Who formulates their developer?

[rodeo_joe1]

IMO, it depends if you want the sort of haphazard "muck about" with developing that Caffenol provides, or something utterly repeatable with a solid chemical basis.

 

Apparently the photographically active ingredient in coffee is caffeinic acid, and not caffeine. I very much doubt that the amount of caffeinic acid in instant coffee is well regulated, as is the dose amount in a pharmaceutical caplet of paracetamol. Or a weighed amount of ascorbic acid, or phenidone. Both of which have a low toxicity. And who would class a strong solution of washing soda as "non toxic"?

[ben_hutcherson]

IMO, it depends if you want the sort of haphazard "muck about" with developing that Caffenol provides, or something utterly repeatable with a solid chemical basis.

 

Apparently the photographically active ingredient in coffee is caffeinic acid, and not caffeine. I very much doubt that the amount of caffeinic acid in instant coffee is well regulated, as is the dose amount in a pharmaceutical caplet of paracetamol. Or a weighed amount of ascorbic acid, or phenidone. Both of which have a low toxicity. And who would class a strong solution of washing soda as "non toxic"?

 

If I were looking for caffeine, my inclination would be to use No-Doz, which(in the US) falls under FDA regulations as a medicine and contain a known 200mg of caffeine per tablets.

 

Even at that, I tend to use reagent grade chemicals, but I realize that's easier for me to say and do than it is for a lot of other folks. I'll also synthesize things if there's an easy way to do so, although that can be a different story. I can also easily assess both whether or not I have the desired reagent and the purity(and do further work to purify it if needed). Again, not everyone has access to the tools to do that.

 

I love the in-situ synthesis of p-aminophenol in your formula for Rodinal, also.

 

BTW, I wrote a teaching lab experiment this year on quantifying the amount of caffeine in various beverages by GC-MS. I can tell you that we had two different kinds of instant coffee in the mix(although brewed coffee is far more common in the US than instant coffee) and both showed different levels of caffeine. Of course, it's also all over the place for brewed coffees, with decaf being on the low end at 10-20mg per 8 oz. and some especially potent ones being over 100mg/8oz.

 

I can only assume that the since the caffeine in the instant coffee is converted to caffeinic acid(I'll have to double check the formulation so see exactly how that's done-I don't have time to look it up now) it's done in such a way that caffeine is in excess. Still, I'm in agreement that I'd prefer something repeatable.

Edited June 2, 2017 by ben_hutcherson

[Bill Bowes]

Hello again. If you follow Reinhold at his blog site you will see that his ideas are based on PRECISE methods of work, not just throwing this n that together. If you also do some more homework you will find that the major brands of instant coffee have as rigid control of their "receipes" as any pharma company does with it's drug manufacturing. People buy the instant coffee for a certain taste, and if you muck about with that taste, you loose their dollars. Almost from the start of his blog, I followed his various "creations" for different film developing. They are repeatable & yield excellent negatives. As mentioned earlier, I still fall back to Caffenol developing for the Copex & Tech-Pan like materials offered on todays markets. In over two years of working these films with various diluted mixes of Rodinol, 510-Pyro & my current Obsidian Aqua, the Coffenol wins out. As an aside, I consider the "taste" of ANY instant coffee horrid! but I always purchased only one major brand during the caffenol days. Aloha, Bill

[rodeo_joe1]

"People buy the instant coffee for a certain taste, and if you muck about with that taste, you loose their dollars. "

 

- Exactly! The coffee is roast and blended for a standardised (horrible) flavour; not for a standardised caffeine or caffeinic acid content.

 

Coffee is a natural product and growing it is weather and soil condition dependent. Therefore its exact chemical composition cannot possibly be accurately regulated.

 

I see no specific brand of instant coffee recommended for Caffenol. If the recipe was a true formula, then the exact type of coffee would be specified.

