1.

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
 2. INRODUCTION

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. The roots of photography
can be traced back to the 10th century A.D. An Arabian scholar of that time, Hassan ibn Hassan,
described the use of the “camera obscura” for his observations of a solar eclipse. The camera obscura
(Latin for ‘dark room’) was a dark box or room with a small hole at one end. When light from a scene
passed through the hole, an inverted image of the scene was projected onto the opposite wall. This is
essentially the principle governing the pin-hole camera used in this laboratory. Using a camera
obscura, an artist could trace the projected image to produce a very accurate depiction of the scene.
Unfortunately, a chemical method for permanently capturing the image would not arise for eight more
centuries.
It had been known since the early 1600's that silver salts were sensitive to light. In 1725, Johann
Schulze demonstrated that a sheet of paper soaked with silver nitrate would turn black upon exposure
to light. This “light sensitivity” was due to the reduction of silver ions to silver metal. In the late 1700's
Sir Humphry Davy and Thomas Wedgwood employed the light sensitivity of silver salts to capture
images of static objects. Unfortunately, these images were not made permanent (fixed) and they
eventually turned completely black with further exposure to light. The first successful photographic
process was developed by Louis Daguerre in 1839. These “daguerreotypes” used copper plates coated
with a thin layer of silver iodide. Upon exposure of these plates to light, silver ions were reduced to
silver metal to produce an image. This image was enhanced by the further reduction of silver ions
using mercury vapor. The image was fixed by removing unexposed silver ions with sodium sulfite.
From these primitive beginnings, the chemistry of photography has progressed significantly. However,
the essential elements of the process have not changed. In this experiment you will take a picture on
photographic paper using a simple pin-hole camera, then develop and fix this picture to give a
“negative” image of the object you photographed. 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:
AgNO3 + KBr →
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. 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.
 3. THEORY AND BACKGROUND
The Pin-Hole Camera: The optics of a pin-hole camera are quite simple. Unlike a typical 35 mm
camera that employs a lens to focus the image onto the film, the pin-hole camera has a small hole that
allows light to enter and expose the film (Figure 1). The optics of the pin-hole camera produce an
image which is reversed horizontally and inverted vertically. The amount of light entering the pin-hole
camera is determined by the size of the hole and the length of time the hole is open.

Photographic Paper:
Photographic paper consists of a layer of silver bromide bound to a plastic support, while
photographic film consists of the silver bromide bound to a clear film support. The silver bromide is in
the form of a very fine powder. This powder is bound to the surface of the support using a transparent
material called gelatin. Gelatin is sufficiently rigid to prevent movement of particles that could cause
image blurring, but it is flexible enough so that it does not crack when the film is flexed. Most
importantly, gelatin is permeable to the developing solutions.
Gelatin, the same substance used in “Jell-O”, is a colloidal protein obtained from animal tissue. The
gelatin protein consists of a long chain of 100 to 300 amino acids. The basic structure of gelatin is
shown in Figure 2. The symbol R represents a group of carbon atoms of unspecified length or
structure. In proteins these R groups may contain occasional atoms of nitrogen, oxygen, sulfur, or
phosphorous. The composition of these R groups has a profound effect on the properties of the film.
Latent Image Formation: The basic process of photography is the focusing of light onto
photographic paper containing silver bromide. The light forms an invisible image on the paper called a
“latent image.” The latent image formation results from a light-initiated oxidation-reduction reaction of
the silver bromide. Bromide ions absorb photons of light (hυ) and are oxidized. The electron from this
oxidation reduces silver ions to silver atoms. As the photographic paper is exposed, small clusters of
silver atoms are formed (e.g. Ag2, Ag3, Ag4). These clusters of silver atoms make up the latent image.
Oxidation: Br¯ + hυ → Br + e¯
Reduction: Ag+ + e¯ → Ag
The latent image is enhanced during the developing process by the reduction of additional silver ions.

Developing the Latent Image: In order to produce a visible image from the latent image,
additional silver must be deposited in the vicinity of each silver atom cluster. This can be done using a
variety of reducing agents. The original daguerreotypes employed mercury as the reducing agent. The
oxidation-reduction reaction was as follows:

Hg (l) + AgBr (s) → HgBr (s) + Ag (s)

This developing process was quite hazardous due to the toxic nature of mercury. Fortunately, mercury
has been replaced by less toxic reducing reagents. Today, the most widely used reducing agent is the
dianion of hydroquinone. Hydroquinone, C6H6O2, is a water soluble weak acid that dissociates
according to the following equilibrium equation
Since this equilibrium lies far to the left, a strong base, hydroxide ion, must be added to hydroquinone
to form the dianion. Hydroxide ion removes two protons from hydroquinone to form the hydroquinone
dianion

