Name________________________________________ SC_____-_____ Date___________

EXPERIMENT 16: BLUEPRINTING: A PHOTOCHEMICAL REDOX PROCESS

Equipment:
Materials:

3 test tubes, 2 beakers, tape. white paper, tracing paper, sharpies, scissors, (optional: photoflood lamp or UV light, Lucite
sheets, binder clips)
Iron (III) chloride (FeCl3), oxalic acid (H2C2O4), potassium iron(III) cyanide (K3Fe(CN)6), ((NH4)xFeyC6H5O7),

Aim: How can we use a redox reaction to prepare a blueprint?

INTRODUCTION.
In this experiment, Prussian blue a dark blue pigment is formed by a series of chemical reactions:
Step 1: Potassium iron(III) cyanide is combined with another iron(III) compound, iron(III) ammonium citrate. Citrate is
a polyatomic ion with three carbons in the +3 oxidation state. When iron(III) ammonium citrate absorbs ultraviolet light,
the iron(III) and one of the C+3 atoms undergo a photochemical redox reaction.
UV light

Fe3+ + C+3

Fe2+ + C+4

equation 1.

Step 2: The Fe2+ product is exposed to potassium iron(III) cyanide, K3Fe(CN)6 , and they react to yield solid Prussian blue
(insoluble precipitate). Iron(III) ammonium citrate and potassium iron(III) cyanide do not react and remain water soluble.

Fe 2+ + K3Fe(CN)6 KFeFe(CN)6(s) + 2K+

equation 2.

Blueprinting is a way of making copies by exposing treated paper through a mask (or stencil) so that Prussian blue forms
in areas exposed to UV light, but not in other areas. After exposure, the unreacted compounds are washed away with
water leaving patterned Prussian blue.The pigment has both iron(II) and iron(III) and strongly absorbs red, orange and
yellow light, but, absorbs blue light less strongly so that it reflects blue light.

PRE-LAB QUESTIONS
1. Assign oxidation numbers. [4 pts]
Fe in FeCl2 ___ C in CO2 ___
C in H2C2O4 ___ Fe in K3Fe(CN)6 ___
2. Which is a balanced reduction half-reaction?
[1 pt]
a. Fe3+ Fe2+ + eb. C+3 C+4 + ec. Fe3+ + e- Fe2+
d. C+3 + e- C+4
3. Circle ionic compounds that are insoluble in
water: [2 pts]
Fe(OH)3 Ca(OH)2 Fe(C2H3O2)2 Fe2(CO3)3
4. In the following equation: [2 pts]
Pb(s) + Pb

+4

2Pb

5. Write two balanced half-reactions and balance

the whole reaction. [4 pts]

Fe+2 + Mn+7 Fe+3 + Mn+4

6. When an atom absorbs light, do its electrons

jump to a higher energy level or fall to a lower
energy level? [2 pts]

+2

a. The oxidizing agent is __________

b. The reducing agent is __________

WEEK 1 PROCEDURE
A. Treat paper with photoactive iron(III) compound
Label a piece of plain white paper (about 3" X 4") with your name and coat it with a solution of iron(III) ammonium
citrate. This may be accomplished by holding the paper by one corner and drawing it over the surface of the ferric
ammonium citrate solution. Allow the paper to dry in the dark. Your teacher will store the paper in a dark envelope for
week 2.
B. Experiment with iron(III), oxalic acid (having C+3) and sunlight
Label four test tubes according to the table below. Add (2-4 mL) of FeCl3 to tubes 1,2, and 3. In test tube 2, add an equal
amount of oxalic acid solution and shake. Pour half of this solution into tube 4. Place tubes 1 and 2 away from the light,
for example under a box. Expose tubes 3 and 4 to sunlight or a photoflood lamp. After 5 minutes record the appearance of
each tube in the table below. Then, add a few drops a few drops of K3Fe(CN)6 to each one and record any changes.
Observations
Before adding
K3Fe(CN)6

1. FeCl3
DARK

2. FeCl3 + oxalic acid

DARK

3. FeCl3 +
LIGHT

4. FeCl3 + oxalic acid

+ LIGHT

After adding
K3Fe(CN)6
[5 pts per box]
1. Which combination of reactants appears to be necessary for a blue precipitate to appear? [3 pts]

2. If the blue precipitate is Prussian blue, then what ion of iron must have been present before adding K3Fe(CN)6? [3 pts]
3.

Write the oxidation numbers for each atom that changes in following unbalanced reaction.
FeCl 3 + H2C2O 4

UV light

HCl + CO 2 + FeCl 2

a. Write the half-reaction for oxidation: [3 pts]

b. Write the half-reaction for reduction: [3 pts]

c. Balance the reaction. [3 pts]

4. Compare this redox reaction to the equation 1 in the introduction section. [5 pts]

WEEK 2 PROCEDURE
C. Prepare a mask for blueprinting .
Prepare a design for your blueprint by either: Drawing a design on tracing paper with a sharpie (lines must be VERY
thick) or by cutting a design into thick paper or aluminum foil (e.g., letters,
snowflakes).
D. Photochemical Redox.
Press the mask flat against the treated paper so that there are no gaps between the
papers. Tape the papers to a window so that the mask blocks some of the light from
hitting the treated paper for about 10 minutes depending the strength of the sunlight.
E. Development of the image
Remove the papers from the window. Dip the treated paper in a solution of K3Fe(CN)6
for a moment, remove it, and rinse the paper with GENTLY running tap water. Let it
dry and attach your blueprint to your report.

1.

Complete parts B, C and D on the flow-chart for the blueprinting process. [10 pts]

A
Fe

3+

Fe

Fe

3+

Fe

3+

Fe

3+

Fe

3+

Fe

3+

UV

dry

3+

Stencil or marker
Where is there a color
change? Label where on
3+
the paper the Fe remains
2+
and where Fe is formed.

Paper w/ iron(III) ammonium citrate

Dip in K3Fe(CN)6

rinse

Label areas of blue and white.

Where is there a color change? Label the area

of the KFeFe(CN)6(s) precipitate.

2.

In terms of the oxidation state of the Fe ions, why did only the sunlight-exposed parts of your blueprint paper
turn blue? [4 pts]

3.

In terms of solubility, why did the unexposed areas become lighter as the paper was rinsed, while the sunexposed areas remained blue? [3 pts]

CONCLUSION [2 pts per blank]

The blueprint process depends upon the

of Fe+3 to Fe+2,

where C+3 acts as the _____________ agent and

the energy in this

________________ (exothermic/ endothermic) reaction is provided by

______________.