Formulae from Melaleuca

Start of extract from Melaleuca:

Lith Developers

On this page are formulae for all of the lith developers I could find. Please note that all chemicals should be mixed in the order given and that proper safety procedures should be followed when mixing the formulae. Goggles, a mask and gloves would be regarded as basic precautions.

Michael Gudzinowicz rather wisely points out that formaldehyde, which is used in many lith formulae, its polymerized form paraformaldehyde and addition products such as the bisulphites, are carcinogenic and should be treated carefully with very good ventilation – preferably in a fume hood.

He offers the advice that instead of using paraformaldehyde, acetone is used. The monomer molecular weight of paraformaldehyde is 30, and that of acetone is 58.08 with a density of 0.788. He suggests therefore, for each gram of paraformaldehyde, substituting 58/(30 * 0.788) = 2.20 ml of acetone. So for 37.5 grams of paraformaldehyde, you’d use 82.5 ml of acetone. He advocates testing this on scrap film with the addition of more acetone if the lith effect does not occur due to the excess of free sulphite.
(Editor’s Note: Personally I have heard that the replacement of paraformaldehyde with acetone is not effective.)

I’m not sure what effect this has on lith printing rather than lith film developing so I am going to stick with paraformaldehyde with care in its use. I’m offering Mike’s advice here for those who are concerned about the use of known carcinogens.

Editor’s Note: All notes following formulae are the original author’s, unless otherwise stated.

This page points to the following lith developers:

What Lith Developers Do

This information was taken directly from an e-mail from Michael Gudzinowicz . It is the best description I’ve found of what Lith Developers do.

(Editor’s Note: Perhaps also see the description provided by Tim Rudman on the Unblinking Eye site. Tim is a recognised master of lith printing in the UK).

Lith Developers are fairly simple mixtures. Hydroquinone is the developing agent, usually present in a concentration of around 20 grams per litre. The free sulphite level must be very low – less than 2 grams per litre. Since the
developer will oxidise quickly, sulphite in the form of an addition product with formaldehyde is frequently used, or formaldehyde, paraformaldehyde or acetone are added to tie up free sulphite. The anti-oxidant properties are retained. The
third component is a base, usually carbonate or mixtures of carbonate, hydroxide or borates. The pH is frequently adjusted to a value around 10.

Although lith developers are often thought of as simply high contrast developers, they have a unique property. In the absence of sulphite, the hydroquinone dianon reduces silver and is oxidised to the semiqinone free radical. The semiquinone is a more powerful developing agent than hydroquinone, and it reduces another silver atom and is converted to quinone. Then quinone reacts with hydroquinone to form two semiquinone molecules. They reduce silver,
generating two quinones. They react with hydroquinone forming four semiquinone molecules. The rounds of reactions result in an exponential inrease in semiquinone concentration, doubling each time. The addition of sulphite will stop these reactions, since it reacts with the semiquinone and quinone removing the possibility of reaction with hydroquinone to generate more semiquinone.

The semiquinone is generated in the emulsion and remains there with a very short diffusion path. Development starts with grains which have multiple centres. The semiquinone concentration rises as those grains are reduced, and
then neighbouring grains are developed which might have just one centre. As the concentration rises a bit more, development spreads explosively (exponential).

What one sees is that development starts slowly in well exposed areas of the film. If a step tablet were used for the exposure, a faint image appears in the well exposed areas. Eventually the developed area reaches a critical density and
semiquinone concentration, and then development takes off, and quickly goes to completion in that step. Then as development proceeds, the next step develops fully.

Essentially one has a two phase development. First the formation of a faint image, then rapid completion in areas receiving the most exposure. This results in a film with very little density in areas with little exposure, and an extremely dense image in areas with a bit more exposure. As expected, the contrast increases with development to a miximum after 1 to 3 minutes, and then decreases as the low value faint images are further developed. Unlike developers with moderate sulphite concentrations, development is restricted to the grain and filaments are not formed. If free sulphite is added (20gm/l), filaments are formed and neighbouring grains are rapidly developed. There is no lag phase and significant semiquinone concentrations are not generated. The developer then acts like a typical MQ or PQ high contrast developer.

