Experiment 1

Cyanotype Blue Printing

Chemical required: 0.5 M Oxalic Acid, 3.5 M diammonium phosphate, ferric chloride,
0.1 M ferricyanide, 0.03 M potassium dichromate, 0.1 M HCl

Apparatus required: 100ml volumetric flask (2), 500 ml beaker (1), glass rod, dropper,
25 ml measuring cylinder (1), 25 ml volumetric flask (1), crystalline dish (3) etc.

Theory: The cyanotype or “blueprint” photographic process is one of several alternative

photographic methods. In blueprinting, ferric ions in an organic-iron complex (such as
ammonium ferric oxalate) are reduced by light. The ferrous ions formed in this reaction are
reacted with potassium ferricyanide to form ferroferricyanide (insoluble blue compound).

2 (NH4)3Fe(C2O4)3 2CO2 + 2Fe(C2O4) + 3(NH4)2(C2O4) (under UV-light)

ferric ferrous

Fe(C2O4) + K3Fe(CN)6 KFe[Fe(CN)6] + K2(C2O4)

8KFe[Fe(CN)6] 2Fe4[Fe(CN)6]3 + 2K4Fe(CN)6

Ammonium iron oxalate has good penetration on paper and a film negative or an object
whose silhouette is to be printed is placed on the paper and the uncovered portion is exposed
to sunlight. Later the paper is treated with ferricyanide solution and the excess ferric oxalate
is washed from the paper. The unexposed and partly exposed parts will have none or less
amount of ferrous iron and so the blue formed there will be less.

Procedure:-
1. Pour 100 mL of 0.5 M oxalic acid into a 400 mL beaker and add 20 mL of the 3.5 M
diammonium phosphate solution and mix well.
2. Place the beaker in your locker or any place, which has subdued light, and add 100 mL of
ferric chloride solution while stirring.
3. If a precipitate is formed, further stirring should dissolve it. Shut the locker and open it
only when required, as the light sensitive ferric oxalate is ready to react.
4. Immerse four pieces of bond paper of size 4” x 2.5” in the freshly prepared sensitizing
solution. Curling the paper into a semicircle and sliding it into the beaker may do this. Rotate
the beaker and make sure that the paper is thoroughly wet.
5. Remove the wet pieces of paper and place them between sheets of filter paper. (Make sure
that the paper which touches the sheet does not have any reducing agents). This should be
done as quickly as possible and in a partially closed locker.
6. The length of time required for drying varies according to the type of print one wants to
make. For opaque objects whose silhouettes are to be made, dry it for 10- 15 minutes. If the
paper is not dried long enough, the edges of the shadows will appear fuzzy. For making prints
from photonegatives, the paper must be dried completely. Moist paper can otherwise affect
the gelatin on the negative.
7. After the paper has dried, remove it from the filter paper sheets, place the opaque object on
the top of the sensitized paper, compress it between sheets of glass and expose to sunlight.

The time required for exposure of a normal print in bright sunlight is about 4-5
minutes. During printing do not hold the glass plates, but lay them on the desk,
windowsill or any flat surface.

8. After the exposure, smoothly dip the paper into 100 mL of 0.1 M ferricyanide solution kept
in a wide-mouthed dish. This as well as the following operations can be carried out in diffuse
light on top of a desk. It is important that the paper is immersed all at once, otherwise lines
will appear on the blue field of the print.
9. Remove the paper and dip it in 100 mL of the 0.03 M potassium dichromate solution for a
minute (dichromate is a well-known contrasting agent in photography). Afterwards, wash the
paper first in 0.1 M HCl and then in tap water.

Make a series of 3-4 exposures, varying the time of exposure to optimize the best
conditions. Use these conditions to obtain the most satisfactory pictures later.
Experiment 2
Acetylation of Ferrocene

The acetylation of ferrocene with acetic anhydride and phosphoric acid is a simple, rapid
reaction which gives a mixture of unchanged ferrocene (I) and acetylferrocene (II). Elution
chromatography of the mixture in a regular chromatography column or a buret results in two
highly colored hands. A yellow band, easily eluted from the column with petroleum ether, is
unchanged ferrocene; and a reddish-orange band, eluted from the column with benzene or
petmleum ether-ether, is acetylferrocene.
An appropriate scale synthesis involves three grams of ferrocene with 10 ml acetic anhydride,
to which two ml 85% phosphoric acid is added carefully with coustant stirring. After about
10 minutes heating on a steam bath (protected by a CaCl2 tube) the contents are poured onto
about 40 g ice. When the ice is melted, the mixture is neutralized to pH 7 with solid NaHCO3.
Approximately 1/2 hr of further chilling is needed to precipitate the brown solid from the
deep orange solution. The solid is collected on a suction filter and washed with water until
the filtrate is pale orange. The solid should be air dried for 15 minutes.
A 0.3-g sample of the brown solid is dissolved in a minimum amount of benzene (1.5-2 ml)
and introduced onto an alumina column with the help of a dropper. Solvent is run out until
the level of deep orange-red solution has fallen to the level of the upper layer of sand. About
2 ml more benzene is added along the walls of the buret to ensure that all of the solution has
entered the alumina column.
The column is filled with petroleum ether for the elution. The unchanged starting material,
ferrocene (yellow), will travel through the column at a faster rate than the product,
acetylferrocene (red-orange). The color observed during the chromatography provide an easy
separation. A deep brown color may be due to an intractable tar. When all the ferrocene has
been separated from the acetylferrocene by elution with petroleum ether, benzene or
petroleum ether-ether is used to remove the acetylferrocene from the column.