Donald Quall's Paracetamol "Rodinal" works! :D

[Ryuji]

Synthesis of phenidone is complicated and messy.

Hydroquinone, catechol, pyrogallol, p-aminophenol have many other industrial uses and I don't expect them to go away, even if silver halide photography is completely dead.

In my opinion, it is not very useful to worry too much about supply of raw chemical stocks.

 

[srs5694]

In my opinion, it is not very useful to worry too much about supply of raw chemical stocks.

Except if you review this thread, you'll see that ZorkiKat, living in the Philippines, does have problems getting raw chemicals, hence his enthusiasm for Parodinal. Perhaps there are ways to get metol, phenidone, hydroquinone, etc. where he is (say, appropriate documentation with imported chemistry so that customs doesn't go nuts, or a local supplier he doesn't know about), but as I'm not familiar with the details of his supply problems, I personally can't offer much advice. Maybe somebody else could.

 

[Ryuji]

I see, I missed that part.

Isn't it possible to buy a small amount of Dimezone S from UK or US and make ascorbate developers? (It's rather straightforward, though a bit messy, to make a sugar type developing agent from glucose or other common sugars. They work similarly to ascorbate.)

Furthermore, isn't it possible to buy D-76 or any of Fuji powder developers? It's not as flexible as raw stocks, but it's certainly possible to customize these developers by changing dilution, and maybe a couple of additives.

 

[Donald Qualls]

Ryuji, one of the big issues is getting anything that ships as a powder past Philippine customs, apparently. They tend to assume it's disguised drugs, and (I'd guess) "test" it until there's nothing left to deliver to the addressee. Otherwise, he'd just order metol, phenidone, dimezone S, etc. from an American or UK supplier, as you've suggested. And the point of the whole thread is that there are *no* B&W developers available in his area (around Manila, wasn't it?).

Say, Zorkikat, another option that might be available to you -- if you can arrange to buy C-41 color developer from a minilab or minilab supplier, that will also work for B&W films, though you'll be pretty much completely on your own for times beyond the known data point that C-41 film in B&W developer usually requires a time a bit longer than Tri-X. That developer is likely to be available, and inexpensive, even if all B&W chemistry specific to photography is gone.

 

[Ryuji]

Ryuji, one of the big issues is getting anything that ships as a powder past Philippine customs, apparently. They tend to assume it's disguised drugs, and (I'd guess) "test" it until there's nothing left to deliver to the addressee. Otherwise, he'd just order metol, phenidone, dimezone S, etc. from an American or UK supplier, as you've suggested. And the point of the whole thread is that there are *no* B&W developers available in his area (around Manila, wasn't it?).

It's hard to believe. Don't they make better "drugs" than most parts of the world? Why do they want to buy stuff from the US or UK? (Ok, maybe amphetamines come from N Korea but that's a different story.)

And, if they don't sell developers, why do they make b&w films available?

There are a lot of comopunds that can be used as a b&w developer, from iron oxalate to color developers, but in terms of image quality it would be best to get some phenidone type agents.

 

[ZorkiKat]

It's hard to believe. Don't they make better "drugs" than most parts of the world? Why do they want to buy stuff from the US or UK? (Ok, maybe amphetamines come from N Korea but that's a different story.)

And, if they don't sell developers, why do they make b&w films available?

There are a lot of comopunds that can be used as a b&w developer, from iron oxalate to color developers, but in terms of image quality it would be best to get some phenidone type agents.

There is still very few available. One is a locally packed version of D72. And I suppose you already know that it, despite being a "universal developer", isn't the best soup to dunk films in. Most of the people who still use the inexpensive BW films are the ID photographers who don't really mind about how their negatives come out. Same people who develop their film in small cups in tiny box-like darkrooms. And they also do that with colour, and when they do, substitute the D72 and F-5 with C41 developer and RA4 blix (obtained from some labs who dispense small amounts of these chemicals). Even the numbers of this breed of photographers is dying- they are now converting to digital (using inexpensive types like the Kodak Easyshare, in conjuction with an inkjet printer). When the demand goes, the supply is cut.

The firm which prepares the D72 is probably not in the business of making developers now. It's hard to maintain production if sales meant just a carton or two every month. I spoke to one store who still had some stocks left- they sold only 1 D72 carton in the last three months.

There could still be a few packs (the remnants of the last stocks imported) of D76 lurking around. One gallon packs which would not be practical for a single user who develops an average of 1 roll per month. Yes, it might be possible for 4 people to divide the developer into four 1-litre/quart volumes. People who want to develop their own films don't really get to know who else is into it. Last week, 5 such people got to meet, not because they sought each other, but because we set up a film developing demonstration.

