Chemiluminescence Notes

chemiluminescence
Fireflies, jellyfish and glow sticks one flies, one lives deep in the ocean and one provides entertainment in night
clubs
Chemiluminescence is the production of light from a chemical reaction. Two chemicals react to form an excited (highenergy) intermediate, which breaks down releasing some of its energy asphotons of light (see glossary for all terms
in bold) to reach its ground state
A + B -> AB* (Excited Intermediate) -> Products + Light
Figure 1: Movement between electron shells

A hydrogen atom in its ground state. A single electron is in shell n = 1. Each shell has its own energy level.
When the hydrogen atom absorbs a quantum (defined amount) of energy, it is promoted to a higher energy
level (shell n = 2) and is now in an excited (high-energy) state. We draw an asterisk (*) next to the molecule to
indicate this.
The electron falls back down to its original position in the ground state (shell n = 1). In the process, a packet
of energy (a photon) is released in the form of electromagnetic radiation. The wavelength depends on the
amount of energy. If the wavelength is within the range of visible light, the electron transition will be
perceived as light of a particular colour.
Luminol, a glow-in-the-dark chemical

The release of a photon of light from a molecule of luminol is a fairly complex, multi-stage process. In a basic
(alkaline) solution, luminol exists in equilibrium with its anion, which bears a charge of -2. The anion can exist in two
forms (or tautomers), with the two negative charges delocalised on either the oxygens (the enol-form) or on the
nitrogens (the ketol-form; see Figure 3, below).
Molecular oxygen (O2) combines with the enol-form of the luminol anion, oxidising it to a cyclic peroxide. The required
oxygen is produced in a redox reaction (i.e. one in which both reduction and oxidation occur) involving hydrogen
peroxide (H2O2), potassium hydroxide and (for example) potassium hexacyanoferrate(III) (K3[Fe(CN)6], also known as
potassium ferricyanide). The hexacyanoferrate(III) ion ([Fe(CN)6]3-) is reduced to the hexacyanoferrate(II) ion
([Fe(CN)6]4-, giving potassium ferrocyanide, K4[Fe(CN)6]), while the two oxygen atoms from the hydrogen peroxide are
oxidised from oxidation state -1 to 0:
The cyclic peroxide then decomposes to give 3-aminophthalate (3-amino-1,2-benzenedicarboxylic acid) in an excited
state, along with a molecule of nitrogen (N2) see Figure 3, below. This decomposition reaction is favoured because
the cyclic peroxide molecule is highly unstable, and the reaction involves breaking some weak bonds. It is also
favoured because of the increase in entropy (disorder) due to the liberation of a gas molecule. When the excited 3aminophthalate drops down to the ground state, a photon of blue light is released.
Chemiluminescence in forensics
Figure 4: Haem group in

haemoglobin
The iron atom (Fe) in the
centre of the porphyrin ring
catalyses the reaction of
luminol
Image courtesy of Chemistry
Review
Forensic scientists use the reaction of luminol to detect blood at crime scenes. A mixture of luminol in a dilute solution
of hydrogen peroxide is sprayed onto the area where the forensic scientists suspect that there is blood. The iron
present in the haem unit of haemoglobin (seeFigure 4) in the blood acts as a catalyst in the reaction described
in Box 1. The room must be dark and if blood is present, a blue glow, lasting for about 30 seconds, will be observed.
The forensic investigators can record this glow by using photographic film, which can be used as evidence in court for
the presence of blood at the scene. (For a teaching activity about forensic science, see Wallace-Mller, 2011.
Because the iron acts as a catalyst, it is only required in trace amounts, therefore only a tiny amount of blood is
required to produce a positive result. This means that blood can be detected even when it is not visible to the naked
eye.
Using luminol at the scene of a crime

One of the drawbacks of using luminol is that the reaction can be catalysed by other chemicals that may be present
at the crime scene, for example, copper-containing alloys, some cleaning fluids such as bleach, and even
horseradish. Clever criminals can clean up the blood with bleach, which destroys the evidence of the blood, but
bleaching the carpet may alert people to the crime sooner. Urine also contains small amounts of blood, which can be
enough to catalyse the reaction of luminol. Once luminol has been applied to the area, it may prevent other tests from
being performed there. However, despite these drawbacks, luminol is still used by forensic scientists as a tool to
solve crime.
In the nightclub
Figure 5: How a glow stick works. Click to enlarge image

When you snap a glow stick and it begins to glow, the light produced is an example of chemiluminescence
(see Figure 5). Glow sticks comprise a plastic tube containing a mixture including diphenyl oxalate and a dye (which
gives the glow stick its colour). Inside the plastic tube is a smaller glass tube containing hydrogen peroxide. When the
outer plastic tube is bent, the inner glass tube snaps, releasing the hydrogen peroxide and starting a chemical
reaction that produces light (see Box 2). The colour of light that a glow stick produces is determined by the dye used
(see Box 3).
Chemiluminescence reactions, such as those in glow sticks, are temperature-dependent. The reaction speeds up as
the temperature rises snapping your glow stick in hot water will produce a fantastic glow, but it will not last as long
as it would at room temperature. Conversely, the reaction rate slows down at low temperature; this is why keeping
your glow stick in the freezer for several hours can allow the stick to glow brightly again when it is removed and
warmed up, long after it would otherwise have stopped glowing. The reaction does not stop completely in the freezer,
but it does slow down so that the glow is barely detectable.
Chemistry of glow sticks
When diphenyl oxalate reacts with hydrogen peroxide (H2O2), it is oxidised to give phenol and a cyclic peroxide. The
peroxide reacts with a molecule of dye to give two molecules of carbon dioxide (CO2) and in the process, an electron
in the dye molecule is promoted to an excited state. When the excited (high-energy) dye molecule returns to its
ground state, a photon of light is released. The reaction is pH-dependent. When the solution is slightly alkaline, the
reaction produces a brighter light.
What makes glow sticks different colours?

