EXPERIMENT VI

PHOTOCHEMICAL REDUCTION OF IRON (III) IONS

THE PURPOSE OF THE EXPERIMENT: to study photochemical reduction reactions and

study their use for blueprints.
INTRODUCTION
Iron is a type of metal that is abundant in nature number two after aluminium. Iron is
mostly in the form of hematite, Fe2O3, magnetite, Fe3O4, limonite, FeO(OH), and siderite,
FeCO3. Ferrous metal dissolves easily in dilute mineral acids. With non-oxidizing acids and
free air, iron will dissolve into iron (II) ions, whereas if there is air or oxidizing acids used, iron
(III) will be produced.
Iron (II) and iron (III) ions can form complexes that are almost entirely octahedral. The
hexacyanoferrate (II) complex ion, commonly known as ferrocyanide, is an example of a very
stable iron (II) complex. This ion can form salt with several cations.
The iron (III) ion in the solution is easily reduced to iron (II) by weak reductors such as
the I- ions.
Fe3+ + I- ↔ Fe2+ + ½ I2
In solution, iron (III) ions form complexes with water molecules as their ligands. This
complex ion has a tendency to experience hydrolysis.
[Fe(H2O)6]3+ ↔ [Fe(H2O)5(OH)]2+ + H+ or
2 [Fe(H2O)6]3+ ↔ [Fe(H2O)4(OH)2Fe(H2O)4]4+ + 2 H+
In this experiment, photochemical reduction of iron (III) to iron (II) will be studied
which is utilized in the printing process. Iron (III) can be reduced by oxalic acid to iron (II) and
the rate of this reaction can be accelerated by irradiating reagents. Iron (II) ions can react with
hexacyanoferrate (III) ions to form a blue complex. The amount of iron (III) ions reduced to
iron (II) by the influence of light can be shown by the thickness of the blue colour (blue turn
bull).
Because redox reactions occur very quickly by the influence of light, to slow down the
reaction process in a printing press so that it can be carried out in laboratory diffusion light,
diammonium hydrophosphate is added to the reagents. If diammonium hydrophosphate is not
added, the process must be carried out in a dark room.
In the printing process, an object whose shadow will be printed is placed on sensitive
paper and the part that is not covered is exposed to sunlight. Then the paper is put into a solution
of hexacyanoferrate (III) ions and unreacted iron (III) oxalate washed with water.
TOOLS AND MATERIALS
a. The tools used:
1. A 400 mL beaker glass
2. Dark room (cupboard)
3. Glass chips
b. Chemicals needed:
1. Oxalic acid
2. Diammonium hydrophosphate
3. Iron (III) chloride
4. Tick paper and tracing paper
5. Hydrochloric acid solution
6. K3Fe(CN)6 0,1 M solution
7. K2Cr2O7 0,03 M solution
PROCEDURE
1. Make a mixture of 100 mL iron (III) chloride ion solution with 20 mL of diammonium
hydrophosphate solution in a 400 mL beaker glass. Store the solution in a dark room
(cupboard).
2. Add 100 mL of oxalic acid to the iron (III) chloride solution in the cupboard, then stir
the solution in the room. After that, close the cupboard and open it only needed.
3. Take four pieces of paper tick, and dip it into the solution in the cupboard. Try to get
all the paper dipped in solution but not damage the paper.
4. Remove the paper and place it between the two-filter paper. Leave the paper in between
two filter paper for 10-15 minutes so the paper dry. If sharper prints will be produced,
the paper must be dried overnight therefore the edges of the print do not expand. This
step is still being done in the cupboard. After drying, this paper is used as sensitive
paper.
5. Make the object to be printed on tracing paper written in Chinese ink, for instance.
6. Place the object on sensitive paper and pinch it with two pieces of glass, then the object
is exposed to light. If exposed to sunlight, the exposure time is 4-5 minutes.
7. Take the sensitive paper that has been irradiated and then dip it in a 0,1 M
hexacyanoferrate (II) ion solution in a 400 mL beaker. Try to get all the paper dipped
into the solution.
8. Remove the paper and dip it in a dilute potassium dichromate solution (0,03 M). Then
wash the paper first with 100 mL 0,1 M and then with tap water.
9. Dry the paper, the blue print will be written according to the writing on the object.
TASK
1. If there are two solutions each containing iron (II) and iron (III) ions, estimate which
solution has a lower pH. Explain!
Answer: the reason that these ions are acidic is because of the pull of the electrons towards
the positive central ion. An ion with 3+ charges on it is going to pull the electrons more
strongly than one with only 2+ charges.

In 3+ ions, the electrons in the O-H bonds will be pulled further away from the hydrogens
than in 2+ ions.
That means that the hydrogen atoms in the ligand water molecules will have a greater
positive charge in a 3+ ion, and so will be more attracted to water molecules in the solution.

If they are more attracted, they will be more readily lost - and so the 3+ ions are more
acidic.

2. Why diammonium hydrophosphate solution can inhibit the redox reaction between iron
(III) ions and oxalic acid?
Answer: