EXPERIMENT VI

PHOTOCHEMICAL REDUCTION OF ION IRON (III)

A. OBJECTIVE

Study the iron (III) reduction as a result of photochemical reaction and understand their
application in blueprints.

B. INTRODUCTION

Photochemical Reaction

Photochemical is part of the chemistry that studies the interactions between atoms, small
molecules, and light (or electromagnetic radiation). As other disciplines, photochemistry using metric
system units. Units and constants are often used include the meter, second, hertz (Hz), joules (J),
moles, the gas constant (R), and Boltzmanns constant. All units and constants are also part of the field
of physical chemistry. Photochemical process is one of the most urgent things considering that the life
on earth is started with utilization of solar power (Tryono, 1994). Study about photochemistry is all of
the phenomenon that connect with adsorption and emission of radiation by chemical sytem. Especially
including spectroscopy phenomenon such as floursence and phosphorsence: chemical reaction that
radiatte light and photostimulate reaction like photograpy, photosyntesis, and all kind of photolisis
reaction. The lights influence to chemical system can be tested with some experiments. If amount of
lights quantity doesnt have enough energy to dissociate their molecules, then amount of energy will
be released as thermal energy (Seilbert W, 1979).

Photochemical reactions involves the absorption of light. An important example of

photochemistry in Nature is photosynthesis, where plants and algae use the energy from light to make
glucose from carbondioxide and water. Photodegradation, where sunlight is used to break down plastic
bags, is an enviromental aspect of photochemistry. Photochemistry can also be found in other areas
such as traditional photography and printing.

In traditional black and white photography, silver salts are used to produce the balck image.
When silver chloride is exposed to light, an electron is tranferred from chloride to the metal ion and
silver metal is produced. It is the silver metal made by this photochemical reaction that produces the
dark colour on the film.

More than fifty years ago, photochemical reaction were commonly used for printing. Because
of their coloring they were called blueprints. Architects and engineers used blueprints because they
allowed them to reproduce exactly the same thing many times.

Blueprinting works by placing a translucent sheet that contains the diagram on top of sentitised
paper and irradiating it with light. The light is obscured by markings on the translucent paper, and the
negative image is produced on the sensitised paper. The paper is developed and then washed in
water. The copy emerges as a light-stable, white line print on blue paper (Laboratory Manual, 2006)

Iron is the second of the metal abundance in earth crust following Al metal. Clean iron is quite
reactive, in the moist condition it can be oxidized and give iron (III) hydrate oxide that unable to
protect because this substance letting another new metal surface to open. The refined iron called
pirofor, their metals are highly soluble in mineral acid. By acid, nor vacuum oxidator, Fe (II) obtained.
If hot HNO3 is used and at the atmosphere, Fe (III) formed. The stong oxidizing reagent such as
concentrated HNO3 or another acids that contain dichromate make the iron into passive form.

The important ores of iron: magnetit, hematit, siderite, pirit, and chalcopirit. At the industrial
field, cast iron is used in frying pan/wok pan. One of the compounds is iron (III) chloride or ferric
chloride. FeCl3 solution in water has acidic characteristic, so thats why it can dissolving iron into
FeCl2. FeCl3 is soluble in water, alcohol, and eter if theres hydrochloride. The function of FeCl 3 are:
(1) in organic chemistry can be used to chlor carrier (as AlCl 3) in chlorination, (2) in medical field, it
can be used as blood coagulation, and (3) in paint industry, can be used as oxidator.

The presence experiment of iron (III) can be done by adding hexasianoferrat (II) ion;
precipitation of Prussian-blue colored iron (III) hexasianoferrat (II) Fe 4 , proving there is iron (III)
exists:

4Fe3+ (aq) + 3 (aq) Fe4

This blue colored compound usually utilized as ink, paint, including blueprint pigment. The
presence experiment of iron (III) gives sensitive reaction by adding potassium tiosianat solution, red-
bricked colored ion occur. This color is so sensitive to be recognized, so the presence of small amount
impurities in iron (III) can be detected.

