Baulkham Hills High School- Year 12

Research and Communication Assessment Task Term4 2011Chemistry of Art (NOTES)

From the earliest times, people have used colours to decorate

themselves and their surroundings.
Identify the sources of the pigments used in early history as readily
available minerals

Early humans used pigments from natural sources such as ochre, clay and charred
wood, which were mixed with a medium (egg yolk, tree and plant gums).

In early history, indigenous populations could only obtain pigments that were readily
available in the environment around them, requiring little or no processing. But they
had a limited pallet and colours were mainly earth colours; red, yellow, black and white.
But over time, more colours came into use. Ochres are natural earths of silica and clay,
owing its colour (yellow to red) due to hydrous or anhydrous Iron (III) oxide.
Over time, the once bright ochre colours in rock paintings can alter due to changing
chemical reactions with underlying rock.

Colour
Black

White

Red

Brown

Source
Charcoa
lPyrolusi
teKaolinChalkGypsum
Haemati
te-

Burnt wood, animal bones, lamp

soot
Manganese(IV) dioxide

Limonit
e-

Chemical
Composition
Allotropes of C
MnO2

Hydrated aluminium silicate

Calcium carbonate
Calcium sulphate dihydrate

Al2O3.2SiO2.2H2O
CaCO3
CaSO4.2H2O

Anhydrous iron(III) oxide

Burnt yellow ochre

Fe2O3

Partly hydrated Fe2O3 iron(III) oxide

hydroxide

FeO(OH)

Yellow

Goethit
Hydrated iron(III) oxide
Fe2O3.H2O
eExplain why pigments used needed to be insoluble in most substances
A pigment is a coloured insoluble solid suspended in a medium. The pigment remains
insoluble such
that as the usually colourless medium dries, the colour
remains. Since pigments are insoluble, it's advantageous as they are not easily
removed when exposed to rain or ground water (i.e. cave, rock paintings). Also,
pigments used in cosmetics and body painting will not dissolve in sweat as they are
insoluble.
Most early pigments contained metal sulphides and oxides, which were insoluble in
most circumstances.

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By: Pratheep Muguntharajah

 Outline the early use of pigments for:

Cave drawings
Self-decoration including cosmetics
Preparation of dead for burial

Early humans used pigments in their cave drawings over 17000 years ago
using basic colours of red, yellow, black and white. Pigments were ground to
powder and combined with a medium (e.g. egg yolk, animals fats), which allows
the pigment to be transferred to the cave wall. They were applied using twig tips,
fingers or brushes of furs and feathers. These were important in Aboriginal art to
depict the Dreamtime, which were not only used on cave walls but also rocks and
bark. The predominate colours in cave drawings are red, yellow, black, and
white. These natural pigments were from red ochre, yellow ochre, kaolin,
charcoal and pyrolusite (Manganese(IV) oxide).
These pigments used to produce these colours came from readily available
minerals, as technology was too limited to
produce a wider range of colours
The pigments were first grinded to a fine
powder, then either applied directly to the
wall as a solid mixed with binder in a
medium as paint
The paints used in cave drawings generally
used saliva, honey from wild bees, or tree
gums as the binder, and water as the
medium

Pigments were also used for selfdecoration (cosmetics). The Aboriginal culture had certain dances and rituals
(e.g. corroboree, coming of age) where the body was
painted using red and yellow ochre. Egyptians used
Black kohl (Sb2S3) as a
black pigment for eyeliner
and eye shadow, Cinnabar
(HgS) was used as a bright
red pigment for lipstick and
rouge, Orpiment (As2S3)
was used as a rich lemonyellow pigment for body
paint and eye shadow, Malachite (CuCO3Cu(OH)2)
was used as a bright green pigment as body paint, particularly around the eyes

In the preparation of the dead for burial, pigments were also used. The
Egyptians painted the dead and the containers in which the body was entombed.
In Tutankhamens tomb, a paint box was found containing powdered gypsum,
orpiment, haematite and malachite, suggesting that these were used in the
preparation of his body. Red natron was used in body scrubs, which were often
buried with the dead along with other cosmetics such as cleansing creams of oil
and lime. The cosmetic pigments above were also used by ancient Egyptian
culture to prepare dead bodies for burial and the afterlife

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The internal organs of a body were often replaced with a fluid

containing a mixture of resins from coniferous trees, beeswax, and
aromatic plant oils. Elemental gold, either as gold leaf or as grinded
powder mixed with saliva and water, was also used to decorate
bodies and burial objects.