 

I also see that pure caffeine can now be bought over the counter as a dietary aid(!). Surely that would be a better basis for a developer? It might actually work out cheaper than piling tablespoons of instant coffee into a developing tank - if indeed caffeine is the active ingredient. Caffeinic acid would be converted to some salt or other by the addition of the necessary alkali accelerator in any case.

[ben_hutcherson]

I also see that pure caffeine can now be bought over the counter as a dietary aid(!).

 

In the US at least, as I mentioned above, it can be bought OTC as a pharmaceutical stimulant. It's marketed under the name No-Doz in 200mg tablets.

 

The fact that it's a pharmaceutical is significant as it falls under FDA regulation, and not the otherwise unregulated supplement market. I'm not trying to start a debate, but a pill made/sold under FDA guidelines must contain the actual stated amount of active ingredient within the specified margin of error.

[James G. Dainis]

No-Doz is still around? We used to take that during final exam all night cram sessions back in college fifty years ago.

[ben_hutcherson]

No-Doz is still around? We used to take that during final exam all night cram sessions back in college fifty years ago.

 

Indeed it is.

 

In fact, I oversee an experiment every year where the students quantitate acetylsalicylic acid, acetominophen, and caffeine in a variety of OTC pain killers and other products by HPLC. There are several products(notably Excedrin) that contain all three, but we also use No-Doz as on.

 

Personally, if I want 200mg of caffeine in my body, I'll drink a couple of cups of coffee :) . If I want it for something repeatable, I'd rather buy tablets with a known amount or, probably for me, just grab the bottle of pure caffeine off the shelf. Not everyone has the luxury of the latter, though.

[glen_h]

There was a story not so long ago, of some teen buying bulk caffeine, maybe 1kg, and then ODing on it.

 

Why do that, instead of No-Doz from the nearby store, I don't know, maybe because it is cheaper.

 

Then his family wanted regulation to stop people from being able to buy it.

 

But one could just as easily OD on No-Doz, as, as far as I know, there is no limit on how many bottles you can buy.

[glen_h]

As for the actual question, it seems to be that it often costs more to buy the separate ingredients.

 

I suspect that there isn't as much economy of scale, as in some popular pre-mixed versions.

 

If you buy reagent grade chemicals from a chemical supply, you are paying extra for the

unneeded purity. (There are a few contaminants that effect development, but otherwise,

photographic grade is pretty low on the chemical purity scale.)

 

Some of the more expensive components will come in larger than desired packages,

such that you never use them up.

[ben_hutcherson]

There was a story not so long ago, of some teen buying bulk caffeine, maybe 1kg, and then ODing on it.

 

Why do that, instead of No-Doz from the nearby store, I don't know, maybe because it is cheaper.

 

Then his family wanted regulation to stop people from being able to buy it.

 

But one could just as easily OD on No-Doz, as, as far as I know, there is no limit on how many bottles you can buy.

 

I've never bought No-Doz, but a quick Google search shows 60 ct. bottles. That's 12g of Caffeine in the bottle. For adults, the LD50 of caffeine is roughly 200mg/kg. For someone who weighs 90kg(~200lbs) that amounts to 90 No-Doz pills, or less than two bottles. If you're more on the order of 55kg(~150lbs) that makes less than a full bottle a lethal dose.

[ben_hutcherson]

And, as a side note, I was putting together an experiment back in the spring semester(GC-MS analysis of caffeine in beverages) and couldn't find any caffeine in the stock room and only about 10g in one of the labs. We hadn't ordered any in years, and I guess that we'd finally used it all up making the standards for the pain tablet experiment I mentioned earlier.

 

I ordered a 1kg bottle, and I'll just say that I can't possibly imagine someone taking that much of it. Like a lot of organic solids, it's very "fluffy" and 1kg mostly fills the 1L size bottle it's packaged in. That would be a lot of powder to ingest, not to imagine that I suspect that being an amine it would have a terribly bitter taste. I've never gone out of my way to taste it, but the small amount I've inhaled(remember, fluffy powder) when weighing it out didn't leave a great taste.

