DTOD in Kodak D94A for motion picture film

[SkipA]

Does anyone know what chemical DTOD is? Kodak says it is C6H14O2S2, but I'd like to know what the common name is so I can order some.

Kodak replaced the old B&W motion picture film D94 developer and R9 potassium dichromate bleach formulas with D94A and R10. The main impetus for this change was to eliminate the heavy metal chromium used in the old bleach. The new R10 bleach is a permanganate bleach.

I always have mixed the D94 developer and R9 bleach from bulk chemicals. I'd like to do the same with the new D94A and R10 bleach, but the new first developer has this DTOD.

Here is the old D94 formula:

Kodak D-94

Water, 50 degrees C (125 F) 750 ml
Kodak ELON (Metol) 0.6 g
Sodium Sulfite (anhydrous) 50.0 g
Hyrdoquinone 20.0 g
Potassium Bromide (anhydrous) 8.0 g
(or 7.0 g Sodium Bromide)
Sodium Thiocyanate (liquid) 9.1 ml
Sodium Hydroxide 20.0 g
Water to make 1.0 L

And the new D94A devloper

Kodak D-94A

Water, 50 degrees C (125F) 750ml
Kodak ELON (Metol) 0.6g
Sodium Sulfite (anhydrous) 60.0 g
Hyrdoquinone 20.0 g
Sodium Bromide 7.0g
DTOD 0.42g
Sodium Hydroxide 20.0 g
Water to make 1.0 L

The formulas are pretty similar. There's no Sodium Thiocyanate in the new D-94A, but there is this new DTOD. Sodium Bromide replaces Potassium Bromide, and the amount of Sodium Sulfite is increased.

The amount of DTOD is less than half a gram per liter of developer. Can anyone suggest what might happen if I just left it out?

 

[Helen B]

DTOD? Dithiaoctane diol? It is a silver halide solvent, so it sounds like a replacement for the thiocyanate, but maybe (I'm not certain, and don't have my reference 'library' here) with better granularity controlling properties because emulsion softening can be a problem when you switch from dichromate to permanganate bleach. I'd be inclined to ask EK - the Motion Picture dept people are always as helpful as they can be - or even Goldschmidt (I think that their name has been mis-spelled by EK in H24-15).

Here it is from ScienceLab at $50 for 25 g.

It is also used in ripening during emulsion manufacture - as is thiocyanate.

I'm not sure if any of that is practically useful - unless you can find a lab able to sell small quantities and you don't mind handling it.

Best,
Helen

 

[SkipA]

Thanks, Helen. I appreciate the info, and especially the link to ScienceLab. It's definitely helpful.

25 grams is enough for 59 liters of developer, but at a cost of $50 (plus hazardous shipping fee...) it certainly makes D94A a considerably more expensive developer than D94. Perhaps I can find a cheaper source, or maybe I'll just stick with D94 after all. I don't think I put enough heavy metals into the environment with the tiny amounds of R9 bleach I use to worry much about it. Or to keep me from rationalizing my use of it.

A couple of the guys from filmshooting.com were wondering about DTOD, too, so I'll point them to this thread.

Thanks again,
Skip.

 

[jim appleyard]

How much of a hazardous material is "enough"? What happens when eveyone discharges a "tiny" amount? Your actions might not affect you, but they might affect someone else.

 

[SkipA]

Jim, hexavalent forms of chromium in the environment come primarily from industrial sources. Chromium is used the production of various types of steel, e.g., chrome steel and stainless steel. Stainless steel contains 11 to 18 percent chromium. Potassium Dichromate and Sulfuric Acid (same as Kodak R9 bleach, albeit perhaps different concentrations?) is used to clean laboratory glassware (non-chromium alternatives are beginning to replace the dichromate versions). An alloy of nickle and chromium is used to produce the heating elements in electric coffeepots and toasters and broilers and ovens and cup warmers and virtually anything else with an electric heating element. It's used in hardened metal cutting tools and in surgical tools. It's used in some leather tanning processes. It's used in the production of pressure treated wood and in concrete cement. It is used along with cobolt in blue and green colored pigments such as eye-liners and other makeup products. It is an airborne byproduct of burning coal. Chromium is used as a film intensifier (less toxic than selenium, by the way), and in tiny quantities as a contrast agent in platinum and palladium paper developers, and also in light sensitive emulsions for alternative photographic processes such as ceramic and enamel processes.