There is also two or three labs which still develop BW film. And expensively too. Quality isn't tops. People who shoot on traditional BW film send their films here for development. Where do these labs get their developers? One uses D72. The other, a more specialised one
gets to use real film developers. At one time, they even offered pyro development. This lab got a large batch of developers from Kodak. It also helped that the owner of this lab regularly travelled abroad where he could pick up a few stuff.

Going back to paRodinal: this developer is so easy to brew that it promises to be the wonder formula for the few remaining BW film shooters here. I myself have distanced myself from D76 and HC110 for two reasons. I wouldn't want to stay around till it disappears- I'd rather move on with something else which would be around longer and revise my working methods to adapt. Second, the Rodinal mystique is not contained phenomenon. It has been able to contaminate us as well. Rodinal hasn't been seen here in the last four decades, and most people only knew about D76 and Microdol even in the heyday of BW film. Being able to brew one so easily using easily
available materials is short of a miracle. It's being a one-shot developer from a long-lasting concentrate is one trait which even makes this developer more appealing.

Brewing stuff is also a pleasure which you aren't a stranger to.

And BTW, I do resent the comment, "Don't they make better "drugs" than most parts of the world?".

 

[gainer]

If you can get ascorbic acid or sodium ascorbate as Vitamin C, you can extend and in some ways improve Rodinal or its acetaminophen analogs. 4 grams of sodium ascorbate per liter of Rodinal 1+50 gives it the activity of Rodinal 1+25 and a little finer grain, but similar acutance. If you use ascorbic acid, add half its weight in sodium bicarbonate (surely you can get baking soda?) and mix the two in a little water until the effervescence subsides, then add that to the diluted Rodinal or Parodinal.

 

[dancqu]

It will be easier for a camera to pass through the eye of
a needle than strange looking powders through customs.

I wonder at such close scrutiny? Is it a way to keep
people employed? Fine tooth combing all that comes
into the country? Dan

 

[gainer]

Just remember that p-aminophenol and ascorbic acid are superadditive for developing film and can be used with several different alkalis to make interesting and usefull developers.
I met an interesting fellow in Santa Ana province in 1946, a Russian gone native, probably connected with the Hukbalahap, who made his own acetylene generator and did much mechanical work for the village. The Philipinos were, and probably still are, very adept at making something useful out of junked Army vehicles. Just a matter of interest.

 

[ZorkiKat]

I wonder at such close scrutiny? Is it a way to keep
people employed? Fine tooth combing all that comes
into the country? Dan

Yes they do. Its the smaller packages which get 'sniffed' more than the giant shipping containers. Powders would arouse much suspicion. Didn't you yourselves in the US had this sort of thing when anthrax powder was found in the mail? And its hard to explain to postal/customs workers what developing agents are. Just slightly harder than explaining why a can of 30 metre Ilford HP5 film shouldn't be opened for inspection.

 

[ZorkiKat]

Just remember that p-aminophenol and ascorbic acid are superadditive for developing film and can be used with several different alkalis to make interesting and usefull developers.
I met an interesting fellow in Santa Ana province in 1946, a Russian gone native, probably connected with the Hukbalahap, who made his own acetylene generator and did much mechanical work for the village. The Philipinos were, and probably still are, very adept at making something useful out of junked Army vehicles. Just a matter of interest.

Thanks Gainer. Interesting story. So you were here in WW2? I've heard of stories about 'lost' Russians here, usually 'white' refugees who escaped the 1917 revolution. The reworked army jeeps evolved into the 'jeepney' which is seen everywhere now. They have grown larger and longer than what was seen in the late 1940s. They are now mainly used for public transport.

Going back to developers- can a combination of paRodinal+sodium ascorbate be able to produce an equivalent to an MQ high contrast/high density developer? Ascorbic acid, as well as the other reagents like sulfite, bromide, carbonate, bicarbonate, borax, etc, needed to brew developers are still available. Its only the developing agents which are hard to get, having limited applications and vitually zero demand at present.

 

[gainer]

Thanks Gainer. Interesting story. So you were here in WW2? I've heard of stories about 'lost' Russians here, usually 'white' refugees who escaped the 1917 revolution. The reworked army jeeps evolved into the 'jeepney' which is seen everywhere now. They have grown larger and longer than what was seen in the late 1940s. They are now mainly used for public transport.

