CHM171L Physical Chemistry 2 Laboratory

2nd Quarter, S.Y. 2017-2018

Photochemistry
Legaspi, Ranaye V., Lojica, Kate M., Maquiling, Kenth Roger A.1, Calderon, Edna J.2
1Students, 2Professor, Physical Chemistry 2 Laboratory, CHM171L B21, School of Chemical Engineering and Chemistry, Mapúa University,
Muralla St., Intramuros, Manila 1002, Philippines
ABSTRACT
Final Report Information
Some reactions take place only in the presence of light or some other
radiation. Since different colored radiations in the range of visible light
Performed 02 December 2017 have different frequencies and hence different energies, all radiations
Submitted 09 December 2017
may not be able to initiate a particular reaction. These reactions are
called photochemical reactions. Photochemistry is the study of chemical
Keywords:
reactions, isomerizations and physical behavior that may occur under
Photochemistry the influence of visible and ultraviolet light. In order to further understand
Photochemical Reactions how photochemical transformation occurs, this experiment utilized the
Cyanotype Process cyanotype process to produce blueprint of an image using two soluble
Homolytic Cleavage iron (III) solutions: Potassium Ferricyanide, and Ferric Oxalate from the
Grotthuss-Draper Law reaction of Ferrous Chloride and Oxalic Acid. These two compounds do
Stark-Einstein Law not react with each other in the dark, but when they are exposed to
ultraviolet light. The reaction forms an insoluble blue compound, blue
iron (III) ferrocyanide, also known as Prussian blue which creates the
blueprint of an image printed in an acetate paper. The result of the
experiment was explained using the two Fundamental Principles of
Photochemistry, the Grotthuss-Draper Law and the Stark-Einstein Law.

INTRODUCTION In traditional black and white photography, silver

salts are employed to produce the black image.
Photochemistry, by definition is the field of
When chlorides of silver is made to be exposed
chemistry that deals with the interactions of light
to light, an electron is transferred from the
and the atoms or molecules of substances.
chloride to the metal ion and silver metal is
Photochemical reactions involve the absorption
produced. The silver metal produced by this
of light. It primarily concerns chemical reactions
reaction produces the dark color on the film.
brought about by the absorption of ultraviolet light,
Moreover, more than five decades ago
of wavelength 100 to 400 nm; visible light, of
photochemical reactions were commonly used
wavelength 400 to 750 nm; or infrared radiation,
for printing. Due to the characteristic color, they
of wavelength 750 to 2500 nm. A classic
were called blueprints. Blueprinting works by
example of photochemistry is photosynthesis,
placing a translucent sheet that contains the
where phototrophic organisms use energy from
diagram on top of sensitized paper and
light to synthesize glucose from carbon dioxide
irradiating it with light. The light is obscured by
and water. Another interesting case, with
markings on the translucent paper, and the
industrial importance is traditional photography
negative image is produced on the sensitized
and printing.
paper. The paper is developed and then washed