If you research it a bit, you'll find websites that identify common products containing chromium, and list uses such as alloys of metallurgy, adhesives, anticorrosives in antifreeze, oils, and paints, automobiles, bleach, blue prints, bricks, catgut sutures, cement, ceramics, chrome plating, chrome steel, copy paper, dental implants, detergents, drywall, electroplating, electric batteries, engraving and lithography, eye shadow, fireworks, floor wax, foundaries (added to sand for bricks), glue, green dyes, ink, mascara, matches, milk testing, mortar, orthopedic products, pacemaker wires, paint (green, orange, yellow), photography (color developing, as well as b&w reversal processes, alternative processes), pigments, plaster, pool table felt, shoe polish, stainless steel, leather tanning, tattoos (green), textile dyes (military green), TV manufacturing, Vitamin supplements, welding, and wood preservatives. I'm sure there are more.

Since you are on this forum Jim, I'm assuming that you are a photographer, and not a mudhut-groveling luddite who believes that humans should abandon modern technology and the comfort and prosperity it brings about in order to return to an agrarian or hunter-gatherer society. Do you work in a darkroom, or just farm the dirty work out to someone else? Do you recapture the silver from your fixer before discarding it? Do you collect your selenium toner and bring it to a hazardous waste facility? If you do, then of course, you have my respect for that.

When I built my darkroom, I visited my city wastewater engineer and asked him about disposing of hazardous chemicals, heavy metals, silver recovery, and so forth. After getting over his incredulity that I took the time to contact him to discuss the matter, he told me that the city wasn't concerned about the metal-bearing effluent produced by home hobbyist darkroom enthusiasts, not even the silver, which is by far the greatest contaminant. He told me I could just dump it down the drain, that the amount that I could produce in a home darkroom wouldn't be detectable in the water treatment plant.

But if you are a luddite, I suggest you give up photography, and modern living. You never know just how much damage your lifestyle may be doing to others.

 

[jim appleyard]

Sorry, but this long-winded excuse that "everyone else does it, so it must be ok for me" doesn't cut it; and I am careful of what I dispose of and how I do it.

 

[fhovie]

Hey Skip - can I quote you on that - That is the best tie raid I have read ... ever! Wow. I am still chuckling here. Thanks. and ... I agree with you. Man was created to dominate the earth. It was created for us - we are not an evil parasite here. And, of course, we do want to take care of it intelligently and to a great degree, we are.

 

[SkipA]

Thanks, fhovie, and feel free to quote me. While I don't subscribe to a belief in creation, I certainly agree that we are as much a part of the world as every other part of nature, and it is in our best interest to care for the earth, our home, and use it intelligently. I do see signs that we are doing better at it. At the same time, there is simply no such thing as zero impact living.

 

[SkipA]

Jim, as photographers, we all have to come to grips with the reality that film and photographic paper production and processing involves the use of a number of organic and inorganic chemicals and compounds, some of which are toxic and environmentally unfriendly, either directly or indirectly. Just think of all the cows whose hooves go into making gelatin for film and paper emulsions, and the impact that raising those cows has on the environment.

Even if you bottle the more ojbectionable effluents you produce and bring them to a hazardous chemical disposal facility, some traces of it will get out into the environment. Not all of it will be rendered 100% harmless.

So you've reduced the tiny amount of heavy metal pollution to an even tinier amount. Good. I do the same with silver, at least. But still, your actions as a photographer might affect someone else. It's just a matter of degree, right? In that case, you might seriously want to give some thought to moving into a mud hut in a clearing in the woods, eschew all modern conveniences and technology and medicine, and yes, your computer, and use of electricity, excessive consumption of forest products, and be careful about the types and quantities of foods you eat (since human waste itself can be harmful in sufficient quantity). Also, be kind enough to limit your reproduction to just the number of children sufficient to replace yourself and your mates, so as to not put more pressure on the earth. And before you finally take leave of the world, kindly insist that your family dispose of you in a green burial site, so at least the earth can get a little bit back of what you took from it.