Going back to developers- can a combination of paRodinal+sodium ascorbate be able to produce an equivalent to an MQ high contrast/high density developer? Ascorbic acid, as well as the other reagents like sulfite, bromide, carbonate, bicarbonate, borax, etc, needed to brew developers are still available. Its only the developing agents which are hard to get, having limited applications and vitually zero demand at present.

I was there directly after the war. I was with the Corps of Engineers as a topographic computer. We were to assist the Coast and Geodetic Survey in first order mapping of the Philipines. I think accurate aerial mapping actually did the job later. I was only in the service for 18 months, 9 of them near Manila. I admired the people more than I can tell here, and was actually sad to have to leave.

It is quite possible to make a high contrast developer with p-aminophenol, ascorbic acid and sodium or potassium carbonate. I haven't tried getting the p-aminophenol from Tylenol, but I don't see why it wouldn't work.

 

[Donald Qualls]

The big trick with gettin your p-aminophenol for other formulae than Parodinal from acetaminophen is that you have to use a moderately strong hydroxide to cleave the acetyl group from the p-aminophenol, and then the developing agent will oxidize very quickly in the strong hydroxide unless you also have a fair amount of sulfite present -- and by that point you've got Parodinal. Carbonate alkali won't work starting with n-acetyl p-aminophenol, because it isn't a strong enough base to drive the reaction, and I don't think I'd want to be in the same room with an ammonium hydroxide solution strong enough to do the job -- which leave lye. I've heard the conversion might be possible using hydrochloric acid, effectively yielding p-aminophenol hydrochloride, but haven't had any reason to try it. It's also possible other very strong bases like phosphates could do the job, but again, I haven't tried it -- and sodium hydroxide is easy enough to get, almost anywhere (except some parts of the USA, where it's restricted as a methamphetamine precursor) that there hasn't been, AFAIK, any work done on reacting the acetaminophen with other bases.

Adding stuff to the Parodinal should work pretty much the same way it would with either Agfa/A&O Rodinal or R-09/F-09/"Original Rodinal" formulae. If you want to wind up with a carbonate developer, you might be able to add carbonate to the working solution of Parodinal -- by the time you dilute 1:50, the sodium hydroxide is at only 0.4% strength, and adding sodium carbonate might materially affect the results (either by propping up the pH against oxidation products, or by buffering it to a lower level and then holding that level, I'm not sure which).

I might have to try neutralized ascorbic acid as an additive with mine, though -- in my case, I'd probably dilute the Parodinal 1:100 and add 2g/L ascorbic acid plus 1 g/L sodium bicarbonate, to get back to the activity of the 1:50 I like so well. It'd make the Parodinal go twice as far, though it wouldn't save any money (ascorbic acid is a lot more expensive than acetaminophen) -- but if it makes finer grain with similar character, it'd be worth a look for the Classic 400/.EDU 400 I use a lot in 4x5...

 

[gainer]

I agree economics is not a good excuse for much of what we like to play with. In the case at hand, availability of ingredients is more of a limitation. We want to give a person as much freedom to play with different formulas as possible given the ingredients available.

He is able to make Parodinal, which should be a pretty good base for a lot of simple variations. The addition of ascorbic acid neutralized by baking soda or washing soda to Rodinal or Rodinal "expedients" is a worthwhile experiment as I reported some years ago. There are other combinations of p-aminophenol, sulfite, ascorbic acid, carbonates, hydroxides, etc. Among these you could find almost any developer characteristic you might want from litho to soft-working fine grain. Sodium ascorbate might make a better additive than ascorbic acid + baking soda for ease of use. A pretty good lith developer can be made from ascorbic acid, lye, sodium sulfite and potassium or sodium bromide. It might be that enough sodium chloride would substitute for the bromide.

I think it is interesting to see how far one can go with commonly available household and garden chemicals. Don't forget the combination of hydrated (slaked) lime or quick lime and washing soda if you cannot get lye.

 

[Ryuji]

Ascorbate won't work as a lith developer. Ascorbate-alone developer will take forever to develop AgX in gelatin, and even then, the contrast won't be anywhere near the classic hydroquinone lith developer.

Quick comment on Donald Qualls's post. Ammonium hydroxide is a bad choice in developer, unless you want unstable developer with high risk of dichroic fog and/or large grain. Also, food grade ascorbic acid is cheaper than acetaminophen, and technical grade erythorbic acid is also cheaper.

 

[gainer]

Ascorbate won't work as a lith developer. Ascorbate-alone developer will take forever to develop AgX in gelatin, and even then, the contrast won't be anywhere near the classic hydroquinone lith developer.