Explain what colour can be obtained through pigments

spread on a surface layer (e.g. paint) or mixed with the bulk
of material (e.g. glass colour)
Surface layer
Pigments can be spread on a surface, and the structure of early paintings included:
o Wood panel/canvas
o Ground
o Underdrawing
o Paint layers (possible gold gilding)
o Varnish
Colour can be obtained through pigments spread on a
surface layer (e.g. paints). The majority of paintings are on
wood panel or canvases, which have been prepared for painting with
layers of ground, as wood and canvas are too rough and absorbent to directly paint on.
For panels, the ground was traditionally a mixture of gypsum with animal glue (gesso).
It was applied as a thick warm liquid and set to a white surface layer which was then
rubbed smooth. Onto this ground the paint layers, pigments mixed with a binding
medium, are added. Historically, paint layers were superimposed to produce complex
colour effects; today, pigments are mixed to achieve this. These paint layers are
protected and the colours given clarity by a layer of varnish.
Metal oxide pigments can be finely powdered and added to a glass mixture before
melting. This mixes the pigments with the bulk of the material to produce coloured
glass. For example, cobalt oxide produces blue and iron oxide produces various greens.
Impurities in these oxides can lead to a wide range of colours.
Other methods
of producing coloured glass:
Flashing involves coating clear glass with a thin layer of coloured red glass
(made by copper (II) oxide) at the molten stage to form a light red coating,
producing ruby glass.

The process of staining involves painting glass with silver

nitrate and then firing it in an oven. According to the number
of times the glass was stained then fired, a range of yellow
tones could be produced.

Describe paints as consisting of:

The pigment
A liquid to carry the pigment

Paint consists of a pigment which gives the colour of the paint. Colorant
pigments add colour to the paint, and extender pigments develop properties of
the paint e.g. gloss. Hiding pigments e.g. titanium dioxide makes the paint
opaque to protect it from UV light. The pigment remains insoluble, so that as the
medium dries, the colour remains.

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The binder causes pigment particles to adhere to one another and to the
surface.
The medium carries the pigment and allows it to be spread over the surface.

Describe a historical example to illustrate the relationship between the

discovery of new minerals and the increasing range of pigments

The discovery of new mineral deposits throughout history, as well as increasing

extraction and refinement technologies, led to an increased range of pigments
available to painters
Examples of new discoveries leading to a wider range of pigments available include
Naples Yellow, chromium pigments, cadmium pigments and cobalt pigments.
NAPLES YELLOW
Chemical composition: Pb3(SbO4)2 [lead (II) antimoniate]
Colour: Yellow
Discovery: Naples Yellow was originally discovered in mineral deposits on the slopes of
volcanic Mt Vesuvius, but was synthetically produced during the 17 th century by the
prolonged roasting of oxides of lead and antimony.
CHROMIUM PIGMENTS
In 1770, an orange-coloured mineral was found in the Beresorf gold mine in Siberia by
chemist
The mineral was analysed, and determined to be a compound of lead and chromium ,
which had been recently discovered by French chemist L. N. Vauquelin
The discovery of vast deposits of the ore chromium, FeO.Cr 2O3 in the U.S. in the 1820s
led to the manufacture of a range of chromium compounds, including many pigments,
including
Chrome yellow (PbCrO4) [lead (II) chromate]- Produced by Vauquelin: When
solutions of lead (II) nitrate and sodium chromate are mixed, lead (II) chromate
precipitates out
Chrome red (PbCrO4.Pb(OH)2) [basic lead (II) chromate]
Chrome green, formed by mixing chrome yellow with Prussian blue

CADMIUM PIGMENTS
Cadmium was first discovered by Stromeyer in 1817, but cadmium pigments were only
produced until the 1840s due to the scarcity of the metal
Pigments include:
Cadmium yellow (CdS)
, prepared by reacting an acid solution of a cadmium
salt (either chloride or sulfide) with hydrogen sulfide gas or an alkali sulfide
Cadmium red (CdS.CdSe)(Calcium sulfide selenide) , which was not prepared
until 1910

Analyse the relationship between the chemical composition of selected

pigments and the position of the metallic component(s) of each
pigment in the periodic table

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By: Pratheep Muguntharajah

Most pigments contain a metal, most of which are

transition metals and are associated with a
specific colour range.
o Iron produces colours in the red-yellow
range
o Copper produces colours in the blue-green
range
o Cobalt produces colours in the yellow-violet
range
o Chromium produces colours in the redyellow range
It is the electron configuration of the transition metals that contribute to the
colour they produce. As the colour of the metal depends on the energy gap
between d orbitals. Different metals have slightly different d orbital energies
due to different electrostatic attraction, shielding and configuration.
The colour is given when the electron absorbs a photon of quantised energy and
it up and back down
Elements such as zinc are colourless as the d orbital is full
Transition metals of
different oxidation states
also exhibit different colours

Solve problems and

perform a firsthand
investigation or process
information from secondary
sources to identify minerals
that have been used as pigments and describe their chemical
composition with particular reference to pigments available and used
in traditional art by Aboriginal people

Ochres: natural earths of silica and clay which owe their colour (red-yellow) to iron (III)
oxide
Red ochre: anhydrous iron (III) oxide [Fe 2O3]
Brown ochre: nearly pure limonite [FeO(OH)]
Yellow ochre: hydrated iron (III) oxide, e.g. the mineral
goethite [Fe2O3.H2O]
o Burning yellow ochre drives off water, converting
it to red anhydrous form

ochres

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By: Pratheep Muguntharajah

Black Pigments:
Manganese (IV) oxide [MnO2]
Charcoal: mainly graphite [C]
o From burnt wood or lamp soot