Having read the material from Richard and Michael about lith developers, I then consulted my copy of Wall “Photographic Facts and Formulas” and discovered, in addition to two formulae, a note that
Hydroquinone deteriorates slowly in air and has good keeping qualities in solution but is very sensitive to cold and should not be used at temperatures below 60 degrees F. It is practically inert at 55 degrees F. I then went to The
Focal Encyclopedia of Photography (Desk edition), Focal Press, London, 1969 and discovered a table comparing lith developers. I’ve modified it slightly and reproduce the modification here (Ed. Note: link broken). It gives a different version of Kodak D-8 which is a bit inexplicable.


Ansco GAF 79

Ansco 79 is a single solution formula which is recommended for its convenience but which has poor keeping qualities. If you are likely to store your chemicals then GAF 79b (a two solution version of this formula) is recommended. If you wish to use a single solution developer, Ansco 81 is recommended as having excellent keeping qualities.

Water (< 32 dec C)

Sodium Sulfite (anh)

Paraformaldehyde

Potassium Metabisulphite

Boric Acid crystals

Hydroquinone

Potassium Bromide

Cold water to make

500 ml

30.0 grams

7.5 grams

2.6 grams

7.5 grams

22.5 grams

1.5 grams

1 litre

This formula should be used full strength. The normal development time for Reprolith film is given as 2 – 3 minutes. The normal development time for Reprolith Orthochromatic Film is 1 – 3 minutes at 20 degrees C.

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Ansco 81

Ansco 81 is a single solution formula which is recommended for its convenience and excellent keeping qualities.

Water (52 deg C)

Hydroquinone

Sodium Sulphite (anh)

Sodium Carbonate (mono)

Citric Acid

Potassium Bromide

Cold water to make

750 ml

35.0 grams

55.0 grams

80.0 grams

5.5 grams

10.0 grams

1 litre

Don’t dilute for use with film. The normal development time is 3 minutes at 20 degrees C.

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Editor’s Note: The GAF formula, and the D-85 formulae that follow, intrigued me in that they used no strong alkali. I eventually discovered that this is due to the Formaldehyde-Sulfite Clock reaction, detailed here:

A clock reaction demonstrates an abrupt appearance of products after a period of time after mixing of the reactants. The formaldehyde-bisulfite-sulfite clock undergoes a rise in pH after a predictable period of time after mixing aqueous solutions of formaldehyde and bisulfite-sulfite.”

This can take an essentially acidic sulfite/(meta)bisulfite & formaldehyde solution from a pH of less than 7 & turning it to pH between 9-11. The reaction uses H+ leaving an excess of the hydroxide ion -OH.
This is quite obviously the explanation for how D85/AN(GAF)79 works.

So the paraformaldehyde dissolves, forms formaldehyde, which in turn reacts with the sulphite/(meta)bisulphite and liberates the hydroxide ion, which in turn forms sodium or potassium hydroxide.”

GAF 79b Paraformaldehyde Developer

This formula I got from an e-mailed message posted by Richard Knoppow in response to a message on rec-photo.darkroom. Richard indicates that this formula might have originated at AGFA. I’ve found that sometimes this formula is given with Solution B made up to one litre rather than three litres. I’ve both checked with references and tried this one out and am confident with the formula given below. In making it up I had a hard job getting the hydroquinone to go into solution. I’m going to read some more about this. Despite the difficulties with the hydroquinone, I had good results with the formula.

NOTE: The use of Paraformaldehyde in this formula necessitates careful handling and the use of proper protective equipment (gloves, mask and eye protection).

Solution A
Water (approx 52 deg C)

Sodium Sulfite, anhydrous

Paraformaldehyde

Potassium Metabisulphite

Cold water to make

750 ml

1.0 grams

30.0 grams

10.5 grams

1 litre

Solution B
Water

Sodium Sulphite (anhydrous)

Boric Acid Crystals

Hydroquinone

Potassium Bromide

Water to make

750 ml

120.0 grams

30.0 grams

90.0 grams

6.0 grams

3 litres

To Use for Films:

Mix one part Solution A with three parts Solution B.