In the reaction of iron (II) with potassium cyanide, there will be brownish-yellow colored
precipitation of iron (II) in excessive reagent, which is got from hexacyanidoferrate (II) ferocyanide
([Fe(CN)6]4-. The reaction is

Fe2+ + 2CN-
Fe(CN)2

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

The dry substance that contains hexasianoferrat(II) alkali, is dissolved when reacted to carbide
iron, alkali cyanide, and nitrogen. By dissolving residue in acid, iron can be detected in this solution.
For the reaction of iron (II) ion with potassium iron hexacyanidoferrate (II) in the vacuum, white
precipitate is occured with the following reaction:

Fe2+ + 2K+ [Fe(CN)6]4- K2Fe[Fe(CN)6]

At the atmosphere, reaction of iron (II) with potassium hexacyanidoferrate (III) light-blue
precipitation is occured. First thing is that hexacyanidoferrate(III) oxidizing iron (II) to be iron (III) so
the hexacyanidoferrate(II) is formed, with the following reaction is:

Fe2+ + [Fe(CN)6]2- Fe3+ + [Fe(CN)6]4-

And this ions join to make Turnbull-blue colored precipitation:

4Fe3+ + 3[Fe(CN)6]4- Fe4[(CN)6]3

Note that the precipitate composition is identic to Prusia-blue. People used to think the
composition is iron (II) hexacyanidoferrate(III) (Fe 3[Fe(CN)6]2. The composition and structure of
Turnbull-blue color and Prussian-blue color are proved by Mossbauer spectroscopy recently. This
precipitations is dissoved by NaOH or KOH where iron (III) hydroxide is precipitated.
 According to Jaka (2012), there are couple things that need to be considered in order to make
iron(III) reduction experiment successful:

a. The cabinets must be completely shut so there is no light when reaction is happened.
b. When mixing oxalic acid and iron (III) chloride, take long time so the solution becomes
homogenous.
c. When dipping the paper ict, keep all parts of it submerged. As a help use the stirring
rod and it can be touched to make sure all parts of the paper ict are covered.
d. Paper ict must be dried completely before into next process.
e. When printing process, make sure the parts of paper ict and mold are not shifted.
f. The light used for the irradiation should be bright enough, it can comes from sunlight
or UV sprectrometry.

C. EQUIPMENT AND MATERIALS

Materials: Equipments:
1M oxalic acid 1 piece glass 400ml beaker
0.1 M diamonium hydrophosphate The cabinets
FeCl3 solution 0.1 M Petridish cups
HVS paper and tracing paper Tweezers
0.1 M hydrochloric solution
K3Fe(CN)6 solution 0.1 M
K2Cr2O7 solution 0.03 M
Filter paper

D. WORK INSTRUCTION

Make a solution of 10ml FeCl3 0,5M in 10ml diammonium hydrophosphate 0,5M in glass
beaker
Keep the solution in dark room
Add 10ml of oxalic acid 1M to FeCl3 and stir
Close the cupboard and open only when
neccessary
Take 2 sheets of paper and dip it into solution

Remove the paper and place it between 2 filter paper for 10-15minutes

Make an object with black ink

Place the object on sensitized paper and nip with two pieces of glass
Hit to the sunlight for 4-5minutes
Then dip into hexasianoferrat (III) ion 0,1M solution, keep all the paper immersed

Next, dip into pottasium dichromate 0,03M solution. Wash the paper with 100ml of
0,1M HCl, followed by tap water and dry it in room temperature
E. OBSERVATION
1. Color of iron(III) chloride solution at first: orange
2. Color of diamonium hydrophosphate
solution at first: colorless
3. Color of mixed solution: bright yellow
4. Color of the solution+ oxalic acid: bright yellow
5. Color of paper after being immersed in the
solution: Prussian blue
6. Printouts:

(40 minutes) (30 minutes)

7. Reactions:
Mixed solution:
FeCl3 (aq)+ (NH4)2HPO4(aq) FePO4(aq) + 2 NH4Cl(aq) + HCl(aq)

Mixed solution + oxalic acid:

2 FePO4(aq) + 3 H2C2O4(aq) 2 FeC2O4(aq) + 2 H3PO4(aq) + 2 CO2(g)

Dipped in hexacyanidoferrate ion:

Fe2+(aq) + [Fe(CN)6]3-(aq) Fe3+(aq) + [Fe(CN)6]4-(aq)
4Fe3+(aq) + 3[Fe(CN)6]4-(aq) Fe4[Fe(CN)6]3 (aq)

Dipped in dichromate ion solution:

[Fe(CN)6]3-(aq) + 3K2Cr2O7(aq) 2 K3[Fe(CN)6](aq) + 3Cr2O72-(aq)

Washed by hydrochloride:
K2Cr2O7(aq) + 2HCl(aq) 2KCl(aq) + H2Cr2O7(aq)