Experiment 4 | Group 7 | December 09, 2017 1 of 6

 CHM171L Physical Chemistry 2 Laboratory
2nd Quarter, S.Y. 2017-2018
in water. The copy emerges as a light-stable,
white-line print on blue paper (Reusch, 2013).
Photochemical reactions may be distinguished by
placing the symbol hν above the path of the
reaction or at the reactant side. This indicates
that energy from radiation must be absorbed for
the reaction to proceed (Klein, 2015).
𝑨 + 𝒉𝝂 → 𝑩
Generally, photochemical reactions are governed
by two laws, known as the the Laws of
Photochemistry. The first one, which is also
known as the Grotthuss-Draper Law, states that
light must be absorbed by a compound in order
for a photochemical reaction to take place. The
absorption of light by a compound, otherwise
known as photoexcitation, is the first step in all
photochemical processes. In this step, the
reactant is elevated to a state of higher energy,
otherwise known as its excited state. This law
provides a basis for the phenomena of
fluorescence and phosphorescence. On the other
hand, the second law of photochemistry,
otherwise known as the Stark-Einstein Law,
states that for each photon of light absorbed by a
chemical system, only one molecule is activated
for subsequent reaction. Mathematically,
𝑬 = 𝑵𝑨 𝒉𝝂
where NA is Avogadro’s number. This law, also
called the photochemical equivalence law,
applies to the part of a light-induced reaction that
is referred to as the primary process. In most
photochemical reactions the primary process is
usually followed by the so-called secondary
photochemical processes that are normal
interactions between reactants not requiring
absorption of light. As a result such reactions do
not appear to obey the one quantum–one
molecule reactant relationship. The law is further
restricted to conventional photochemical
processes using light sources with moderate
Experiment 4 | Group 7 | December 09, 2017
intensities: that is, high-intensity light sources
such as those used in flash photolysis and in
laser experiments are known to cause so-called
bi-photonic processes (the absorption by a
molecule of a substance of two photons of light)
(Skoog, Holler, & Crouch, 2007).
In the current experiment, the effect of light on
chemical reaction was visualized using the
reagents, ferric chloride (FeCl3), oxalic acid
(C2H2O4), potassium ferricyanide [K3Fe(CN)6],
and water.
EXPERIMENTAL SECTION
A. Preparation of Reagents
The experiment required three reagents to begin
with the cyanotype process: Ferric Chloride,
Oxalic Acid, and Potassium Ferricyanide.
Distilled water was also used in the experiment.
Ferric Chloride is a corrosive and hazardous
chemical. Prolonged exposure with this
compound may cause brown discoloration of the
eyes and excessive iron build-up in the body
causing nausea, stomach pain, vomiting,
constipation, and black bowel movements. Oxalic
acid is also harmful when swallowed and in
contact with the skin. Potassium ferricyanide has
low toxicity, but can still be hazardous to the eye
and the skin.
Wearing of protective gloves, protective clothing
and eye goggles are a necessity to avoid
complications.
B. Methodology
Photochemistry deals with the study of reactions
occurring under the influence of light. Hence, in
this experiment, both the presence and absence
of light will be crucial, and so it is important to
have conditions in which the light is reduced and
is maximized. In the experiment, a dark room
was provided, and it was made sure that the
2 of 6
 CHM171L Physical Chemistry 2 Laboratory
2nd Quarter, S.Y. 2017-2018
weather is sunny. Before the experiment, an
image was printed in an acetate paper. The
design should contain dark colors, suggestively
black.
To start with the experiment, one gram of ferric
chloride and oxalic acid were placed together in a
small beaker, and 50 mL of water was then
added. In a separate beaker, one gram of
potassium ferricyanide was also dissolved in 50
mL of water. In an area where the light was
reduced, the two solutions were mixed in a flat
tray. A filter paper was immersed into the solution,
wetting all parts thoroughly. Immediately, the
paper was withdraw and the excess solution was
drained. Afterwards, the acetate paper containing
the image was put over the filter paper. The tray
was then transferred into a place where it can be
exposed to strong sunlight. As the filter paper
turns blue, the acetate paper was removed and
the filter paper was washed with water and dried.
C. Treatment of Results
The reaction between the Ferric Oxalate and
Potassium Ferricyanide was discussed to
understand how Photochemistry works. The
blueprint resulted from the experiment was
explained using the Grotthuss-Draper Law and
the Stark-Einstein Law.
RESULTS
Figure 1. Resulting blueprint produced by the reaction of
Potassium Ferricyanide and Ferrous Oxalate with sunlight
Experiment 4 | Group 7 | December 09, 2017
DISCUSSION
a. Legaspi, Ranaye V.
Electron gets excited to a higher orbital level
when a molecule or atom in the ground state
absorbs light. When light is imparted to a
molecule in a quantity roughly equal to the
energy gap between the Highest Occupied
Molecular Orbital (HOMO) and Lowest
Unoccupied Molecular Orbital (LUMO), an
electron can be promoted from the HOMO to the
LUMO and bond cleavage can occur.
In order to be absorbed, a photon's energy has to
match an energy difference within the compound
that is absorbing it. For instance, in the case of
visible or ultraviolet light, the energy of a photon
is roughly in the region that would be appropriate
to promote an electron to a higher energy level.
Different wavelengths would be able to promote
different electrons, depending on the energy
difference between an occupied electronic
energy level and an unoccupied one. Other types
of electromagnetic radiation would not be able to
promote an electron, but they would be coupled
to other events. Thus, one reason a photon may
or may not be absorbed has to do with whether
its energy corresponds to the available energy
differences within the molecule or ion that it
encounters.
A photochemical reaction is a chemical reaction
initiated by the absorption of energy in the form
of light. This reaction causes the molecules to
undergo a transient excited state causing a
change from their physical and chemical
properties. When this occurs, these molecules
tend to form a new structure, or combine with
each other or other molecules, causing a
prolonged chemical chain reaction. The
photochemical reaction observed in the
3 of 6
 CHM171L Physical Chemistry 2 Laboratory
2nd Quarter, S.Y. 2017-2018
experiment occurred from Photochemical
Blueprint, also known as Cyanotype Process.
Cyanotypes are produced by the incidence of
strong ultraviolet light and are based on the light
sensitivity of iron (III) complex. In the experiment,
Ferric Chloride was reacted with Oxalic Acid as
its acid donor. The iron (III) ions are reacted with
the oxalate ions, producing Ferric Oxalate.
3C2 H2 O4 + 2FeCl3 →
yields
2FeC2 O4 + 6HCl +2CO2
Upon dissociation with water, the iron (III) oxalate