[tomspielman]

A lot of the technological advances in photography have revolved around increasing the predictability of the results/reducing the risk of bad results. Whether it's auto-exposure, auto-focusing, auto bracketing, wide latitude film, or finally, - digital sensors with uniformly placed pixels rather than the far less uniformly arranged crystals found on films.

 

I think one reason to shoot film vs digital is exactly for the randomness. Deciding to hand-process vs machine process also introduces variability. Can anybody really manage to repeatedly agitate exactly the same way at exactly the same precise intervals?

 

Even with with the same camera and lens, sitting on a tripod taking shots of a stationary object a fraction of a second apart, you will not get the same image twice. They might be close enough for most people not to notice unless zoomed in really close, but the difference will be there.

 

Obviously, there's more risk in film photography and more time involved per image taken. So there is a natural desire to have a certain degree of predictability too. The question is, how much does the natural variance in the active ingredient in the same brand of instant coffee really matter, especially when you consider the variability of all the other things involved in shooting and processing film?

 

Do I shoot film because I get better results? Mmmmm.... I like the look of film, but I also enjoy the process and Caffenol adds a little bit of extra fun.

Edited June 17, 2017 by tomspielman

[ben_hutcherson]

Obviously, there's more risk in film photography and more time involved per image taken. So there is a natural desire to have a certain degree of predictability too. The question is, how much does the natural variance in the active ingredient in the same brand of instant coffee really matter, especially when you consider the variability of all the other things involved in shooting and processing film?

 

Do I shoot film because I get better results? Mmmmm.... I like the look of film, but I also enjoy the process and Caffenol adds a little bit of extra fun.

 

I guess it's a difference in philosophy.

 

I approach the technical aspects of film photography as a scientific exercise. I know that the medium I use(in color, the process type and film stock, in B&W the film stock, developer, etc) will introduce its interpretation, but I consider it part of my job as a photographer to learn and understand how the medium will dictate the appearance of the final product. Knowing the medium allows me to use its strengths/weaknesses to my advantage in my composition.

 

Thus, I want predictable results from a film stock, not an element of randomness. I guess that's a side product of my background as a scientist, but the chemist in me also wants reproducible results in a developer when I'm formulating it myself.

 

BTW, this is a side note and no one has brought this up in this thread, but along those same lines I DETEST the use of "analog" in reference to film photography. Film grains are either there or they're not. Density forms from increased grains in a certain area, not from one individual grain becoming more intense. That's as opposed to "digital" photography, where each pixel on the sensor has a response proportional to the amount of light falling on it.

[tomspielman]

I'm glad I used the word "film" instead of analog. :)

 

But I do agree with you. I've gotten into some long discussions on digital vs "analog" in a different forum. I expressed the opinion that "digital" really applies to way images are stored, not captured. The person I was discussing this with disagreed mightily. He went on to say that film is "organic" and that it works much more like the human eye does relative to photo-sensors. Which I thought was interesting since I'd be hard pressed to name many things less organic than film. It's not like there are Ektar plants and Kodachrome trees.

 

FWIW I probably find film interesting for reasons a bit different than you since you are a chemist. My field is computers and though imaging is not something I have much expertise in, I don't see it as magic. Film is much more magic to me, - a non chemist.

[glen_h]

I think the one I remember is:

 

Teen's death prompts FDA to take aim at powdered caffeine

 

but it seems that last month a teen died from a latte, a Mountain Dew and an energy drink.

 

I presume everyone knows that all these chemicals are insecticides.

Nicotine, caffeine, and morphine are intended to keep insects from eating the plant that makes them.

 

As far as coming from plants, the original flexible film was cellulose nitrate, and now is usually cellulose triacetate, where cellulose comes from pants, made by linking sugar molecules together in long chains. The acetate comes from acetic acid, which also comes from plants. (I am not sure that it always comes from plants.) And gelatine is a protein, also produced by living organisms. Then there is the backing paper and, in the early days, wooden spools.

