4
2-
are strong oxidising agents because they contain many oxygen atoms. These are readily
able to absorb more electrons because most oxygen atoms only have six in their outer shell.
!"# "%&'( )&''( *,



In general, transition metal ions in which the metal has a high oxidation state tend to be strong
oxidising agents e.g. +6 in Cr2O7
2-
. The strength of an oxidising agent depends on the ease with
which the compound will accept electrons (and hence be reduced).



3#-4&56 F 8 3+@+'65( 3+,4@5G H+0$

Hydrated Ions
A hydrated ion is an ion in which a specific number of water molecules is associated with each
formula unit and is formed when an ionic substance dissolves in water, with the ions disassociating
and being surrounded by water. E.g. Cu
2+
forms blue Cu(OH2)4
2+
in aqueous solution. Hydrated
ions are examples of complex ions or coordination complexes.

Complex Ions and Ligands
In a complex ion, a central metal ion is surrounded by a group of anions or molecules called
ligands. The number of ligand atoms bonded to the central atom is the coordination number.
Examples of ligands include anions, such as Cl
-
and CN
-
, and polar molecules, including H2O and
NH3.

Compounds that contain complex ions are known as coordination compounds.


Due to the definition of Lewis acids and bases, ligands act as Lewis bases in complex ions. The
coordinate covalent bond forming between the ligand and the metal ion is therefore an
acid/base interaction. As all ligands are bases, they must have at least one unshared pair of
electrons that can be used to form a coordinate covalent bond to a metal ion.

The charge on the metal complex is equal to the charge on the metal ion (its oxidation state) plus
the sum of the charges on the ligands.

Chelated Ligands
Chelated ligands are ligands that have more than one donor atom. Ligands with two or more
donor atoms tend to form rings around the complex ion. Chelate comes from the Greek word
meaning 'crab's claw', with these ligands surrounding the metal ion like a crab claw.

!"# "%&'( )&''( *-



Bidentate ligands have two lone pairs of elections, both of which can bond to the central metal
ion. This includes the oxalate or ethanedioate ion (
-
OOC-COO
-
) or ethylenediamine.

Quadridentate ligands have four lone pairs, all of which bond to the central metal ion. An
example is haemoglobin, which consists of an iron (II) ion surrounded by a complicated molecule
known as haem. Haem is a hollow ring of carbon and hydrogen atoms, at the centre of which are
4 nitrogen atoms with lone pairs. A globin molecule and a water molecule then attach onto the
spaces above and below the iron ion.

A hexadentate ligand has 6 lone pairs of electrons. The best example is EDTA
(ethylenediaminetetraacetic acid) which is most commonly used as a negative ion (EDTA
-4
). The
EDTA ion entirely wraps up a metal ion using all of its lone pair of elections. This allows for medical
uses e.g. heavy metal poisoning.



Colours of Transition Metal Complexes
Different colours are seen in metal complexes because the energies of the d-orbitals are affected
by both the metal ions and its surrounding ligand groups. As there are separations in the energy
gaps between d-orbitals, the frequencies of the photons absorbed, and therefore the colour, is
affected.

Importance of Models
Models are important in explaining:
" How metal ligands form
" Why certain geometrical shapes are preferred
" Why these compounds are brightly coloured and
" Why some ligands can chelate

Valence Bond Theory
An extension of the Valence Bond Theory explained that bonding in the formation of complexes
depends on the orbitals available, the tendency of the ions or groups to share a pair of elections,
the number of molecules placed around a central ion and the geometry assumed by the ligands.
It assumes that all coordinate bonds are entirely covalent.

Example 1: Mn
2+
+ 4Cl
-
! MnCl4
2-
The Mn
2+
has the electron configuration of 1s
2
2s
2
2p
6
3s
2
3p
6
. One pair of
electrons on each chloride ion can form a covalent bond with the 4s
and each of the 4p orbitals on the manganese ion. This therefore
forms the sp
3
complex, which is tetrahedral in shape.



As Cl
-
is a weak field ligand, there was no forced pairing. As the complex ion has unpaired
electrons, it is paramagnetic i.e. it is attracted in a magnetic field. Valence bond theory
postulates that the electrons from the ligands are donated into the hybridised 4s and 4p orbitals.

Example 2: Fe
3+
+ 6CN
-
# Fe(CN)6
3-
The Fe
3+
ion has the electron configuration 1s
2
2s
2
2p
6
3s
2
3p
6
.
In this instance, the extra pairs of electrons of the cyanide
ions occupy the d, s and p orbitals of the metal ion and
the Fe
3+
is surrounded by six cyanide ions.

As CN is a strong field ligand, it creates forced pairing. Two unpaired electrons enter into orbitals
already with electrons, leaving two pairs and one unpaired. This creates empty d-orbitals for
incoming elections, allowing for the formation of hybridised d
2
sp
3
type orbitals. As there is one
unpaired electron a 3d orbital, the ion is very weakly paramagnetic. As only the inner d orbitals
are used, it is an inner orbital complex.

Example 3: Fe
3+
+ 6H2O # Fe(H2O)6
3+

As water is a weak field ligand, there is no
forced pairing. Instead, the 6 pairs of
electrons have to enter into the next 6
available orbitals, thus leading to sp
3
d
2

hybridisation. Again, it is paramagnetic but it forms an outer orbital complex because outer d-
orbitals are involved.

Crystal Field Theory
The Crystal Field Theory assumes that the bonds between the ligand and the metal ion are
completely ionic, with the ligand and metal ion being infinitesimally small, non-polarisable point
charges.

A crucial aspect of the theory uses the fact that as an approaching ligand nears a charged
particles, disturbances are caused in the electron clouds of both the ion and the ligand. This
affects the orientation and energies of the d-election orbitals and produces a new set of
unequally spaced energy states.

In a free atom, the d-electrons are said to be degenerate as they is an absence of an electric
field. If a field is applied in particular directions, the degenerate levels are separated into two or
more sets of levels, with the magnitude of the separation depending on the arrangement of the
ligands.

In the octahedral case, two orbitals are concentrated in regions of space pointing directly at the
bonding electrons of the ligands while the others are concentrated in regions away from the
bonding electrons. These electrons would prefer to be as far as possible from the electrons of the
ligands, leading to a separation into two sets: 3 at a lower energy and 2 at a higher energy.

If the transition metal ion has electrons in the d-orbitals, the electrons will enter the split d-orbitals
so that the lowest energy levels fill first. They will only pair when there is an energy advantage.

The ammonia ligands in the cobalt complex produce
a strong field, resulting in a large separation between
the energies of the orbitals. Less energy is used in
overcoming the repulsion of another electron in two
of the lower orbitals than would be needed to
promote two electrons to the higher orbitals. This is a
low-spin complex.
!"# "%&'( )&''( *.



The water ligands in the cobalt complex produce a weak field and therefore the separation
between the energy levels is less. The electrons remain unpaired, since the energy used to
promote two electrons to the higher levels is less than would be needed to overcome the
repulsion of another electron in two lower energy levels. This is therefore known as a high-spin
complex.

The crystal field theory can therefore explain the colours of transition metals. Electrons in the lower
d levels may absorb photons and move to higher d levels (d-d transitions). E.g. the violet colour of
the Ti(H2O)6
3+
ion occurs when the single d-electron absorbs a photon and moves to one of the
higher d-levels. The light transmitted by the solution will be white minus the green photons
absorbed i.e. violet.