Processing of the Black & White Materials
11
Development of Black & White Photographic Materials
The development of photographic materials is based on the fact that a chemical reaction
Ag+ + e- → Ag0
i.e., the reduction of silver ions to metallic silver (by the development solution) proceeds more easily in the case of exposed silver
halide grain than for the unexposed grain. This is due to the presence of very small metallic silver specks at the halide grain. These
particles are known as latent images and act as catalysts during reduction.
There are two types of development, commonly known as physical and chemical development:
• chemical development: reduction of exposed grains of silver halide (silver ions) to metallic silver by developing a solution;
• physical development: deposition of free silver ions (form solution) upon suitable nuclei, that have been formed in the silver
halide grains by light (i.e. latent image).
Chemical Development
The chemical development – reduction of sliver halide to metallic silver - could generally be expressed by following chemical
equation: (eq.01)
OH O
+ -
2 AgBr + 2 Ag + + 2 H + 2 Br
OH O
silver bromide + hydroquinone silver + 1,4 benzoquinone + bromhydric acid
Where:
silver bromide = exposed photographic emulsion,
hydroquinone = reduction agent (developer),
developed metallic silver = picture,
1,4 benzoquinone (quinone) = oxidized developing agent,
H+ + Br¯ = bromhydric acid
The developing agents
Development is an essential element of solution development. It is a weak reducing agent that selectively converts only exposed
silver halide grains (with latent image), into metallic silver particles that produce a visible black and white image. Unexposed grains
are not developed.
There are many types of development agents. It is not possible to mention them all. So there is only a brief overview of some of them:
Inorganic compounds
They are not used very often in these days: NH2– NH2 (hydrazine), NH2OH (hydroxylamine), Fe+2 salts (e.g. collodion process FeSO4) ...
Benzendiols and their derivates
They have two hydroxyl groups fixed on benzene ring. The most important developers of this kind are:
OH OH
OH
OH
hydroquinone pyrocatechol
12 The Chemical Principle of Photography
Phenylenediamines and their derivates
The substances that have fixed two amino groups on benzene ring:
NH2 NH2 NH3+
NH2 _
2Cl
NH2 NH3+
1,2 phenylenediamine 1,4 phenylenediamine 1,4 phenylenediamine dichloride
Aminophenols and their derivates
The substances that have fixed one hydroxyl group and one amino group on benzene ring:
OH OH
NH2
NH2
4-aminophenol 2-aminophenol
Very well known and often used are the derivates of aminophenols: hydroxy-N-methylaniliniumsulphate (metol)
and p-hydroxyphenylglycine (glycin):
(+)
NH2 CH3 NH2 CH2COOH
(2-)
SO4
OH OH
metol glycin
2-hydroxy-N-(2-hydroxyethyl)-aniliniumsulphate is a very succesful reducing agent used in Agfa ultrafine developer Atomal:
(+)
NH2 C2H4OH
(2-)
OH SO4
atomal
Processing of the Black & White Materials
13
Developers with three active groups fixed on the benzene ring
The most important substances of this group are:
OH OH
(+) (-)
OH NH3 Cl
OH
(+) (-)
NH3 Cl
pyrogallol Amidol
Heterocyclic compounds
Heterocyclic compounds (the organic substances that contain the heteroatoms in their rings). The widest spread heterocyclic
compound is phenidone (Ilford):
N
NH
O
phenidone
Ascorbic acid acts as developing agent as well:
OH
O O CH CH2OH
OH OH
ascorbic acid
In fact, there are a huge number of other substances that can be used as development agents. Not all of them can be mentioned
in this brief report.
14 The Chemical Principle of Photography
The role of sodium sulfite
The equation (eq.01) describes the basic chemical processes that occur during development and could very well serve to explain
essentials concerning developers and chemical developing in general.
Development is a reversible chemical process. That is, it can proceed towards the products and / or in the opposite direction (back
to the silver bromide and the developing agent). If we want the chemical reaction to proceed in the right direction (toward metallic
silver), we should remove the reaction products from the mixture.
The products that should be removed are oxidized hydroquinone, i.e. benzoquinone (1,4 benzoquinone) and hydrobromic acid.
Their excess would really stop development. The metal silver particles play no role – they are not a part of the liquid reaction mixture.