Charcoal

Manganese

(IV) Oxide
White Pigments:
Chalk: calcium carbonate [CaCO3]
Kaolin: hydrated aluminium silicate [Al2O3.2SiO2.2H2O]
Gypsum: calcium sulfate dihydrate [CaSO4.2H2O]

Gypsum
Kaolin

Calcium Carbonate

Process information from secondary sources to identify the chemical

composition of identified cosmetics used in an ancient culture such as
early Egyptian or Roman and use available evidence to assess the
potential health risk associated with their use
Pigment/min
eral
Malachite

Azurite

Cinnabar

Orpiment

Composition

Cosmetic

Health Risks

basic copper
carbonate
[CuCO3.Cu(OH)2]
basic copper
carbonate
[2CuCO3.Cu(OH)2]
mercury (II) sulfide
[HgS]

Eye/body colouring

harmful if inhaled , can be irritant to

the eyes and can cause
gastrointestinal discomfort

Rouge, lipstick

Arsenic trisulfide

Yellow eye shadow

Mercury is toxic by ingestion,

inhalation or skin contact.
Accumulated poison can cause
damage to the Central Nervous
System
Arsenic is toxic by ingestion or skin

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By: Pratheep Muguntharajah

Realgar
Kohl

[As2S3]
Tetraarsenic
tetrasulfide [As4S4]
Stibnite: antimony (III)
sulfide [Sb2S3]

Orange-scarlet
eye/body colouring
Used as
eyeliner/mascara
to darken
eyebrows and
eyelids

Manganese (IV) oxide

[MnO2]

Galena [PbS]

Black copper (II) oxide

[CuO]

Soot from
fire

Carbon black [C]

Black eyeliner

White lead

Basic lead carbonate

[2PbCO3.Pb(OH)2]
Lead tetroxide
[PbO2.2PbO]

Face powder

Minium/red
lead

Face/body
colouring

contact. It is a suspected carcinogen

(cancer causing agent)
Symptoms: nausea, vomiting,
diarrhoea. Antimony will cause liver or
kidney damage if inhaled or ingested.
It can cause skin or eye irritation.
Prolonged skin contact may cause skin
burns.
Symptoms: Sluggishness, weakness in
legs, fixed facial expression, emotional
disturbances. Harmful by inhalation or
ingestion. May cause lung damage,
CNS impairment, and reduce fertility in
men
Symptoms: abdominal pain,
constipation, headache. Harmful by
ingestion or inhalation. Accumulated
poison may cause mental retardation
and/or death.
Can cause skin irritation.
Gastrointestinal discomfort if ingested
in large amounts, causing vomiting
and diarrhoea. May cause ulceration of
the respiratory tract
Respiratory irritant. Harmful by
ingestion or in inhalation. May contain
carcinogenic organic molecules.
Symptoms: abdominal pain,
constipation, headache. Lead is toxic
by ingestion or inhalation. It is both an
acute and a chronic poison.
Cumulative poison causes mental
retardation and death

Identify data, gather and process information from secondary sources

to identify and analyse the chemical composition of an identified range
of pigments
Aboriginal
Pigment/minera

Colour

Chemical Composition

Chemical

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By: Pratheep Muguntharajah

l
Red ochre
Yellow ochre

Red
Yellow

Anhydrous iron (III) oxide

Hydrated iron (III) oxides, e.g. the mineral

Formula
Fe2O3
Fe2O3.H2O

Brown ochre
Manganese (IV)

Brown
Black

goethite
Nearly pure limonite
Manganese (IV) oxide

FeO(OH)
MnO2

oxide
Charcoal
Kaolinite

Black
White

Mainly graphite
Hydrated aluminium silicate

C
Al2O3.2SiO2.2H2

Chalk
Gypsum

White
White

Calcium carbonate
Calcium sulfate dehydrate

O
CaCO3
CaSO4.2H2O

Egyptian/Roman:
Pigment/mineral

Colour

Chemical

Chemical Formula

Malachite
Azurite
Vermillion/Cinnabar
Orpiment
Realgar

Green
Blue
Red
Yellow
Orange-

Composition
Basic copper carbonate
Basic copper carbonate
Mercury (II) sulfide
Arsenic trisulfide
Tetraarsenic

CuCO3.Cu(OH)2
2CuCO3.Cu(OH)2
HgS
As2S3
As4S4

Egyptian blue/Blue

scarlet
Blue

tetrasulfide
Calcium copper silicate

CaO.CuO.4SiO2

frit
White lead
Minium/Red lead
Massicot
Verdigris

White
Red
Yellow
Blue-green

Basic lead carbonate

Lead tetroxide
Lead (II) oxide
Basic copper (II)

2PbCO3.Pb(OH)2
PbO2.2PbO
PbO
Cu(CH3COO)2.2Cu(O

acetate

H)2

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By: Pratheep Muguntharajah