The dyes used in glow sticks are conjugated aromatic compounds (arenes). The degree of conjugation is reflected in
the different colour of the light emitted when an electron drops down from the excited state to the ground state.
iving glow sticks
A firefly glowing
Image courtesy of Terry Priest;
image source: Flickr
Have you ever walked along a beach at night and seen sparks of light around your feet? Or been in the countryside
at night and seen fireflies flitting about? These are examples of bioluminescence and around 90% of deep-sea life
also exhibits this strange phenomenon. These organisms have evolved to produce light because it has many useful
functions. Glowing can be used as a lure to catch prey, as camouflage or to attract potential mates. Some bacteria
even use bioluminescence to communicate.
The term glow worm describes the larvae of several species of insect, including fireflies; some of them glow to scare
off predators, whereas other species use their glow to attract prey. There are species of squid and crustacean that
can release clouds of bioluminescent liquid to confuse predators while they make their escape. Creatures living deep
in the ocean have evolved to produce mainly blue or green light because it transmits well through seawater. This is
because blue light has a shorter wavelength than red light, which means it is absorbed less readily by particles in the
water.
Figure 6: The structure of

firefly luciferin.
Click to enlarge image
Review (structure)
Bioluminescent reactions use ATP (adenosine triphosphate) as a source of energy. The structure of the lightproducing molecules varies from species to species, but they are all given the generic name luciferin. The structure of
firefly luciferin is shown in Figure 6, left. When fireflies glow, the luciferin is oxidised to produce an excited complex,
which falls back down to the ground state, releasing a photon of light, just like the chemiluminescent reaction of
luminol described in Box 1. However, fireflies do not use hydrogen peroxide and potassium hexacyanoferrate(III) to
oxidise luciferin; instead they use molecular oxygen and an enzyme called luciferase (this is also a generic name
luciferases vary from species to species).
Aequorin was first

discovered in the jellyfish
Aequorea victoria
Image courtesy of Typoform /
the Royal Swedish Academy of
Sciences (RSAS)
Luciferase
Luciferin + O2 Oxyluciferin + Light
There have been a number of experiments investigating aequorin, a protein found in certain jellyfish, which produces
blue light in the presence of calcium (see Shaw, 2002, and Furtado, 2009) and can thus be used in molecular biology
to measure calcium levels in cells. Some scientists have come up with other ideas for utilising bioluminescence in the
future, for example self-illuminated Christmas trees. Can you think of any other exciting potential uses for this
amazing natural phenomenon?
Anion: an atom (or group of atoms) that bears a negative charge.
Click to enlarge image

Review
ATP: adenosine triphosphate occurs in all known life forms. It is the primaryenergy currency in cells. ATP is formed
from ADP (adenosine diphosphate) and phosphate during energy-yielding reactions (such as the oxidation of
glucose), and is broken down (to ADP and phosphate) to release this energy in order to drive unfavourable reactions.
Bioluminescence: The production of light by living organisms. Bioluminescence may result from the absorption of
light (fluorescence orphosphorescence, e.g. in many deep-sea fish) or from a chemical reaction
(chemiluminescence, e.g. in fireflies).
Catalyst: A substance that makes a reaction occur faster, but that does not undergo a permanent chemical change
during the reaction (i.e. is not used up in the reaction). Catalysts work by providing an alternative route for the
reaction that is lower in energy.
Chemiluminescence: A type of luminescence in which the electrons are excited by a chemical reaction, for example
the reaction of luminol described in Box 1.
Conjugated: Conjugated systems mainly arise in chemistry when there are double bonds next to each other. The
atoms in a conjugated system are held together by covalent bonds and have alternating single and multiple bonds
(mainly double bonds, but triple bonds are also capable of being in conjugation). Alkenes are flat; conjugated systems
must always be planar to allow delocalisation of the electrons throughout the system. The dye molecules in Box
3 are all examples of conjugated compounds.
Covalent bonds: Bonds between two atoms where a pair of electrons are shared between them.
The electrons in benzene are

delocalised in a conjugated
system
Review
Delocalised: When molecules have conjugated bonds, the electrons are free to move around throughout the entire
conjugated system. These are referred to as delocalised electrons. The electrons in a benzene ring are delocalised,
and this is why all the carbon-carbon bonds are the same length.
Fluorescence: A type of luminescence in which the electrons are excited by light, e.g. in the security markings on
banknotes.
Luminescence: The production of light, usually at low temperatures, for example by chemical reactions or electrical
energy. Incandescence, in contrast, is light generated by high temperatures.
Phosphorescence: As fluorescence, but the glow lasts for longer (according to some definitions, over 10
nanoseconds), for example glow-in-the-dark stickers.
Photon: A quantum (packet) of light energy.

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chemiluminescence

Figure 1: Movement between electron shells

Luminol, a glow-in-the-dark chemical

Figure 4: Haem group in

Using luminol at the scene of a crime

Figure 5: How a glow stick works. Click to enlarge image

Chemistry of glow sticks

What makes glow sticks different colours?

iving glow sticks

Figure 6: The structure of

Aequorin was first

Click to enlarge image

The electrons in benzene are

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