Sodium sulfite as a refreshing agent for hydroquinone
Thus, the development solution must contain some substance that decreases the amount of oxidized developmental agent
(benzoquinone). For B&W developers, the added substance is sodium sulfite, which reacts with quinone:
O OH
SO3Na
+ Na2SO3 + 2NaOH
O OH (eq.02)
Hydroquinone monosulphonate (as well as hydroquinone) acts as reducing agent1 and develop silver halide. After next development
it is converted into benzoquinone sulfite that reacts with sodium sulfite again:
O OH
SO3Na SO3Na SO3Na
+ Na2SO3 + 2NaOH
O OH
(eq.03)
The hydroquinone (natrium) disulfonate is then stable substance and play no role in developer solution.
Sodium sulfite plays another role in the developer solution. Protects the development agent against air oxidation. Air oxygen
oxidizes sodium sulfite much more easily than the developing agent. This prolongs the life of the developer. Therefore, sodium sulfite
is present in much greater amounts than necessary for the regenerating of the developing agent.
There is a third reason for using more sodium sulfite, especially for very fine grain developers. It acts as a silver halide solvent.
During development, the silver halide grains are etched and partially dissolved. Part of the dissolved silver is immediately reduced (by
developer) and a very fine colloidal form of metallic silver is produced. This colloidal metallic silver is then deposited on the developed
silver. This kind of developer is called semi-physical.
1
but a bit weaker then hydroquinone
Processing of the Black & White Materials
15
Influence of pH value
Another product of the developing reaction – hydrobromic acid – changes the acidity of the developer (see eq. 01). It is evident
that high acidity (low pH) could slow the rate of development. In other words, the more alkaline the solution is, the faster the
development takes place. Thus, the developer solution should be less or more alkaline (pH higher than 7) throughout the whole time
of development and, of course, throughout the lifetime of the developer.
(The specific rate of development depends not only on alkalinity, but of course on the type of developing agent also.)
Whether the solution is alkaline or acid, it depends on concentration of hydrogen ions [H+] in it. This concentration is expressed as a pH value.
How to understand this term:
In addition to molecules of water the pure water also contains ions – hydrogen ions H+ (or H3O+) and hydroxyl ions OH–. These ones was came to existence
due to spontaneous dissociation (decomposition) of water: H2O <–> H+ + OH– . This reaction is reversible – it proceeds by the same speed in both directions.
The amount (concentration) of the hydrogen ions in the pure water is therefore constant. 1 litre of water contains 10-7 grams of H+ (= 0,000 000 1 g H+).
If this quantity is expressed by the negative decimal logarithm, we got number 7. This number is called pH value. So: pH= -log[H+] . The pure water gets pH=7.
It is evident that pure water is dissociated just only a little. If an acid is added to the pure water, this acid dissociates much more then water: HBr <–> H+ + Br– .
The concentration (amount) of hydrogen ions grows up. The pH therefore shows a smaller value – less then 7,0.
If some alkali is added to the pure water, this alkali dissociates much more then water: NaOH <–> Na+ + OH–. The concentration (amount) of hydrogen
ions decreases due to the high possibility of synthesis of hydrogen ions with hydroxyl ions; pH therefore shows a high value – higher than 7.0 (max 14).
In this way the pH value expresses the acidity/basicity(alkalinity) of the solutions.
strong acidity pH = 0 – 5
weak acidity pH = 5 – 7
neutral pH = 7
weak alkalinity pH = 7 – 9
strong alkalinity pH = 9 – 14
Since hydrobromic acid is a very acidic substance, it must be removed (neutralized) from the developing solution. This is partially
accomplished by treatment with sodium sulfite, that is present in the developing solution for the refreshing developing
agent. However, sodium sulfite control is not enough.
Thus, the pH is better controlled by the addition of a suitable alkali salt such as K2CO3 (potassium carbonate / potash) and / or
Na2CO3 (sodium carbonate) and / or Na2B4O7·10 H2O (borax) and / or NaBO2 and / or NaOH (sodium hydroxide).
Very often the pH is controlled by adding so-called buffers to the developer solution. A special feature of buffers is the ability
to maintain the pH at a stable level regardless of other substances present (or added) in the reaction mixture. Buffers are usually
a couple of an acid and an alkali salt of that acid (or a mixture of two salts). The most commonly used buffers in developer solutions are:
H3BO3 and Na2B4O7.10H2O
CH3COOH and CH3COONa (acetic acid and sodium acetate)
KH2PO4 and Na2H PO4.
