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C 141 (Expt. No. 10) NAME : _______________________________________ BATCH : _________ ROLL No.

: ________________________ SIGNATURE : _________________________________ DATE : __________

AIM To study the photochemical




of ferric

oxalate in cyanotype



THEORY The quite cyanotype long-lasting or blueprint photographic blue. distinct reactions : complexes ferric to are reduced and with citrate react process is one of several alternative photographic methods, which relies on the normally on in 2 photoreduction of ferric ions. Cyanotypes are

and are relies present ferric ions

Cyanotype (a) by (b) the called

chemistry ions light (for


organic-iron ammonium are form

example, formed to blue,

ammonium ferrous potassium

oxalate) ; allowed an insoluble blue compound



Fe4 [Fe(CN)6]3 . 15 H2O.

The structure of Prussian blue has hexacoordinate Fe (II) bound through the carbon atoms, and To hexacoordinate achieve the in Fe (III) bound through the of the nitrogen atoms, forming an extended by also water water cubic framework. stoichiometry, reduces some cubic otherwise one - fourth ligand in the Fe (II) sites thus lattice. ferric oxalate are as created. are occupied and water are There molecules. This occupy molecules the number of bridging empty sites positions crystal cyanide groups, molecules

The chemical equations for follows : (a)

the reactions involved in blueprinting with

Under UV light, ferric oxalate (or its ammonium salt) gets reduced to ferrous oxalate, with the release of CO2 ,

2 (NH4)3 Fe (C2O4)3 (ferric)

2 CO2 + 2 Fe (C2O4) + 3 (NH4)2 (C2O4) (ferrous)


The ferrous




potassium ferricyanide

to form


(Prussian blue), Fe (C2O4) + K3Fe(CN)6

K Fe [Fe(CN)6] 2 Fe4 [Fe(CN)6]3 +

K 2 (C2O4) 2 K4 Fe(CN)6

8 K Fe [Fe(CN)6]

MATERIALS Oxalic acid,

REQUIRED diammonium hydrogen phosphate, ferric chloride, potassium ferricyanide,

potassium dichromate,

HCl solution

PROCEDURE 1. Pour 50 ml of 0.5 M oxalic acid into a 250 ml beaker. Add 10 ml of 3.5 M diammonium hydrogen phosphate solution, and 2. mix well.Keep the beaker in subdued light. Add 50 ml of ferric chloride while stirring. If a precipitate is formed, further stirring should dissolve it. Keep this solution inside the cupboard, since the ferric oxalate light. 3. Immerse 4 pieces of bond paper (4 x 2.5) prepared sensitizing solution (ammonium iron in the freshly oxalate solution). is sensitive to

Rotate the beaker and make sure that the paper is thoroughly wet. 4. 5. 6. Remove the wet pieces of paper, and This should be done as quickly as After the paper has dried, between Expose minutes. During printing, do not hold the glass plates, but lay them on the desk, sheets of to sunlight. is about 45 glass. place them between sheets possible. sheets. and compress it sensitized paper, of filter paper.

remove it from the filter paper top of the

Place the opaque object on the

The time required for exposure of a normal print in bright sunlight

windowsill, or any flat surface. 7. After the exposure, smoothly in dip the paper into 50 ml of 0.1 M potassium

ferricyanide solution, kept

a wide-mouthed dish.

8. 9.

Remove the paper and dip it in 50 ml of 0.03 M potassium dichromate 1 minute. Wash the paper first in Make a series best conditions. 0.1 M HCl, and then in tap water. to

solution for

of 2 3 exposures,

varying the time of exposure

optimize the



conditions the


obtain of


most for

satisfactory pictures. each picture.