Quick comment on Donald Qualls's post. Ammonium hydroxide is a bad choice in developer, unless you want unstable developer with high risk of dichroic fog and/or large grain. Also, food grade ascorbic acid is cheaper than acetaminophen, and technical grade erythorbic acid is also cheaper.

Ryuji, are you speaking from experience or from theory? I once did a Q&D side-by-side test of hydroquinone and ascorbic acid as lith developers. I seem to remember very similar gradations with an edge in film speed to the hydroquinone. I'll try again. Maybe it was too quick or too dirty.

 

[ZorkiKat]

Ryuji, are you speaking from experience or from theory? I once did a Q&D side-by-side test of hydroquinone and ascorbic acid as lith developers. I seem to remember very similar gradations with an edge in film speed to the hydroquinone. I'll try again. Maybe it was too quick or too dirty.

I once OD'd (overdosed!) a developer, a sort of shot-in-the-dark brew with metol in it. It developed with rather high contrast. If I remember it right, it was based on D72 type (no hydroquinone though) but had about 20 grammes of ascorbic acid in it. Does that count?

Jay

 

[Donald Qualls]

I wouldn't think a developer with a huge amount of developing agent that thus produces high contrast (effectively due to overdevelopment) is quite the same as a lith developer. The characteristic of lith developers, with materials that suit them, is "infectious development" which is caused by developer oxidation products that increase development rate -- most common developers are either neutral in this regard or are restrained by their reaction products (the latter effect is partly responsible for bromide drag due to insufficient agitation with some formulae). This characteristic is used with what would be, in common developers, massively overexposed print materials to produce a very characteristic print appearance.

Hydroquinone is a developing agent that, in the absence of other agents and in suitable conditions of preservation and pH, is accelerated by its oxidation products; its analog ascorbate or erythorbate (more correctly, L-ascorbate that functions as a vitamin and D-ascorbate that doesn't) seems likely to give similar results, though it might require slightly different solution conditions to work best.

 

[Donald Qualls]

Quick comment on Donald Qualls's post. Ammonium hydroxide is a bad choice in developer, unless you want unstable developer with high risk of dichroic fog and/or large grain. Also, food grade ascorbic acid is cheaper than acetaminophen, and technical grade erythorbic acid is also cheaper.

No argument on either count -- however, generic acetaminophen is cheap enough to be very accessible, and is often easier to find than untableted ascorbic acid or erythorbic acid.

I wasn't suggesting use of ammonium hydroxide in a developer, only that it was the only other material I've read of that for certain can be used to cleave acetaminophen to p-aminophenol -- but the solution strength required to do so would make it mandatory to work under a fume hood; I'd much rather deal with anhydrous sodium hydroxide or strong solutions of same, since they at least mostly stay in the beaker or graduate instead of flying through the air...

However, I *have* used ammonium hydroxide in a developer with repeatably good results -- I used it to control pH in my HC-110 based, rapid fixer monobath. Since HC-110 already uses an ammonium-based alkali, I figured I wouldn't introduce anything horrible by using it to offset the acidity of the rapid fixer concentrate, and the results I got were well within the range normally expected from a monobath.

 

[Ryuji]

However, I *have* used ammonium hydroxide in a developer with repeatably good results -- I used it to control pH in my HC-110 based, rapid fixer monobath. Since HC-110 already uses an ammonium-based alkali, I figured I wouldn't introduce anything horrible by using it to offset the acidity of the rapid fixer concentrate, and the results I got were well within the range normally expected from a monobath.

I don't know what final pH did you reach, etc., but the following is a general description.

You can find a dissection of HC-110 here.

Dead Link Removed

The alkaline agents used in this developer are monoethanolamine and diethanolamine. They are primary and secondary amines, and they have weaker silver halide solvent effect than ammonium hydroxide, especially at high pH. (Ammonium hydroxide's solvent effect is pH dependent, in relation to its pKb.) HC-110 incorporates PVP to solve the dichroic stain that may be caused by the amines. However, I'm not certain if this in HC-110 is sufficient to counteract the additional solvent effect introuced by the ammonia and rapid fix, if the bath pH is high enough.

Anyway, historically, ammonia-pyro developer was used before the ammonia was replaced with carbonate or caustic alkalis. The replacement was very much well received in terms of stability of development.

I don't think there's a good reason to use ammonia in any developer today.

 

[gainer]

Menwhile, I did repeat what I thought was my comparison experiment, and did not get the results I thought I got. I have had an attack of viral meningo-encephalitis in the interim which did bad things to my memory circuits.