 

[jim appleyard]

Skip, I'm curious. You've asked me if I dispose of certain chemicals in a proper way by taking them to a hazardous waste area, but yet you're going to dump a chemical with chromium down the drain???

 

[SkipA]

Yes. I wanted to know if you adhere to the same high standards that you set for others.

As it pertains to photochemicals, you assert that you do. I congratulate you. You haven't mentioned how far you take your philosophy in other aspects of your life. It's clear you use a computer and electricity, but you haven't mentioned whether you use a car, have any cement or mortar or brick or pressure treated lumber in your home, use stainless steel or tanned leather, watch TV, use adhesives, glues, antifreeze, green, yellow, or orange paints or other similarly pigmented products, use appliances with electric heating elements, etc. These things all either contain chomium, or chromium is used in their manufacture. Many of these products end up in landfills where they may eventually permeate barriers and enter the soil, or may be carried off by rainwater runoff, and so forth.

When I built my darkroom three years ago, I discussed my use of various photochemicals with the city water engineer. He didn't regard my projected use to be significant. Even so, I precipitate silver out of my fixer before disposing of the liquid down the drain. It's easy to do, and since I use a fair amount of fixer, it seems reasonable.

I bought a pound of potassium dichromate eighteen months ago, and I know I've used less than half of it. I occasionally use selenium for toning prints and even more infrequently for enhancing negatives. And when I'm done with either of these two solutions, I simply pour them down the drain. I use such small quantities of these solutions that I see no particular reason to obsess about it.

 

[Pakman777]

OP was 2004 . . . still, for the record, just wanted to say that "DTOD" stands for 3,6-Dithia-1,8-octanediol, or referred to by Kodak as 1,2-di(hydroxyethylthioethane). One supplier has it for $37.70 for 25 grams, and is easily located through a Google search using 3,6-Dithia-1,8-octanediol for the search.

 

[Alan Johnson]

1. DTOD is mentioned in the Film Developing Cookbook 2020. I tried to get some in Europe, UK and US from well known suppliers , without success. Appears the markup and cost of shipping mean that it is unlikely to be available as a solvent anytime soon.

 

[albada]

DTOD is CAS 5244-34-8
My notes say it's a halide solvent, and can replace thiocyanate.

Mark Overton

 

[KPA40]

1. DTOD is mentioned in the Film Developing Cookbook 2020. I tried to get some in Europe, UK and US from well known suppliers , without success. Appears the markup and cost of shipping mean that it is unlikely to be available as a solvent anytime soon.

I purchased my DTOD from S3-Chemicals (s3-chemicals.de) in December 2020. DTOD is not in the standard assortment of the company; but it was a special order. For 25g I paid 37.50 EUR + VAT and shipping costs. In total 49.30 EUR.
They also made me an offer for 250g for 140.00 EUR + VAT + shipping costs.
By the way, the manufacturer of my DTOD is TCI, Tokyo Chemical Industry Co., LTD.

Olaf

 

[Anon Ymous]

I purchased my DTOD from S3-Chemicals (s3-chemicals.de) in December 2020. DTOD is not in the standard assortment of the company; but it was a special order. For 25g I paid 37.50 EUR + VAT and shipping costs. In total 49.30 EUR.
They also made me an offer for 250g for 140.00 EUR + VAT + shipping costs.
By the way, the manufacturer of my DTOD is TCI, Tokyo Chemical Industry Co., LTD.

Olaf

I bought 50g of it back in 12/2019 from Suvatlar for about 25€. No idea how much it would cost today, or if they still stock it.

 

[KPA40]

I bought 50g of it back in 12/2019 from Suvatlar for about 25€. No idea how much it would cost today, or if they still stock it.

You lucky boy. Before I inquired at S3-Chemicals, I had inquired at Suvatlar. Mr. Suvatlar replied that he had checked again but unfortunately he no longer had any stock and the chemical was no longer listed in his suppliers' directories. It looks like I was a year too late .
Olaf

 

[Raghu Kuvempunagar]

What's special about DTOD compared to Thiocyanate?