F. DISCUSSION
The aim of Photochemical reduction of ion iron (III) is study about reduction of iron (III)
reaction in photochemical process and learning of utilization in blue printing. First, 25 ml of FeCl 3 0.1
M mixed with 25 ml of (NH4)2HPO4 0.1 M in glass beaker. This step must be done at dark room, due to
slow the reduction reaction from Fe3+ to Fe2+ that rapidly reacts when it is objected to sunlight, either in
addition of oxalic acid in the next step. This reaction occurs spontaneously, because iron (III) ion tends
to settle on the condition of Fe3+ and form bond which is very stable with PO 43- ion, so iron(III) ion in
this structure has lower energy. The equation of reaction is:
FeCl3 (aq)+ (NH4)2HPO4(aq) FePO4(aq) + 2 NH4Cl(aq) + HCl(aq)

The mixed solution is added with 25ml of oxalic acid. This adding process still in dark room,
because oxalic acid is strong oxidator so the addition of oxalic acid is to reduce Fe3+ to Fe2+ . The
following reaction is:
2 FePO4(aq) + 3 H2C2O4(aq) 2 FeC2O4(aq) + 2 H3PO4(aq) + 2 CO2(g)
 Two pieces of paper dipped in those solution. The dipping process is done in dark room and
took 15 minutes long. After dipped into solution, papers must be dried by placing it in between two
filter papers. The function of filter paper is to absorp solution in paper ict so it speed up the drying
process. Filter paper has bigger pores rather than sensitised paper, so it can absorp the solution that
covered on paper ict and the drying process will go faster. The drying process took 15 minutes long
aswell, the papers ict then used as sensitised paper.

While waiting for the sensitised paper in the dark room dried, we were setting up a pattern or
writing on each the tracing papers using boardmarker. Next, the object on tracing papers placed on the
top of sensitised paper then clamped using object glass.

Because on that day was raining, the irradiation process is done under the UV rays with the
variation of time: AREMA (30 minutes) and JUARA (40 minutes), after all papers is objected to the
UV rays according to its various time, sensitised paper is dipped in potassium hexacyanidoferrate (III)
[K3Fe(CN)6], potassium dichromate (K2Cr2O7), HCl solution and washed it with flowing water
sequentially.

The function of hexacyanidoferrate (III) ion is to sharpen the pattern on sensitised papers by
forming a blue colored complex so its proving the presence of iron ion. The reaction is oxidation from
Fe2+ to Fe3+ by hexacyanidoferrate (III) ion. The following reaction is:
Fe2+(aq) + [Fe(CN)6]3-(aq) Fe3+(aq) + [Fe(CN)6]4-(aq)
And those ions re-reacted:
4Fe3+(aq) + 3[Fe(CN)6]4-(aq) Fe4[Fe(CN)6]3 (aq)

From the reaction above, the Prussian-blue colored product is obtained due to the pattern on
tracing papers that blocking UV rays, the result on sensitised papers were some parts had lighter color
based exactly like the written pattern. Next, sensitised papers is dipped in K2Cr2O7 solution that has a
function to bonding the impurities of hexacyanidoferrate(III) ion and to bonding the excessive
hexacyanidoferrate(III) ion that used. Then washed with HCl, this aim to bonding the impurities that
had not been disappeared from potassium dichromates leaching. After that, to have a good result the
sensitised paper washed by flowing water. Washing by water has a function to eliminate the impurity
ions that left and excessive HCl used. The equation reaction when it washed by HCl solution is:
K2Cr2O7(aq) + 2HCl(aq) 2KCl(aq) + H2Cr2O7(aq)

The ferrioxalate complex absorbed light at the blue end of the visible light spectrum resulting
in an internal electron transfer reaction in which Fe3+ is reduced to Fe2+. Potassium
hexacyanidoferrate(III) K3[Fe(CN)6], then reacted with the Fe2+ ions to produced a component with a
deep blue color called Prussian blue. This allowed us to detect if the ferrioxalate complex had
undergone photochemical reduction and also gave the blue color in the blueprints.
In this experiment were done only 2 various of time which are 30 minutes and 40 minutes.
Theoritically, the result shows that the longer of exposure time then the color will be seen more clearly.
There is a connection between exposure time and written pattern, the longer exposure needed then the
longer time possiblity of reduction of Fe3+ into Fe2+ is needed. So, the Prussian blue color is more
clearly to be seen. In this experiment, the good result was the sensitised paper that got exposure time of
30 minutes under UV rays. This is the opposite result when considered with theory because the 40
minutes exposure will get better result rather than 30 minutes due to the longer exposure needed then
the longer time possibility Fe3+ to reduction into Fe2+ and the color will be seen more clearly.
 There are factors that influenced in photochemical experiment, those factors also affecting the
color of the result:
1. Exposure time
This factor has important role in photochemical reaction because exposure time
affecting color of the result. Exposure under sunlight or UV rays actually is to reducing
Fe3+ into Fe2+, but every object has ideal/maximum exposure time to reach maximum
color. So it can say that 30 minutes is ideal time to expose the sensitised paper under
UV rays rather than 40 minutes of sensitised paper.
2. Wavelength
Wavelength of light affect the reaction, white light is made up of different colors with
different wavelengths. Blue light has the shortest wavelength and red light has the
longest wavelength in the visible spectrum. But because this experiment is done in
exposure under UV rays, it cant be differentiate between the result under the sunlight
due to raining day on that time.

