Experiment 35 BLACK AND WHITE PHOTOGRAPHY 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: 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 pl! 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. INTRODUCTION: The roots of photography can be traced back to the 10" century A.D. An Arabian scholar of that time, Hassan ibn Hassan, described the use of the “eamera obscura” for his observations ofa solar eclipse. ‘The camera obscura (Latin for ‘dark room’) was a dark box or room with a small hole at one end. When light ffom 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 ofthe scene. Unfortunately, a chemical method for permanently capturing the image would not arise for eight more centuries Ithad been known since the early 1600's that silver salts were sensitive to Hight. In 1725, Johann Schulze demonstrated that a sheet of paper soaked with silver nitrate would turn black upon exposure to 35-1light, This “light sensitivity” was due to the reduction of silver ions to silver metal. In the late 1700's Sit 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 fo light. The fist 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 (o silver metal to produce an image. This image was enhanced by the further reduetion 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 pieture ‘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. BACKGROUND: ‘The Pin-Hole Camera: The optics of a pin-hole camera are quite simple. Unlike a typical 35 mm camera that employs a fens 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, Camera Box Photographic Paper Figure 1. Optics of the Pin-hole Camera. Photographic Paper: Photographic paper consists ofa 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 its flexible enough so that it does not crack when the film is flexed. Most importantly, ‘gelatin is permeable to the developing solution: 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 « 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 ofthe film, RATE RRP HAA pa UE 1 ml yy a ec es) Figure 2. The Structure of Gelatin, 535-2Latent Image Formation: The basic process of photography is the focusing of light onto photographie 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-intiated oxidation-reduction reaction of the silver bromide. Bromide ions absorb photons of light (hv) 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 (eg, ‘Ag:, Ags, Ag). These clusters of silver atoms make up the latent image Oxidation: Br + hy > Br+e Reduction: Agito > Ag ‘The latent image is enhanced during the developing process by the reduction of additional silver 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 (I)+ AgBr (s) > HgBr (s) + Ag (s) ‘This developing process was quite hazardous due to the toxie nature of mereury. Fortunately, mercury has been replaced by less toxic reducing reagents. Today, the most widely used reducing agent is the dianion of hydroquinone. Hydroquinone, CaH,O:, is a water soluble weak acid that dissociates according to the following equilibrium equation: OH o- + = HO OH OW CH,0. CAHLOs 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 HI o + 20H~ + ou oO CHO, t,o, hydroquinone 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 5353Oxidation: o ° _ + 2e CHO, CHO, hydroquinone dianion suinone Reduction: 2Ag’ +2¢ —2Ag ‘The overall oxidation-reduetion reaction is: Cat CHO. ‘The developer solution is maintained in the pl 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 ofthe latent image greatly enhance the rate of reduetion ‘of additional silver ions. In essence, the silver atoms of the latent image act as catalysts forthe reduction of silver ions with which they are in contact. The developer can and will reduce all the silver ions inthe 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 surfuce 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 10 prevent any further reduction of silver ions, Since the developer solution is only active above pl = 7, the development process ean 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, @ 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. 35-4‘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 jons by exposure to light (as with Davy and Wedgwood’ 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, $40] , is used to dissolve silver bromide by forming the Ag(S,03)y° complex ion. The overall dissolution reaction is, AgBr (s) + 28,0." (ag) — Ag(S:0,)2" (aq) + Br (aq) ‘The Final Rinse: After the photographie 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 tur 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 ot sean it into a ‘computer and produce the image digitally. This negative of @ negative would be a positive image (Figure 3). This, in essence, is how positive photographs are produced. Modern photographic film, when ‘developed, produces « 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” photographie paper with a positive latent image. Developing the film will result ina positive image on the paper. Figure 3. Negative and Positive images. 535-5PROCEDURE: 1 Load the pin-hole camera Prior to turning off the lights, make sure the top of your pin-hole ‘eamera 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 photographie paper are different. The shiny side of the photographic paper must fice 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 ean enter. Go outside and take a picture. Point the camera (pin-hole towards the subject) and pee! back the ‘ape 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 ot 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 ofthe paper. a. The Developer. Using tongs, place the photographic paper into the developer. Since a quick, even weiting 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 inthe developer and tur 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, soit is necessary to “lead your image” a litle. Normally the image will appear in 15 to 20 seconds, at which time you should be ready to put it into the stop bath ». The Stop Bath. Next, use the tongs to place the paper in the stop bath using the procedure above. The paper should remain inthe stop bath for approximately 1 minute. ¢. The Fixer. Following the stop bath, use the tongs to place the paper inthe fixer. The paper should remain inthe fixer for approximately 1 minute 4. Permawash. Following the Fixer bath, use the tongs to place the paper inthe 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 atthe picture and try again. You will ake two pictures during this lab. Use your experience ‘with the first picture (exposure time, developing time, et.) t0 improve your second picture REFERENCES: 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. 35-6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: 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. Procedure: 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: a reducing agent~to reduce the exposed silver halide grains to metallic a preservative--to prevent reaction of the reducing agent with oxygen from the air, an activator--to activate the reducing agent, 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+H20), the activator. 4, sodium bromide (NaBr), the restrainer. wpe vesaus 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. Black and White 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. Tum 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 itis 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 Varisc setting Exposure time Developing time 2 5S (iF nec ary, or more) Best conditions 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-H20) 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 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. 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. 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).