Chemistry Project

Black and White photography

Basic Idea:

Film is composed of layers. Many layers. These are different for color,
slide, black and white, and instant film but all contain millions of light-
sensitive silver halide crystals (what we call grain) that you expose when
you pop the shutter. While the other layers are crucial, for our purposes
we will be looking at the light sensitive layers. Color film has three layers
of silver halide: red, blue, and green.

Slide film has a few more layers than C-41:

Photographic paper and film consist of a gelatin emulsion with silver
halide grains layered onto either paper or film base. The halides that are
often used are chlorine, bromine and iodine, although bromine is the most
common. The silver halide grains are crystalline structures of silver ions
and halide ions in a lattice structure, shown in figure one. Even though the
grains are held together by chemical bonds and are very stable, there is
some movement allowed of atoms and electrons throughout the structure.
Electronically, there are different energy levels in the grain: the valence
band and the conduction band. Electrons in the valence band are localized
around the atom to which they belong. Those in the conduction band are
free to move through the grain. When photons from light come into
contact with a grain, an electron is ejected from the valence band of the
halide into the conducting band of the crystal. This electron will then
combine with a moving silver ion forming atomic silver. The place where
this occurs is the latent image center. When three or four of these events
occur at the same location, an aggregate or clump of silver metal is
produced. Three or four atoms are necessary for the latent image center
to be stable.
The latent image is invisible to the eye, but after further development, the
atomic silver will create dark areas due to its color. The latent center
serves as a catalyst for the development in the darkroom. The formation
of silver metal is logarithmically proportional to the intensity of light.
Therefore places where more light hits the emulsion will have more latent
image centers and appear darker on the film. In creating the print, light is
shown through the negative, so areas that were originally dark then
receive less light and appear brighter.
Typical developer is made up of four different components: the developing
agent, the accelerator, the restrainer, and the preservative. The
developing agent is a reducing agent; this means that it reduces the silver
halides to metallic silver. Reducing agents in the developer donate
electrons to the silver halide grains. The electrons enter the conduction
band of the compound and reduce more ionic silver to atomic silver. This
occurs more rapidly and more completely in grains where photons already
initiated this process. This is how the development is chemically
accelerated at places in the photo that are brighter and avoided in places
that received little to no light stimulation. Reduction always occurs with
oxidation; they are a paired reaction. As the reducing agent donates
electrons, it loses elections and becomes oxidized. It can also become
oxidized by oxygen in the air and subsequently become less effective.
When the reducing agent has no more electrons to donate, the developing
process cannot occur. To help slow this process, a preservative is added. It
is a chemical that protects the reducing agent from being oxidized. The
purpose of the accelerator is evident from the name, as well as the
restrainer. The balance between the two is important to the developer.
The accelerator helps create a chemical environment favorable to the
reducing agent. A basic solution deprotonates the reducing agent, freeing
up electrons to be donated. So the accelerator is a chemical that makes
the developing solution more basic or alkaline. The restrainer has an
opposing affect; it stops the developing agent from developing an image
too quickly. If this were to happen, areas that were not exposed to much
light, where there is not already a latent image center, would get
developed.
These homemade developers are extremely simplistic in that they are
only comprised of the reducing agent and the accelerator; in fact they
contain two reducing agents. In Caffenol and Wineol, caffeic acid is the
primary reducing agent. Vitamin C or ascorbic acid acts as a secondary
reducing agent. Many commercial developers utilize two reducing agents
because the combination results in superadditivity. The reduction potential
or activity of two developers is greater than just the sum of the two. This
effect will speed up the developing time without compromising tonality.
Fast developers develop low contrast with high mid-tone detail. This is due
to the high activity of the developer. If the reducing agent is very active
then it can reduce grains that did not have latent image centers. This
causes low contrast and less detail in the final image. Slow developers on
the other hand, create more contrast. These reducing agents are less
active and there is more discrimination between grins with latent centers
and those without. The pairing of two reducing agents compromises these
effects; the speed and the contrast.
The purpose of the fixer is to dissolve the unreduced silver halide
molecules left on the paper after development. This is a way of preserving
the image because if these grains are not removed, they can continue to
be reduced by sunlight and degrade the image. This degradation causes a
purple hue on the image and the loss of fine details. Silver halides alone
are insoluble in water, so a reaction must occur in order to remove them.
A typical fixer is sodium thiosulfate (Na2S2O3). The reaction with silver
halides creates a complex that makes the silver halide dissolve. Although
silver halides are practically insoluble, a very mall portion of dissociated
silver and halide ions will be present. The complex ion that is formed with
thiosulfate is more stable than the silver ion, and thus, more of it is
created and less ionic silver is left behind. More silver halides will
dissociate to maintain equilibrium and eventually most will be dissolved.
The reaction equation for this interaction is shown below. 𝐴�+ + 2�2�3 2−
↔ [𝐴�(�2�3)2 ] 3− Sodium thiosulfate is an outdated fixer due to its slow
fixing time, about five to six minutes. Commercial fixers, called “fast
fixers,” add other ingredients to speed up this time
The only possible household alternative with foundation in chemical
properties is ammonia. Silver chloride is soluble in dilute ammonia, and
silver bromide is soluble in concentrated ammonia. Silver iodide is not
soluble in any concentration of ammonia, but the percentage of iodide in
photographic papers is quite small. The solubility is increased for the
same reason as above, the complex ion formed between ammonia and
silver ions is more stable, causing the formation of more ions and the
dissolution of more silver halides. The reaction between silver and
ammonia is shown below.
𝐴�+ + 2𝑁�3 → [𝐴�(𝑁�3)2 ] +
A final wash in water is necessary to rinse off the dissolved silver halides
as well as residual chemicals on the paper. The thiosulfate fixer makes a
compound that is soluble in water, so the leftover silver halides rinse off in
the water. The fixer itself also must be removed because it itself can
degrade the image. It decomposes to form acid that reacts with the silver
to form silver sulfide. This compound makes a yellow-brown staining over
time.
Experiment:

Purpose: 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.

Procedure: NOTE: Weigh out all of the materials needed for Section 2
before doing Section 1.
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.

Wastes: The developer and the stop bath can be put down the drain with
the water running. Used fixer has silver in it and must be put in the
acqueous waste container.

Section 1: Determining the Optimum Conditions

Steps:

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 youur Results section.

Trial Distance to paper Variac setting Exposure time

Developing time

2
 3

5 (if necessary, or more)

Best conditions
____________________________________________________________

Section 2: Preparing your own developer

Steps:

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.

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: 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.

Place a print in the iron toning solution for 5 minutes. What happens? How
does the length of time in the toning solution affect the print? Test this by
placing a 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: 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).

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: Place a print in a 400 ml beaker containing about 100 ml

of 20% sodium thiosulfate solution for 5 minutes. 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? (Note: In
your Results section, include the prints by taping them in the appropriate
section).

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.