In the presence of silver ions, the hydroquinone dianion acts as a reducing agent and becomes oxidized
to quinone. The oxidation and reduction half-reactions are:
The developer solution is maintained in the pH range of 10-12. This pH ensures that sufficient
hydroquinone dianion is present to develop the latent image.
Up to this point we have ignored several obvious questions regarding the development reaction. Why
does the reduction of silver ions only occur in the vicinity of the silver atoms of the latent image? Why
doesn't the hydroquinone dianion reduce all the silver ions in the photographic paper? The key to these
questions lies in the fact that the silver atoms of the latent image greatly enhance the rate of reduction
of additional silver ions. In essence, the silver atoms of the latent image act as catalysts for the
reduction of silver ions with which they are in contact. The developer can and will reduce all the silver
ions in the film if development is extended for too long. Consequently, the photographic paper is
developed until the image sufficiently darkens, but the development is stopped before all the silver ions
are reduced.
The resulting image is a negative of the original image. The negative image appears dark where the
object was light and appears light where the object was dark. The silver atoms on the paper seem dark
because the reduced silver on the photographic paper is formed into very small, evenly dispersed
particles. When light hits the surface of the developed photographic paper, the silver particles diffract
light and appear dark.

The Stop Bath: When the development process is completed (i.e. when sufficient silver has been
reduced to give the desired image density), the film is placed into a stop bath. The purpose of the stop
bath is to prevent any further reduction of silver ions. Since the developer solution is only active above
pH = 7, the development process can be stopped by washing the photographic paper in a dilute acid
solution. The acid converts the hydroquinone dianion back to hydroquinone, thus stopping further
reduction of silver ions. In this experiment, a dilute solution of acetic acid is used as the stop bath. It is
important that the film is removed from the developer just before it is fully developed because the
gelatin holds some of the hydroquinone dianion and it takes time for the acid in the stop bath to diffuse
into the gelatin layer to protonate the trapped developer.

The Fixer: After the developing reaction is stopped, what remains is a silver image superimposed on a
background of pale yellow silver bromide. This silver bromide was not reduced in the development
process and it must be removed or the image will ultimately darken due to gradual reduction of the
silver ions by exposure to light (as with Davy and Wedgwood's original photographic images). In
order to remove the silver bromide from the photographic paper it must be converted into a soluble
substance. This can be accomplished by addition of a substance which will form a strong complex with
silver ions. There are many substances that form soluble complexes of silver ions. In this experiment,
the thiosulfate ion,
The Final Rinse: After the photographic paper has sequentially passed through the developer, the stop
bath, and the fixer, it must be thoroughly rinsed with water. This is done to help preserve the image
because residual thiosulfate ions will turn the photo yellow and cause the image to fade.
Obtaining a Positive: In this experiment, you will obtain a negative image on photographic paper. To
produce a positive image from this negative you could either take a picture of the negative or scan it
into a computer and produce the image digitally. This negative of a negative would be a positive image
(Figure 3). This, in essence, is how positive photographs are produced. Modern photographic film,
when developed, produces a negative image on a transparent background. A positive is produced by
shining a light through the negative onto a piece of photographic paper. This is termed “exposing” the
photographic paper and gives an “exposed” photographic paper with a positive latent image.
Developing the film will result in a positive image on the paper

Figure 3. Negative and Positive images

The Final Rinse: After the photographic paper has sequentially passed through the developer, the stop
bath, and the fixer, it must be thoroughly rinsed with water. This is done to help preserve the image
because residual thiosulfate ions will turn the photo yellow and cause the image to fade.
Obtaining a Positive: In this experiment, you will obtain a negative image on photographic paper. To
produce a positive image from this negative you could either take a picture of the negative or scan it
into a computer and produce the image digitally. This negative of a negative would be a positive image
(Figure 3). This, in essence, is how positive photographs are produced. Modern photographic film,
when developed, produces a negative image on a transparent background. A positive is produced by
shining a light through the negative onto a piece of photographic paper. This is termed “exposing” the
photographic paper and gives an “exposed” photographic paper with a positive latent image.
Developing the film will result in a positive image on the paper.
 4. EXPERIMENTS
MATERIALS:
Pin-hole camera, black and white photographic paper, safe-lights, developer bath, stop bath, fixer,
water bath, development trays and tongs.

PURPOSE:
The purpose of this experiment is to understand the chemistry involved in producing a black and white
photographic print.