[ben_hutcherson]

Anything that contains carbon-carbon bonds is organics. That applies to the substrate in film, the gelatin, and all the developers I know of.

 

CCD and CMOS sensors both contain organic compounds in their construction.

[tomspielman]

Silver halides? Organic?

[ben_hutcherson]

Silver halides? Organic?

 

No, but as I said gelatin and the polymer base are.

 

Also, the dyes in color film are all organic compounds. The Bayer pattern filters on CCD/CMOS sensors are also organic compounds

[rodeo_joe1]

Wow! This thread has taken a slight side turn since I last visited. Randomness, serendipity and lethal doses. Who'd have guessed?

 

I dropped by to ask Ben if he knows whether it's Caffeine or Caffeic acid that's the active ingredient in Caffenol?

 

The internet claims it's Caffeic acid, but also claims that Caffeic acid is present in nearly all plantlife. Its stated concentration in coffee is only 0.03mg per 100gms, which would make it the most potent developer known! Since Phenidone is used at a rate of 250mg/litre or thereabouts, that would make Caffeic acid about 4 orders of magnitude more powerful.

 

Reading further I discover that Sage leaves contain a hundred times more Caffeic acid than coffee. Anyone for Sagenol? Teanol? Earl Grayenol?

 

Something seems not to add up in all this. Any enlightenment Ben?

 

Another alternative is that it's neither Caffeine nor Caffeic acid, but the power of wishful thinking on the part of Caffenol devotees that's the developing agent.

Edited June 20, 2017 by rodeo_joe|1

[ben_hutcherson]

Wow! This thread has taken a slight side turn since I last visited. Randomness, serendipity and lethal doses. Who'd have guessed?

 

I dropped by to ask Ben if he knows whether it's Caffeine or Caffeic acid that's the active ingredient in Caffenol?

 

The internet claims it's Caffeic acid, but also claims that Caffeic acid is present in nearly all plantlife. Its stated concentration in coffee is only 0.03mg per 100gms, which would make it the most potent developer known! Since Phenidone is used at a rate of 250mg/litre or thereabouts, that would make Caffeic acid about 4 orders of magnitude more powerful.

 

Reading further I discover that Sage leaves contain a hundred times more Caffeic acid than coffee. Anyone for Sagenol? Teanol? Earl Grayenol?

 

Something seems not to add up in all this. Any enlightenment Ben?

 

Another alternative is that it's neither Caffeine nor Caffeic acid, but the power of wishful thinking on the part of Caffenol devotees that's the developing agent.

 

That's actually a really good question, and one to which I don't intuitively have an answer. Neither actually jumps out at me as having a site that can be easily oxidized.

 

When a good chemist doesn't know, though, he experiments.

 

As it so happens I have both caffeine and caffeic acid on hand. It should be easy to mix up each in a solution with sodium carbonate and see what happens when you add in a small amount of silver bromide. Even if I can't visually see it, I should be able to do it in-situ in a UV-VIS cuvette. Both caffeine and caffeic acid absorb in the UV range, and any chemical change that comes about from them being oxidized by the AgBr should show up as a change in λmax.

 

I do note with some interest that most caffenol "recipes" that I find also specify the inclusion of ascorbic acid, something which is well known as a reducing agent. I remember when caffenol was first making the rounds, it was described as being a VERY slow developer-I can't help but wonder if, like you said, something else was actually behind the development. I suspect coffee contains a small amount of ascorbic acid-it may be that's the active ingredient anyway, and in current ascorbic acid forumulæ the coffee is on there "because."

[ben_hutcherson]

Alright, after a bit of experimenting I can pretty safely say that caffeic acid and NOT caffeine is the active reducing agent. I will give a full write-up later this evening, including photographs.

[rodeo_joe1]

Thanks Ben!

 

Sooo, maybe Sagenol, Thymenol, Red Vinol or Black Chokeberrinol are on the cards?