The pH of the developing solution is adjusted according to the intended purpose of the developer. For rapid developers (positive
and graphical ...), the pH is higher (more alkaline) - from about 11 to 12. For normal developers (negative), the pH is adjusted from
approx. 7.5 to 9.5.
16 The Chemical Principle of Photography
Antifogging agents
Photographic materials could be affected by fog. It can be seen from equation 01 that the bromide ions present in the reaction
mixture (on the right side of the equation) slow the development down. A small amount of bromide ions causes a decreas of the fog.
Therefore, potassium bromide is added to the development solutions. The appropriate (needed) amount of bromide ions
depends on the type of development agent present. Development solutions containing a metol as a developing agent usually
develop without fog and are almost unaffected by the addition of bromide. Development solutions that contain combination of
developing agents (such as hydroquinone and metol or hydroquinone and phenidone) require more bromide.
The amount of bromide ions depends on the type of photographic material. The presence of bromide ions reduces the sensitivity
(speed) of the photographic material. This is very undesirable in the case of negative films. On the other hand, the fog is not
so problematic in the case of negative materials. Thus, in negative developer solutions, bromide is very often absent and / or is only
present in very small amounts – approximately 0.1 - 1.0 g per litre of solution of developer.
In the case of positive processing (unlike negative materials), fog is strictly undesirable. Thus, potassium bromide is present in
an amount of from about 0.5 to 5.0 grams per litre of developer solution.
As the speed of the negative films increases, the risk of fog formation also increases. For this reason, special organic substances
are added to the developer solutions as anti-fogging agents. These substances are called stabilizers. Most stabilizers are organic
heterocyclic compounds and are added to the development solutions in an amount of 0.01 to 0.1 g per litre. In the following review
are a few examples. Of course, this short overview does not names all types of stabilizers.
H H
N SH N
Imidazole derivates N N
O2N
S S
Thiazole derivates OH SH
N N
H H
N N
Triazole derivates N N
N H3C N
Tetrazole derivates
N S S N N
N N HS N
N N N N N N
Many stabilizers slightly change the color of the developed silver. That is why they are added to positive development solutions to
provide black and white positive prints in some colour tint. The best known stabilizer capable of coloring positive prints is 1H-benzotriazole:
H
N
N
N
1H-benzotriazole
Processing of the Black & White Materials
17
Additives adjusting water hardness
Tap water contains many dissolved minerals (mostly calcium bicarbonate Ca(HCO3)2 and calcium sulphate CaSO4). This phenomenon is
called water hardness. Dissolved minerals do not affect (/spoil) acid baths (fixer and stopp bath). However, in alkaline solutions, the presence
of dissolved minerals can be problematic – it can cause precipitation during preparation and/or during storage of the developer solution.
It is possible to remove part of the soluble salt present in tap water by boiling it and then filter off the precipitated salt. However,
some salts are not removable from water simply by cooking. Thus, in these cases, special additives such as hexametaphosphates
((K2.2Na0.8PO3)x = M19 and / or (NaPO3)� = Calgon) are added to the developer solutions. These substances inhibit the crystallization
of calcium and magnesium salts from solutions. Hexametaphosphates are added in an amount of about 1 to 3 grams per litre.
There are another substances that can fix magnesium and calcium ions (and others) and that are able to form stable water-soluble
compounds with them. They are called chelating agents. The best known is Chelaton 3 (EDTA)
(CH2COONa)2 N-CH2-CH2-N(CH2COOH)2. 2H2O
Chelaton 3
Other additives
Other additives that provide special purposes may be included in the developer solution. They are not commonly used, only in special
developer baths. These additives include hardeners, anti-swelling agents, developing accelerators, speed enhancing agents and others.