takes on a variety of forms in solution with
varying numbers of oxalate ions and water
molecules. Visible light photons lack the energy
to break the coordinate bond between the
oxalate ion and the iron (III) ion, but ultraviolet
light has the sufficient energy to break the bond
between the two ions homolytically, leaving one
electron behind on the iron (III) ion and
converting it to iron (II) iron. The oxalate ion
becomes a radical anion.
However, this radical ion is also unstable and
combines with another identical ion to become
stable oxalate ion again. That is why the reaction
mixture is combined with Potassium Ferricyanide
solution, so that the reactants are all present
together when the mixture is exposed to light.
The iron (II) ions produced react with
hexacyonoferrate (III) ions to reduce the iron by
donating an electron.
Fe2+ + [Fe(CN)6]3– → Fe3+ + [Fe(CN)6]4–
Upon exposure to sunlight, the ferrous oxalate
reacts with Potassium Ferricyanide to produce
Ferric Ferrocyanide. This reaction creates the
Prussian blue color of the solution which was
initially pale yellow-brown.
Although the blueprint produced in the cyanotype
process is dominantly in Prussian blue, there are
some white areas marking the design of the
Experiment 4 | Group 7 | December 09, 2017
image in the acetate paper. When the filter paper
with the acetate paper on top of it was exposed
to sunlight, the dark colors from the design
blocks some areas from the light, and hence
there are areas in the paper that remained
unreacted with the ferric ferrocyanide solution.
This is because only the light absorbed by the
system result to a photochemical change, as
stated by the Grotthuss–Draper Law. These
absorbed photons according to the Stark–
Einstein Law caused physical or chemical
change, which is the change of color of the
solution from golden-yellow to blue.
a. Lojica, Kate Ann M.
. Photochemical reaction, a chemical
reaction initiated by the absorption of energy in the
form of light. The consequence of molecules’
absorbing light is the creation of transient excited
states whose chemical and physical properties differ
greatly from the original molecules. These new
chemical species can fall apart, change to new
structures, combine with each other or other
molecules or transfer electrons, hydrogen
atoms, protons, or their electronic excitation energy to
other molecules. Excited states are
stronger acids and stronger reductants than the
original ground states.
Photochemistry is the underlying mechanism for all of
photobiology. When a molecule absorbs a photon of
light, its electronic structure changes, and it reacts
differently with other molecules. The energy that is
absorbed from light can result in photochemical
changes in the absorbing molecule, or in an adjacent
molecule (e.g., photosensitization). The energy can
also be given off as heat, or as lower energy light, i.e.,
fluorescence or phosphorescence, in order to return
the molecule to its ground state. Each type of
molecule has a different preference for which of these
different mechanisms it uses to get rid of absorbed
photon energy, e.g., some prefer fluorescence over
chemistry.
4 of 6
 CHM171L Physical Chemistry 2 Laboratory
2nd Quarter, S.Y. 2017-2018
There are two basic laws for Photochemistry. (1) The
first Law of Photochemistry states that light must be
absorbed for photochemistry to occur. This is a
simple concept, but it is the basis for performing
photochemical and photobiological experiments
correctly. If light of a particular wavelength is not
absorbed by a system, no photochemistry will occur,
and no photobiological effects will be observed, no
matter how long one irradiates with that wavelength of
light and (2) The Second Law of Photochemistry
states that for each photon of light absorbed by a
chemical system, only one molecule is activated for a
photochemical reaction. This law is true for ordinary
light intensities, however, with high-powered lasers,
two-photon reactions can occur, i.e., the molecule is
raised to a higher energy state than produced by
single-photon absorption.
One of many commercial processes of photochemical
reactions are photography. A photograph is an image
made by a photo-chemical reaction which records the
impression of light on a surface coated with silver
atoms. The reaction is possible due to the light-
sensitive properties of silver halide crystals.
b. Maquiling, Kenth Roger A.
Many neutral or negatively charged species,
such as the oxalate ion, can bond with metal ions.
Species that bond to metals in this way are called
ligands. Water, as it is known, forms quite weak
bonds with metal cations. When ligands are
added to a solution containing a water complex,
they will replace some or all of the water
molecules, forming new complexes. Such
reaction was exhibited in the experiment, when
oxalic acid was mixed with ferric chloride. The
new complex formed was the ferrioxalate ion,
with chemical formula [Fe(C2O4)3]3-. Each oxalate
ion forms two bonds with the ferric cation,
thereby being a bidentate ligand. When the
ferrioxalate complex absorbs light energy, it
undergoes photoreduction, where light causes an
internal electron transfer. The ferric cation is
Experiment 4 | Group 7 | December 09, 2017
reduced to the ferrous cation, and one of the
oxalate groups is oxidized to carbon dioxide. The
reactions proceed as follows.
𝑶𝒙𝒊𝒅𝒂𝒕𝒊𝒐𝒏: 𝑪𝟐 𝑶𝟐−
𝟒 + 𝒉𝝂 → 𝟐𝑪𝑶𝟐 + 𝟐𝒆
−
𝑹𝒆𝒅𝒖𝒄𝒕𝒊𝒐𝒏: 𝟐𝑭𝒆𝟑+ + 𝟐𝒆− → 𝟐𝑭𝒆𝟐+
𝑶𝒗𝒆𝒓𝒂𝒍𝒍: 𝟐𝑭𝒆𝟑+ + 𝑪𝟐 𝑶𝟐−
𝟒 + 𝒉𝝂 → 𝟐𝑪𝑶𝟐 + 𝟐𝑭𝒆
𝟐+
The ferricyanide ion from the added potassium
ferricyanide, K3[Fe(CN)6], will then react with the
formed ferrous ion, forming the insoluble
Prussian Blue, Fe4[Fe(CN)6]3, adhering to the
fibers of the cloth or paper, and producing the
blueprint of the image, with the exposed portions
being blue and the covered portions being white.
The covered portions were white simply because
they were not exposed to light, and thus no
reduction reaction for the ferric cation occurred
and no Prussian Blue was formed.
𝟑−
𝑭𝒆𝟐+ + 𝑭𝒆(𝑪𝑵)𝟔 → 𝑭𝒆𝟑+ + [𝑭𝒆(𝑪𝑵)𝟔 ]𝟒−
𝟑−
𝟒𝑭𝒆𝟑+ + 𝟑𝑭𝒆(𝑪𝑵)𝟔 → 𝑭𝒆𝟒 [𝑭𝒆(𝑪𝑵)𝟔 ]𝟑
The experiment was successful in demonstrating
a common photochemical reaction, which
involves the redox reaction between an oxalate
group of the ferrioxalate complex and the ferric
cation due to absorption of light energy.
Moreover, the experiment was also able to
demonstrate the first law of photochemistry,
otherwise known as the Grotthuss-Draper Law,
which states that for a photochemical reaction to
proceed, energy from radiation must be absorbed
first. This was demonstrated in the experiment by
observing that the exposed portions of the final
image formed turned blue, indicating that a
reaction occurred (formation of Prussian Blue),
while the covered parts were white, indicating
that no reaction occurred, due to the fact that
there was no exposure to light and light energy
was not absorbed. In addition, the experiment
was also a success in familiarizing the
researchers of the techniques and methods of
5 of 6
 CHM171L Physical Chemistry 2 Laboratory
2nd Quarter, S.Y. 2017-2018

