Chemistry in Black and White Photography

ABSTRACT

This experiment is designed to illustrate the purpose of the

different components of a photographic developer. It will also
illustrate the chemistry of the toning process. Specifically, you will
determine the role of one component in the developer and identify the
importance of reaction duration as a variable in the toning of black
and white prints. For the first part, be specific. Indicate which
component you are omitting. Discuss the role of that component in
your conclusion section.

INTRODUCTION

Traditional black and white photography utilized a chemical

process that has been observed since ancient times – that of the photo-
sensitivity of silver (Ag) compounds. This ability was harnessed by
the19th century photography pioneers by coating silver halides
(molecules of Ag and halide gases) in an emulsion of gelatin onto a
glass or plastic backer. The process of making traditional film has not
changed much from the basic chemical reactions discovered in the
1800’s. Initially, elemental silver is reacted with nitric acid to form
silver nitrate.
Complete and balance the reaction below:

Ag (s) + HNO3 → AgNO3 + H2

Identify the element oxidized and that reduced in the above equation.

The silver nitrate is then converted to the silver halide (usually

bromide) by fuming the film with potassium bromide.

Complete and balance the next reaction:

KBr + AgNO3 → AgBr + KNO3

The AgBr is an ionic compound that forms a crystalline
structure in grains. What does it mean to be an ionic compound? The
film now is ready for exposure and the creating of the intended image.
Stored within a light sealed container, the AgBr film is a uniform
darkish yellow.

AgBr powder
The light exposure occurs when an opening allows light to enter the
dark container and strike the film. These “storage” containers that
subsequently allow light exposure are more commonly referred to as
cameras.

THEORY

In the first section of this experiment you will determine a set of

optimum conditions for developing a contact print using a light bulb
for exposure and a standard, already-prepared developer. Two factors
are important in determining the optimum conditions. The first is the
amount of light hitting the photographic paper. This depends on the
intensity of the light, the length of the exposure and the distance of
the light from the paper. The greater the amount of light hitting the
paper, the darker the print since more silver halide grains are exposed.
This assumes all other conditions are held constant. The directions for
the first part are listed in Section 1.

In the second section of the experiment you will prepare a

developer by weighing out and mixing the necessary chemicals. You
will then use the conditions determined in the first part to prepare a
contact print with your own developer.

Most photographic developers have several components in common.

These are:

1. A reducing agent--to reduce the exposed silver halide grains to

metallic silver,
2. A preservative--to prevent reaction of the reducing agent with
oxygen from the air,
3. An activator--to activate the reducing agent,
4. A restrainer--to increase the contrast between light and dark
areas in the print.

In your developer the chemicals will be:

1. Metol , the reducing agent.

2. Sodium sulfite (Na2SO3), the preservative.
3. Sodium carbonate (Na2CO3•H2O), the activator.
4. Sodium bromide (NaBr), the restrainer.
Procedure:
Section 1: Determining the Optimum Conditions

1. Obtain several sheets of photographic paper. Caution: this paper

is, of course, very sensitive to light.
2. Place approximately 100 ml each of developer, stop bath, fixer,
and distilled water into 400 ml beakers; label each beaker.

3. Set up the exposing light as shown in the Figure below.

4. Using only safety lights remove a piece of photographic paper
from its storage space and place it directly under the light with
the emulsion side up. Place the negative on top of the paper and
put a glass slide on top of the negative.
 5. Turn on the light for 30 seconds to expose the paper. Using only
the safety light, observe the paper. Does it appear to have
changed?
6. Develop the print (still under safety light) by placing it in the
beaker containing the developer for 60 seconds (caution: use
tongs), then the stop bath for 60 seconds, the fixer for 5 minutes
and the distilled water for 5 minutes. While the paper is in the
developer and stop bath, be certain that you agitate it. Place the
print on a paper towel to dry. Record the temperature of the
developer.
7. Try to improve the print. If it is too dark, reduce the exposure or
the developing time. The exposure can be reduced by reducing
the exposure time, raising the bulb, or reducing the setting on
the Variac. If the print is too light, the opposite remedies should
be applied. Be certain to keep an accurate record of your
conditions for each experiment. A Table such as shown below
works well. Your goal here is to find the conditions for the best
print possible. You will use these conditions in the subsequent
section for your developer. Put 1/2 of each print next to the
conditions in your Results section.

Section 2: Preparing your own developer

1. Prepare your own developer by dissolving 2.0 g Na2SO3, 0.25 g

sodium bromide, NaBr, 0.6 g metol, and 2.0 g of sodium
carbonate (Na2CO3·H2O) in distilled water and dilute to 100
ml. Be sure to dissolve these chemicals in the order listed.
 2. Expose and develop a contact print again according to your
optimum conditions of Section 1. Record your results. Try to
improve the print.
3. How does this print compare with that of Section 1?
4. Prepare 8 extra prints for the toning experiments. Make these
prints as soon as possible after your determination of the optimal
conditions.
5. What happens if...? What happens if you prepare a developer
but leave out one of the ingredients? Try it and record your
results.

Section 3: Toning

[Note: these experiments can be performed in regular light].

Iron Toning:

1. Prepare an iron toning bath by mixing 10.0 ml of ferric

ammonium citrate (10% solution), 10.0 ml of K3Fe(CN)6 (10%
solution) and 100 ml of a 10% solution of acetic acid in a 400-
ml beaker. This solution can be safely disposed of in the sink.
2. Place a print in the iron toning solution for 5 minutes. Place the
print in the toning bath for only 2 minutes. Try another time for
the toning bath. Rinse the print in deionized water briefly, and
record your results.
Copper Toning:
3. Prepare a copper toning bath as follows. Dissolve 0.54 g of
K3Fe(CN)6 and 2.65 g of potassium citrate in 100 ml of H2O. In
a separate beaker, dissolve 0.66 g of copper sulfate and 2.65 g of
potassium citrate in 100 ml of water. Mix equal volumes of the
two solutions just prior to use. (Copper is a heavy metal.
Dispose of this solution in the aqueous waste container).
4. Place a print in your bath for 5 minutes and rinse What do you
see? How does the length of time in the bath affect the result?

Sepia Toning:

1. Place a print in a 400 ml beaker containing about 100 ml of 20%

sodium thiosulfate solution for 5 minutes.
2. Without rinsing, immerse the print in a beaker containing the
prepared hydrochloric acid for 30 minutes then rinse in distilled
water. (Both of these solutions can be put down the drain with
the water running). What do you observe? How does length of
time in the acid bath affect the result?
3. (Note: In your Results section, include the prints by taping them
in the appropriate section).
Conclusion

For your conclusion describe the role of the chemical which you left
out of the developer. Refer to the mechanism of the action of the
black and white developer as described by your lab instructor and in
the handout. Also draw a conclusion about the effect of time on the
progress of the toning reaction.

References:

1. www.google.com
2. M. Philip, Advanced Chemistry (Physical and Industrial)
Published in South Asia by Foundation Books New Delhi
(2003) p. 168.
3. Chris Knud-Hansen, Conflict Research Consortium (1994).