To Use for Lith Printing:

I’ve tried various dilutions and have discovered that the best effects for lith printing were achieved with the following mix:

  • 300 ml part A
  • 900 ml part B
  • 100 ml of Old Brown
  • 8 litres of water

I had to use a big 16 by 20 tray to cope with this volume of developer. Perhaps because of the volume, I discovered that I was able to get quite a few more prints out of a mix than I’d ever achieved with Kodalith RT. The prints came up faster also which makes it a more productive session. Sometimes waiting for 15 minutes for an image to appear palls a little.

I also found that at lower levels of dilution the tones were more brown than pink on the Renaissance paper I was using.

Editor’s Note: It seems odd to mix up 3 litres of Solution B and then to use a dilution that requires three times the volume of B than A. The actual ratio described here works out at 1+3+26, plus the ‘old brown’.
Perhaps best to reduce the quantities of chemicals in Solution B to one-third those suggested and make up to one litre. Then use a dilution of 1+1+26 or 1+1+19? I will try this.

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Kodak D-85

This version of Kodak D-85 isn’t very stable and I’d advocate using the two solution version provided elsewhere on this page.

Water (125 F)

Sodium Sulfite (anh)

Paraformaldehyde

Sodium Bisulphite

Boric Acid Crystals

Hydroquinone

Potassium Bromide

Cold water to make

500 ml

30.0 grams

7.5 grams

2.2 grams

7.5 grams

22.5 grams

1.6 grams

1 litre

To Use with Films:

Use undiluted with a development time of 1.5 to 2.25 min.

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Kodak D-85 (two solution version)

In the same burst of e-mail messages on rec.photo.darkroom, Michael Gudzinowicz gave a two solution version of Kodak D-85.

Solution A

Water (125 F)

Sodium Sulfite

Boric Acid Crystals

Hydroquinone

Potassium Bromide

Cold water to make

500 ml

36.5 grams

9.4 grams

28.0 grams

2.0 grams

1 litre

Solution B

Water (90 F)

Sodium Bisulphite

Sodium Sulphite

Paraformaldehyde

Water to make

500 ml

11.0 grams

1.0 grams

37.5 grams

1 litres

To Use with Films:

Mix 4 parts solution A with 1 part Solution B.

To Use for Lith Printing:

No data.

(Editor’s Note: see The Master Photographer’s Lith Printing Course, by Tim Rudman)

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Wall’s Normal Hydroquinone Developer

Solution A

Water

Sodium Sulfite,dessicated

Hydroquinone

Cold water to make

500 ml

100.0 grams

20.0 grams

1 litre

Solution B

Water

Potassium Carbonate

Water to make

500 ml

120.0 grams

1 litres

To Use with Films:

Mix equal parts solution A and Solution B.

To Use for Lith Printing:

No data.

(Editor’s Note: see The Master Photographer’s Lith Printing Course, by Tim Rudman)

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Eastman D-9 Hydroquinone – Caustic

Solution A

Water

Sodium Bisulfite

Hydroquinone

Potassium Bromide

Cold water to make

500 ml

22.5 grams

22.5 grams

22.5 grams

1 litre

Solution B

Cold Water

Sodium Hydroxide

1 Litre

52.5 grams

Note:

Cold water should always be used when dissolving sodium
hydroxide because considerable heat is evolved and if hot water is used the solution will boil violently and may spatter and cause serious burns on the hands or face.

To Use with Films:

Mix equal parts solution A and Solution B. Wall notes
that films should be washed thoroughly after development and before fixing to avoid stains.

To Use for Lith Printing:

No data.

(Editor’s Note:see  The Master Photographer’s Lith Printing Course, by Tim Rudman)

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Kodak D-8 Lith Developer

Richard Knoppow provided also, this formula which dispenses with paraformaldehyde. Richard’s formula is as follows:

Water (90 degress F)

Sodium Sulfite (anh)

Hydroquinone

Cool before adding-
Sodium Hydroxide

Potassium Bromide

Water to make

750 ml

90.0 grams

45.0 grams

37.5 grams

30.0 grams

1 litre

Richard notes that the solution should be stirred thoroughly before use. He also suggests that a less alkaline version which will give nearly as much contrast can be obtained by reducing the amount of Hydroxide to 28 grams per liter. He also wisely notes that one should be very careful mixing the hydroxide as it produces a lot of heat going into solution and can cause boiling and splattering. Sodium Hydroxide should only be added to COLD solutions.