LEARNING OBJECTIVES:
By the end of this experiment, the student should be able to demonstrate the following proficiencies:
1. Describe the formation of a “latent image” on black and white photographic film/paper.
2. Explain the development process and the role of the silver atoms in developing the image.
3. Explain the effect that the pH of the “stop bath” solution has on the developer and the developing
process.
4. Describe how the “fixer” (the complexing agent, thiosulfate ion) fixes the image.
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. Load the pin-hole camera. Prior to turning off the lights, make sure the top of your pin-hole
camera is open and the rails inside are clear of obstructions. Under safe-light conditions, insert
the photographic paper into the rails inside the camera box. The sides of the photographic paper
are different. The shiny side of the photographic paper must face the pin-hole! The dull side
must face the back of the box. Do not touch the shiny side of the paper. When the camera is
loaded, carefully close and seal the top. Make sure the pin-hole is covered and there are no gaps
where light can enter.
2. Go outside and take a picture. Point the camera (pin-hole towards the subject) and peel back the
tape covering the pin-hole. Exposure times will vary depending upon conditions. The exposure
time can be as short as 6 seconds on bright sunny days and as long as to 2 minutes on dark
overcast days. The subject and the camera must remain stationary during the exposure. Because
the exposure times for the pin-hole cameras are so long, the clearest images are obtained when
the camera is supported on a very stable surface and the subject is stationary.
 If the camera or subject moves, multiple images or blurring may result.

3. Develop the image. Under safe-light conditions open the camera and remove the photographic
paper. Do not touch the shiny surface of the paper.

a. The Developer. Using tongs, place the photographic paper into the developer. Since a quick,
even wetting of the gelatin is necessary, the paper should be slid into the solution from an edge with
the face (shiny side) down. Use the tongs to gently agitate the paper while it is submerged in the
developer and turn the paper over after approximately 5 seconds. Continue to agitate the paper until the
image begins to appear then remove the paper from the bath using the tongs. The paper will continue
to develop after the paper has been removed from the developer, so it is necessary to “lead your image”
a little. Normally the image will appear in 15 to 20 seconds, at which time you should be ready to put it
into the stop bath.
b. The Stop Bath. Next, use the tongs to place the paper in the stop bath using the procedure above.
The paper should remain in the stop bath for approximately 1 minute.
c. The Fixer. Following the stop bath, use the tongs to place the paper in the fixer. The paper
should remain in the fixer for approximately 1 minute.
d. Permawash. Following the fixer bath, use the tongs to place the paper in the Permawash. The
paper should remain in the Permawash for 1 minute before being rinsed thoroughly with distilled water
and allowed to dry on paper towels.
4. Look at the picture and try again. You will take two pictures during this lab. Use your
experience with the first picture (exposure time, developing time, etc.) to improve your second picture.

5. RESULT
By this experiment is to understand the chemistry involved in producing a black and white
photographic print.
 4. EXPERIMENT

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.
5. In your developer the chemicals will be:
6. 1. metol, the reducing agent.
7. 2. sodium sulfite (Na2SO3), the preservative.
8. 3. sodium carbonate (Na2CO3•H2O), the activator.
9. 4. sodium bromide (NaBr), the restrainer.

Section 1: Determining the Optimum Conditions

Steps:
1. Obtain several sheets
of photographic paper.
Caution: this paper is, of
course, verysensitive to
light. Place
approximately 100 ml
each of developer, stop
bath, fixer, and distilled
water into400 ml beakers;
label each beaker.

2. Set up the exposing

light as shown in the
Figure below. Black and
White

3. 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.
4. 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?
 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 andstop bath, be
certain that you agitate it. Place the print on a paper towel to dry. Record the temperature of
the developer.
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 printpossible. 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.

Section 2: Preparing your own developer Steps:

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.

Expose and develop a contact print again according to your optimum conditions of Section 1.
Record your results. Try to improve the print.
How does this print compare with that of Section 1?
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 regularlight].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
labinstructor and in the handout. Also draw a conclusion about the effect of time on the
progress of the toning reaction

5. RESULT
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.
 6. BIBLIOGRAPHY
1. M. Philip, Advanced Chemistry (Physical and Industrial) Published in South Asia by
Foundation Books New Delhi (2003) p. 168.
2. Chris Knud-Hansen, Conflict Research Consortium (1994).
3. This laboratory is a modification of: Experiment 12 - Black and White Photography,
CHEMTRAILS, Second Edition, Department of Chemistry, U.S. Air Force Academy, 1996-
1997.
4. Chemistry in Black and White Photography | Chemistry Science Fair Project
(seminarsonly.com)
5. Black and white - Wikipedia