 

I still find it hard to believe that as little as maybe 0.3mg/litre of Caffeic acid are enough to develop more than a couple of AgX "grains".

 

I once tried a pure Ascorbate + alkali developer with zilcho results after 10 minutes immersion. So I'm pretty sure that whatever's going on involves a superadditivity effect.

 

Of course there are reducing agents that have been rejected (as developers) in the past because they don't differentiate between exposed and unexposed silver halides. Is it possible to reduce (sorry!) the concentration of such a reducer to the level where it develops a latent image?

[glen_h]

Thanks Ben!

(snip)

 

Of course there are reducing agents that have been rejected (as developers) in the past because they don't differentiate between exposed and unexposed silver halides. Is it possible to reduce (sorry!) the concentration of such a reducer to the level where it develops a latent image?

 

In many developers, there is an agent that actually does the reduction of silver in silver halide, and then another, often sulfite, that reduces the oxidized developer back to the active form. That is, sulfite is a stronger reducing agent, but mostly doesn't reduce the silver in silver halide. The actual active agent doesn't need to be in high concentration if it is restored fast enough.

 

I have never been interested in trying caffenol, so I don't even remember if it has sulfite.

[ben_hutcherson]

Okay, so as promised here is sort of the "master" experiment.

 

I didn't photograph as much as I should have, but this should give you an idea.

 

First of all, I took 200mL of DI water then added 10g sodium carbonate. Once it was completely dissolved, I added 1g caffeine, and a few hundred milligrams of AgI.

 

I left this heating and stirring for several hours, but the solution remained unchanged. It was clear and colorless with undissolved AgI on the bottom.

 

I didn't have a LOT of caffeic acid, but I added about 200mg, and within a couple of minutes I had this

 

 

I decanted a small amount of it off

 

 

I THOUGHT that this was elemental silver, but just to make sure I did a little classical chemistry and added nitric acid. The black flakes readily dissolved in nitric acid.

 

 

And, just as a double check, I added sodium chloride and got a white precipitate. That can be assumed to be AgCl.

 

Finally, I ran a side experiment that I didn't do as much with where I added sodium carbonate and a few hundred milligrams of caffeic acid. This is what it looked like when I put AgI in it.

 

[tomspielman]

Spearmint is easy to grow and would smell better but I wonder if it has other ingredients that would render it unusable.

 

I believe caffenol was developed (snicker) to prove that everyday household items could be combined to make a developer. Adding in Vitamin-C powder made it work better but was kind of cheating because it's not something that most people keep lying around or that can be found in many grocery stores.

 

As time has gone on, instant coffee is no longer very common in the home, -not in US households at least. Washing soda can be found in fewer and fewer grocery stores. I honestly don't know what its intended use is. In my case, D76 is actually easier to come by since there's a photography supply store a few blocks from where I work. So Caffenol's raison d'être may not really apply anymore, or for not much longer.

 

One practical advantage Caffenol has, is that now that I've purchased the ingredients I have enough to last me a very long time given that I only need to mix as much as I need. What I was told with D76 is that you need to use the entire packet because you can't guarantee the uniformity of the mixture if you only use part of it. Of course, once you prepare it, it's good for 6 months or so, but the Caffenol ingredients I have will last much longer than that.

 

The other advantage people will state is that you can vary the amounts of the individual ingredients you use to get different results. With D76 all you can do is vary the dilution.

 

I think that part of the appeal of Caffenol is that it uses ingredients that people recognize even if it's rare to find them in a single store anymore. For that reason, there is kind of a "Wow" factor. "You mean, that really works?"

 

Yes, it does.

 

And I think that is a valuable thing for film photography. It has become an expensive hobby if you don't process your own film. People are under the impression that it's hard to do, - and it really isn't. Caffenol makes it seem even more do-able, even if in reality it's much easier to use a traditional developer.

Edited June 21, 2017 by tomspielman