To Use with Films:

Mix 2 parts stock solution and 1 part water.

To Use for Lith Printing:

No data.

(Editor’s Note: see The Master Photographer’s Lith Printing Course, by Tim Rudman)

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Ilford ID-13

I’ve not been able to find out much about this developer other than it is for line and screen negatives.

Solution A

Water

Hydroquinone

Potassium Metabisulphite

Potassium Bromide

Cold water to make

750 ml

25.0 grams

25.0 grams

25.0 grams

1 litre

Solution B

Cold Water

Sodium Hydroxide

1 Litre

50.0 grams

Note:

Cold water should always be used when dissolving sodium hydroxide because considerable heat is evolved and if hot water is used the solution will boil violently and may spatter and cause serious burns on the hands or face.

To Use with Films:

Mix equal parts solution A and Solution B immediately before use. This solution has very poor keeping qualities. With normal exposures development is complete in 2.5 to 3 minutes.

To Use for Lith Printing:

Editor’s Note: These notes are from Brian Keen’s website, where I came across his recommendation to try this.

“I use 100ml part A plus 100ml part B and dilute with 1000ml water to give 1200ml.
To this I add 100ml of old brown. This is about the right amount for a 12×16 tray.
Using the developer soon after mixing while it is still warm will keep the development time down. I discard the developer after 3 prints.”

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Packo Lith Developer

Water (< 32 dec C)

Sodium Sulfite (anh)

Sodium Formaldehyde bisulphite

Hydroquinone

Sodium Bromide

Sodium Carbonate (mono)

Ascorbic Acid

Cold water to make

500 ml

3.0 grams

25.0 grams

12.0 grams

2.6 grams

23.0 grams

5 grams

1 litre

This formula should be used full strength. The normal development time for film is given as 2 minutes..

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DuPont D-7

Water (< 32 dec C)

Sodium Sulfite (anh)

Paraformaldehyde

Sodium Bisulphite

Boric Acid crystals

Hydroquinone

Potassium Bromide

Cold water to make

500 ml

60.0 grams

15.0 grams

5.0 grams

15.0 grams

45.0 grams

3.0 grams

1 litre

This formula should be used diluted 1 +1. The normal development time for film is given as 2 minutes.

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Welliver & Krizka Lith Developer

Michael Gudzinowicz provided this formula with the comments that stability has always been a problem with lith developers and most only have a working life of 2 hours or so. Ascorbate extends life by a small amount, but interferes with activity. By using metaborate as the base, the open tray life of this developer has been extended to 8 hours.

Water (< 32 dec C)

Hydroquinone

Sodium formaldehyde bisulphite

Sodium Carbonate

Sodium metaborate

Potassium Bromide

Cold water to make

500 ml

15.0 grams

50.0 grams

20.0 grams

20.0 grams

1.5 grams

1 litre

I’ve got no information about using this developer

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Acetonitrile Antioxidant Developer

Another approach to increasing the storage life of a lith developer has been to use acetonitrile as an antioxidant.

Water (< 32 dec C)

Sodium Carbonate (mono)

Paraformaldehyde Sodium Bisulphite

Potassium Bromide

Hydroquinone

Sodium Sulphite

Acetonitrile

Cold water to make

500 ml

50.0 grams

45.0 grams

2.0 grams

18.0 grams

2.0 grams

10.0 grams

1 litre

I’ve no information about dilution but that film should be developed for 2.75 minutes at 20 degrees C.

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2 Responses to Formulae from Melaleuca

  1. Pingback: Kodak D-85 Developer Test | Real Photographs

  2. Simon Yeo says:

    does anyone have a formula for the now unavailable Kodalith Fine Line developer ?
    best wishes,
    Simon Yeo. (UK)

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