My experiment as I remembered it was a teaspoon each of hydroquinone, potassium bromide and sodium hydroxide in a pint of water in one case, substituting a teaspoon of ascorbic acid for the hydroquinone in the other. It is true that the hydroquinone mix showed the exponential buildup of density expected of infectious development: nothing much happened to a two-minute snip test in the first minute, and very dense black in the second. Nowhere near this density was reached in the ascorbate mix.

With respect to the use of ammonium hydroxide, Hurter and Driffield used both ammonia and carbonate, and settled on the carbonate as being much superior, showing many curves to support the conclusion.

Triethanolamine is a sort of analog of ammonia with ethanol in place of each hydrogen in NH3. I suppose it would be better to use it to control HC110 than ammonia.

 

[Ryuji]

My experiment as I remembered it was a teaspoon each of hydroquinone, potassium bromide and sodium hydroxide in a pint of water in one case, substituting a teaspoon of ascorbic acid for the hydroquinone in the other. It is true that the hydroquinone mix showed the exponential buildup of density expected of infectious development: nothing much happened to a two-minute snip test in the first minute, and very dense black in the second. Nowhere near this density was reached in the ascorbate mix.

This is expected.

The use of the term "infectious development" is somewhat subject to argument these days. Generally, infectious development means a process in which unexposed grains are developed in the vicinity of heavily exposed grains. This is the case with modern lith films and lith developers containing hydrazine and/or tetrazolium derivatives. However, in classic hydroquinone-only lith developers, this does not happen to any significant degree. What happens is a process in which lightly exposedgrains are developed in the vicinity of heavily exposed grains, where the same lightly exposed grains would not be developed otherwise. Many photographic scientists and engineers who work in the field of high contrast films/developers reserve the term "infectious development" for hydrazine/tetrazolium type system, not for classic hydroquinone-only lith system.
(Except, there aren't many those people any more.)

Triethanolamine is a sort of analog of ammonia with ethanol in place of each hydrogen in NH3. I suppose it would be better to use it to control HC110 than ammonia.

Triethanolamine, a tertiary amine, is a weaker base than ammonia. They are not very good substitutes. Carbonate is a better substitute for ammonia, but with no silver-halide solvent effect. Triethanolamine is a very mild alkaline agent that is suitable as a buffering agent in low pH fine grain developers, such as DS-10.

However, there are MANY amines that can be used in developers, some of which are quite effective.

 

[gainer]

Certainly hydroquinone alone has a long induction period during which nothing appears to be happening. However, the development rate is accelerating. A simple snip test as I did would show that, and that is probably what I saw. We would have a difficult time proving infectious development. A grid of exposed and unexposed lines would show widening of the exposed lines with infectious development, but where do we find an emulsion that has absolutely no fog density in "unexposed" areas?

What causes the acceleration of the development rate? There was no sulfite, only hydroquinone, NaOH, and NaBr.

 

[Ryuji]

Certainly hydroquinone alone has a long induction period during which nothing appears to be happening. However, the development rate is accelerating. A simple snip test as I did would show that, and that is probably what I saw. We would have a difficult time proving infectious development. A grid of exposed and unexposed lines would show widening of the exposed lines with infectious development, but where do we find an emulsion that has absolutely no fog density in "unexposed" areas?

What causes the acceleration of the development rate? There was no sulfite, only hydroquinone, NaOH, and NaBr.

With modern technology it's easy to make emulsion with essentially no gross fog density, as long as the speed is kept modest. Graphic art materials are generally slow (ASA 1 to 25 range if measured with continuous tone b&w negative criterion is used). So it's simple.

You should study literature before writing about it. It's easy to prove that point by making two batches of emulsions. One batch will be exposed, and the other not. Then blend the emulsion, coat and develop. You can also arrest development when development is premature and observe the specimen in electron microscope. (This requires cooling in liquid nitrogen, a liberal dose of powerful desensitizer, or both to prevent "printing out" of the emulsion in electron beam.)

Anyway, there are lots of techniques that are used in photographic science.

In the old days of classic lith processing, films were exposed twice. One is flash exposure (some overall non-image specific exposure) and the other is imagewise exposure, usually a continuous tone image exposed through screen (grid). So films processed in hydroquinone-only developers contained enough number of lightly exposed grains everywhere.

 

[gainer]

I gather from your exhorting me to read before I write that in your opinion, only those comments that are quotations from others are to be written. How did those others come to their conclusions? Why are there differences in opinion among them? Do you really think I did not read the literature that is available to me? Perhaps you should reread some of it yourself, especially that which applies to triangular-shape halide crystals.