The light affect redox reaction of iron(III) oxalate, where the longer light is objected to the
sample that contains iron(II) then the color thats obtained is sharper/more clearly. As theoritically, it
says that the amount of light influences iron(III) to iron(II) reduction and will be seen as the sharpen
blue color that formed. The influential of light to this reaction has major affect because the light will
fasten the reduction itself. (Syamsidar HS, Ahmad Yani, loc.Cit).

Many neutral or negatively charged species, like the oxalate ion, can bond with metal ions.
Species that bond to metals in this way are called ligands. Water forms quite weak bonds to metal ion.
When ligands such as oxalate or ammonia are added to a solution containing a water complex, they are
able to replace some or all of the water ligands to form new complexes such as ones you make in this
experiment. This figure shows some example of complex ions.

Figure.1 Some Example of Oxalate, Water and Ammonia Metal Complexes

Each oxalate ion forms two bond with the iron(III) ion. As it attaches with two teeth, the
oxalate ion is called a bidentate ligand. Other ligands, such as water and ammonia are called
monodentate as they can only form one bond with metal ion.

Ferrioxalate, the complex ion used in this experiment, has the formula [Fe(C2O4)3]3-. Its
systematic name is tris(oxalato)ferrate(III) ion and it is synthesised by adding oxalic acid to iron(III)
nitrate, as shown this figure bellow:

Figure.2 The Synthesis of Ferrioxalate

When the ferrioxalate complex absorbs light energy, it undergoes photoreduction, where the
light causes an internal electron transfer. Iron(III) is reduced to iron(II) and one of the oxalate groups is
oxidised to CO2, as shown this figure:

Figure.3 The Photochemical Reaction of Ferrioxalate

Potassium hexacyanidoferrate(III), K3[Fe(CN)6], reacted with Fe2+ ions to produced a deep blue
color called Prussian blue. This allowed us to detected if the ferrioxalate complex had undergone
photochemical reduction reduction and gave the blue color in the blueprint.

G. CONCLUSION

Photochemical reduction of Iron(III) is one of the reaction that needing the sunlight exposure or
it can be replaced with UV rays. Fe 3+ is reduced to Fe2+ and Prussian blue colored-sensitised papers
were obtained. In addition, the longer of exposure time then the color will be seen more clearly. But in
this experiment, the good result is 30 minutes exposured sensitised paper. This is due to couple of
factors that influence photochemical reaction: exposure time, and wavelength. Every sensitised paper
has ideal/maximum exposure time and wavelength to reach maximum color. The application of
blueprints is used by architects and engineers, they allowed them to reproduce exactly the same thing
many times when they are about to design a building.

F. SUGGESTION

1. This experiment must done in dark room. If the laboratory doesnt have dark room, the
cabinets is the best choice to be the dark room in this experiment.
2. Pick the cabinets who have larger room so person who must be operating in cabinet can
move easily.
3. To get various results of photochemical reduction experiment, you can add mica paper,
paperboard to compare with paper ict.
 4. You can also add the various of light exposure by under UV rays and compare it to
sunlight but it depends on weather. If the weather isnt well, the UV rays is only the best
choice.
5. If using the UV rays as exposure light, you also can get the various wavelength to
compare.

G. REFERENCE

Cotton, F. Albert dan Geoffrey Wilkinson. 2009. Basic Inorganic Chemistry. Terj. Sahati Suharto,
Kimia Anorganik Dasar. Jakarta: UI-Press

Hendari, Jaka, Percobaan-6-Jaka, scribd.com.8 April 2012. www.scribd.com. Diakses pada tanggal
18 Maret 2017

HS, Syamsidar dan Ahmad Yani. 2012. Penuntun Praktikum Kimia Anorganik. Makassar: UIN Alaudin
Makassar

Laboratory Manual. 2006. School of Physical, Enviromental and Mathematical Sciences, University of
New South Wales at Australian Defence Force Academy.

Tim Dosen Kimia Anorganik. 2017. Inorganic Chemistry Manual Labwork. Semarang: Chemistry
Laboratory UNNES