image formation by using photochemical Master Organic Chemistry:

reactions. https://www.masterorganicchemistry.com
/2013/08/30/radical-reactions-why-is-
CONCLUSIONS AND RECOMMENDATIONS
light-or-heat-required/
As the reaction proceeds, the silver atoms grow into
APPENDIX
clusters, which are large enough to scatter light and
A. Results of the Experiment
produce colors in a pattern identical to that of the
original light source. Photography utilizes this
chemical principle to record color and black and white
images. Silver salt chemistry remains the preferred
method of recording high quality images, despite
advances in electronic technologies.

There are three key steps involved in making a

photograph: exposing the film to light, developing the
image, and printing the photograph. While there are
other types of photographic films, such as polaroid
and slide films, and other mediums in which to
B. Reactions Involved
develop photographs.
Oxidation: C2 O2−
4 + hν → 2CO2 + 2e
−
Upon doing the experiment, the objectives were Reduction: 2Fe3+ + 2e− → 2Fe2+
successfully met and the experiment was done Overall: 2Fe3+ + C2 O2−
4 + hν → 2CO2 + 2Fe
2+

accordingly. 3−
Fe2+ + Fe(CN)6 → Fe3+ + [Fe(CN)6 ]4−
3−
4Fe3+ + 3Fe(CN)6 → Fe4 [Fe(CN)6 ]3
REFERENCES
Klein, D. (2015). Organic Chemistry. John Wiley
and Sons, Inc.
Reusch, W. (2013, May 5). Photochemistry.
Retrieved December 11, 2016, from
Photochemistry:https://www2.chemistry.
msu.edu/faculty/reusch/virttxtjml/photche
m.htm
Skoog, D. A., Holler, F. J., & Crouch, S. R.
(2007). Principles of Instrumental
Analysis, Sixth Edition. Thomson
Brooks/Cole.
Royal Society of Chemistry (2017). Making and
Using Blueprint Paper. Retrived from
RSC Website: http://www.rsc.org/learn-
chemistry/resource/res00001591/making
-and-using-blueprint-paper?cmpid=
CMP00004334
James (n.d.). Radical Reactions: Why Is “Light”
Or “Heat” Required? Retrieved from

Experiment 4 | Group 7 | December 09, 2017 6 of 6