 

[Pakman777]

Folks, I appreciate all the good feedback. It is helpful.

Raghu: Nothing that I am aware of chemistry-wise, only that it is the difference (please correct me if I am wrong, anyone) between D-94 (Thiocyanate) and D-94A (DTOD).

On this question, I would like to know from those who really know (is Ian Grant still around?) about actual benefits of both formulas. I am planning on processing Trix 7266 Super 8 and 16mm reversal film, as reversal film (not negative).

Alan: My apologies; I stand corrected. I too have had no luck actually purchasing DTOD in the US after broadly stating that it is available through a number of retailers via simple Google search. The two I attempted to order DTOD from (AK Scientific and Sigma Aldrich, aka Millipore Sigma) required licensing as a business with a commercial address or an institutional affiliation. Photographers Formulary provided an odd reaction, stating that not only did they not stock it, but that "none of the items you have listed" (D-94, D-94A formulas) were available from them, which was an odd response, as clearly most of them are. Will call them shortly to follow up. I seem to have touched a nerve somehow.

Final question that I have regarding all this: Are B&W reversal kits available from Kodak for TriX 7266 to those of us who do not have Super 8 and 16mm processing machines, but simply process our own using either LOMO, JOBO or Morse tanks?

Thanks for your anticipated responses.

 

[AgX]

Final question that I have regarding all this: Are B&W reversal kits available from Kodak for TriX 7266 to those of us who do not have Super 8 and 16mm processing machines, but simply process our own using either LOMO, JOBO or Morse tanks?

Kodak only lists bulk kits:
https://www.kodak.com/en/motion/page/black-and-white-reversal-kit-chemicals

the same for their catalog:

 

[Pakman777]

I have a feeling with this post I may be leading to a new thread regarding B&W reversal processing (specifically for TriX 7266).

My question is the bleach mixture after first developers D-94 (R-9 Bleach) and D-94A (R-10 Bleach) in the reversal process.

The Kodak H-24 module 15 (Processing KODAK Motion Picture Films, Module 15, Processing Black-and-White Films) states "KODAK Bleach R-10 should not be used with KODAK Developer D-94." R-9 seems to be recommended for use with D-94.

However, FilmLab.org cautions against even using R-10 bleach even with D-94A: "Avoid using R10 bleach [with D-94A] which is often a source of problems." They then recommend using only R-9 bleach (see attachment/insert).

Has anyone else encountered problems using D-94A that they can directly attribute to R-10?

Here is my bottom line for asking these questions: I am currently only concerned with processing Trix 7266. I cannot afford to waste this expensive film by undue experimentation; I am trying to gain the benefit of others experience - perhaps even hard lessons learned - prior to embarking on this. I am trying to begin my movie film processing with a winning combo (looks like D-94 or D-94A, use R-9 bleach only) at this point, and not experiment right off the bat with expensive errors.

Hopefully this can help others as well.

I deeply appreciate feedback from those who have experience with these bleaches.

 

[Pakman777]

Kodak only lists bulk kits:
https://www.kodak.com/en/motion/page/black-and-white-reversal-kit-chemicals

the same for their catalog:
View attachment 298427

Thanks for your response.

Yeah, I was looking at that. When I see "developer starter" and "replenishment" I assumed these are more designed for automated processes, not the home processor like me using a manual system.

Thanks again for the response.

 

[Anon Ymous]

@Pakman777 I'm not entirely sure if going from a thiocyanate containing developer to a permanganate bleach without a very good wash is safe. Perhaps this was reason for the switch.

 

[Pakman777]

@Pakman777 I'm not entirely sure if going from a thiocyanate containing developer to a permanganate bleach without a very good wash is safe. Perhaps this was reason for the switch.

Thanks. That is helpful to know, in any case.

 

[AgX]

Thanks for your response.

When I see "developer starter" and "replenishment" I assumed these are more designed for automated processes, not the home processor like me using a manual system.

Yes, but as an amateur one can run a replenoshed process too. Or one just can add starter at each run and discard the baths after this. The issue with the Kodak offer is just the sheer size.
For amateur volumes reversal kits, yout got in Europe quite some choices: Adox, Bellini, Foma, Wehner.