Examples of developers
Negative developer (“D 76”) Positive developer (A115; FV101)
Methol ....................................... 2,0 g Methol ...................................... 2,0 g
Na2SO3 (anhydr.) .................... 100,0 g Na2SO3 (anhydr.) ..................... 25,0 g
Hydroquinone .......................... 5,0 g Hydroquinone .......................... 6,0 g
Na2B4O7 . 10 H2O ..................... 2,0 g Na2CO4 (anhydr.)..................... 33,0 g
Water to ............................ 1000,0 ml KBr ............................................. 0,5 g
Water to ............................ 1000,0 ml
Extra finegrain negative developer
Perfectol
Methol ........................................... 6,0 g
Na2SO3 (anhydr.) .........................100,0 g
NaCl ............................................. 33,0 g
Na2B4O7 . 10 H2O ........................... 2,0 g
Water to ................................ 1000,0 ml
18 The Chemical Principle of Photography
Physical Development
Physical development is based on a different principle than the chemical one. It is the deposition of free silver micro-particles
(present in developer) on suitable nuclei, which has been formed on the silver halide grains by light (ie the latent image). Free colloidal
particles of silver are brought by the development solution where they are created by chemical reduction of silver nitrate. Physically
developed negatives provide a very fine grain and in the past was used for very large prints.
The processing involves two steps:
Fixing (1st step)
In the first stei the exposed photographic film is fixed. The fixer should not have an alkaline pH. It should be neutral or weak acid due
to the careful dissolution of the silver halide. After fixing, only the silver micro-nuclei (latent image) remain in the emulsion layer. As a
fixer, a 3% sodium thiosulfate solution (Na2S2O3) is usually used. Fixing takes much more time, of course. Therefore, it is better to test
fixing time before. As the latent image nuclei are very small, it is recommended to overexpose the film (+ 4– 8 EV) to make them larger.
Note: Not only fixation but also next washing must be done in total darkness. The silver thiosulfate complexes must be completely
removed from the emulsion layer. Further processing steps can be done under light.
Developing (2nd step)
The developer consists from two parts:
Part A
metol 2.0 g
citric acid 5.0 g
water 100.0 ml
Part B
Silver nitrate 0.1 g
water 1.0 ml
Both solutions are mixed together just before development. The developin takes aproximately 15 minutes. Next washing should
be done in distilled water. Usually, silver deposits not only on the silver cores in the emulsion layer, but also on the surface. Those
should be carefully cleaned out from the film surface using cotton wool.
Fixing and Washing of B&W Photographic Materials
Fixing removes the undeveloped portion of silver halide from the emulsion. Since the silver halide is insoluble in water, it is converted
to soluble thiosulfate complexes. The chemical reaction proceeds in three steps:
AgBr + Na2S2O3 → Na[Ag(S2O3)] + NaBr
Na[Ag(S2O3)] + Na2S2O3 → Na3 [Ag(S2O3)2]
Na3[Ag(S2O3)2] + Na2S2O3 → Na5 [Ag(S2O3)3]
Σ AgBr + 3 Na2S2O3 → Na5[Ag(S2O3)3] + NaBr
The first step product is invisible but (!) insoluble. Only the second and third products are soluble, that is, they are removable
from the emulsion layer. However, they are only produced in a fresh fixer. Therefore , it is very important to treat the photographic
material with fresh fixer and to follow the recommended time of fixing. If the film/print is not properly fixed (despite being clear as
glass), unwanted stains will appear after some time.
The same applies to washing. The photographic material should be washed long enough because the silver complexes need
a relatively long time to escape from the emulsion layer. If they are not sufficiently washed and remain in the material after a period
of time, the silver ion complex will be converted to metallic silver, resulting in the stains.
Fixers are usually sufficiently acidic to stop development at once. But, sodium thiosulfate decomposes in acidic solutions and
the decomposition product is sulphur. Therefore, sodium (and/or potassium) metabisulfite is added, which reacts with the sulphur
and converts it back to the thiosulfate. Sodium (and/or potassium) pyrosulfite (disulfite) then acts as both an acidic agent and a
regenerating agent.
Fixers are differing according to rate of fixing: 1. acid fixer – works normally ; 2. rapid fixer – work more rapidly because of presence
ammonium ions; 3. express fixer - works most rapidly, contains ammonium thiosulfate instead of sodium thiosulfate.
Processing of the Black & White Materials
19
Questions:
1. What is the chemical development?
2. What is a developer from a chemical point of view?
3. What are the best known trade names of developing agents?
4. What pH value indicates acid/neutral/alkaline solution?
5. Why has to be natrium sulfite in developer?
6. Which developers are developing more rapidly - negative or positive?
7. Which substance is usually used as an antifogging agent
