Help. What's wrong with my negatives?

[MattKing]

You’re much too kind. Those instructions are definitely not “best effort”. They could/should have consulted an instructional designer or run a quick focus group to assess the quality of their instructions. They flubbed it…

Whether they did or not, it still may aid eventual users.
The instructions were probably put together by Cinestill, because I doubt Photo Systems has anyone left from the time they marketed directly to the retail market - think Unicolor.

 

[dcy]

So with each of the parts you have to be able to measure to the nearest 0.1 ml? 44ml of B, 95ml of B and 94ml of C isn't good enough?

You don't have to measure 0.1 mL if you make the entire 2.5L of developer all at once. You just dump the entire bottle.

If I wanted to do fractional amounts, I would be tempted to add a little bit of water to each solution independently so it becomes a round-number volume. For example, part B is 43.8 mL. I could pour it into a graduated cylinder that measures 50 mL, add water to the 50 mL mark, and then pour it back into the bottle. Now I have a slightly more dilute version that is easier to divide by 2 or 5. If I wanted to divide it in thirds, I'd fill the graduated cylinder to the 48 mL mark.

 

[dcy]

I repeat my suggestion that you help Photo Systems by reaching out to them.

Yeah. I will do that tonight.

When you are trying to sell a product, despite all your best efforts, it is really hard to tell when your potential customers are going to read your instructions in a way that you didn't expect or intend them to.

Yeah. The instructions do implicitly kind of suggest that water goes in first, and it's an easy thing to assume if you're used to mixing chemistry.

And while I wouldn't have done what you did, I can totally understand why you did.

Yeah. Normally I mix chemistry with 80-90% of the water first. I know that the mixing order of the active ingredients is important, but I didn't think about how the concentration would be important too.

If I had thought of it, I could've used one of the gallon jugs of distilled water. With a little planning, you don't even need to mark 2.5L on the jug:

Step 1: Measure 2,150 mL of water and put it in the jug.
Step 2: Pour Part A into a graduated container and fill to the 200 mL mark. Pour into the jug.
Step 3: Pour Part B into a graduated container and fill to the 50 mL mark. Pour into the jug.
Step 4: Pour Part C into a graduated container and fill to the 100 mL mark. Pour into the jug.

That would've worked just fine.

 

[MattKing]

You don't have to measure 0.1 mL if you make the entire 2.5L of developer all at once. You just dump the entire bottle.

If I wanted to do fractional amounts, I would be tempted to add a little bit of water to each solution independently so it becomes a round-number volume. For example, part B is 43.8 mL. I could pour it into a graduated cylinder that measures 50 mL, add water to the 50 mL mark, and then pour it back into the bottle. Now I have a slightly more dilute version that is easier to divide by 2 or 5. If I wanted to divide it in thirds, I'd fill the graduated cylinder to the 48 mL mark.

Adding water to the little bottles may severely shorten the storage life of the unused portion - I would not recommend that approach!

 

[dcy]

Adding water to the little bottles may severely shorten the storage life of the unused portion - I would not recommend that approach!

Really? ... Just going from 43.8 mL to 50 mL is enough to severely shorten its life?

I realize that adding a lot of water will bring in, at a minimum, oxygen. But I hoped that a little bit of distilled water wouldn't be a problem.

 

[MattKing]

Yeah. The instructions do implicitly kind of suggest that water goes in first, and it's an easy thing to assume if you're used to mixing chemistry.

It is even easier to assume if you have used the old instructions before. Many of us have been following such mixing instructions for decades, and I can't think of any that don't suggest starting first with water - usually at least most of the water necessary.
On the subject of instructions, the book "Zen and the Motorcycle Maintenance" has a couple of gems.
The main character in the book is a technical writer who does that sort of thing - he rights instructions for products.
In one part of the book he observes that when he goes to a client to take on such a task for a particular product, he needs insight into that product. His observation is that one of the problems he had to deal with is that, at least initially, the person who is often assigned to him for that insight is not what he needs: the most knowledgeable or understanding or end-user savvy person in the organization. Rather, the person who the organization assigns to heelp him with his task is the one that the organization can most easily do without for the time it takes to get the task of writing instructions done .
There is a very good possibility that the person who put those instructions together had one of two shortcomings. They either:
1) had so much experience mixing photo-chemicals up for use, that they didn't even think of the possibility that new users wouldn't assume that water should go in first; or
2) had so little experience mixing up photo-chemicals for use, they didn't understand that the order mattered.

 

[MattKing]

Really? ... Just going from 43.8 mL to 50 mL is enough to severely shorten its life: ?

I realize that adding a lot of water will bring in, at a minimum, oxygen. But I hoped that a little bit of distilled water wouldn't be a problem.

One example: the old, viscous HC110 developer.
If you try to develop film in the pure syrup, nothing happens.
Without water, it is incapable of developing film.
Adding even a little water makes the mixture fundamentally different - it goes from being close to inactive to being a very active reducing agent.
And it immediately starts the storage life "clock".
Adding small amounts of water will have different affects on different components, but as much of the reason for mixing smaller quantities is to extend the usable life of the kit, I wouldn't suggest accelerating the deterioration.
Use a small graduate that permits accuracy to the nearest ml instead.

 

[koraks]

Really? ... Just going from 43.8 mL to 50 mL is enough to severely shorten its life?

You add not just water; there's oxygen in the water. For some concentrates (but not these particular ones), you may be adding water to a system that's based on a different kind of solvent. Having said that, in the case of these particular concentrates, it won't make a whole lot of difference. Parts A and C are stable as long as you re-seal whatever bottle they're in; they will tolerate being diluted a little for measurement purposes. Part B is inherently problematic and you can count on it starting to deteriorate the moment you open the bottle. Adding extra water to it will accelerate the process a little.

That would've worked just fine.

I'd start by following the manufacturer's instructions to the T.

 

[dcy]

You add not just water; there's oxygen in the water.

The sentence after the one you quoted mentioned oxygen. The reason I suggested adding just a little water was to hopefully add just a little oxygen. --- Hoping it wouldn't be a lot more than the oxygen you've already added by opening the bottle.

For some concentrates (but not these particular ones), you may be adding water to a system that's based on a different kind of solvent.

Yeah. But I was talking about these particular ones. I wouldn't have suggested if it was something like PC-TEA.

I'd start by following the manufacturer's instructions to the T.

In this instance, the manufacturer did not explicitly outline steps. When we say that they kind of imply that the water goes first, we're being generous. The table shows water in the first column, so it kind of implies it goes in first. But that's being generous because if you were to interpret the table that way literally, they'd technically be telling you to measure 2175.6 mL of water. Obviously, that's not how anybody mixes the developer, so clearly that's not what the table is supposed to imply. Clearly the table is really just giving totals, not enumerating steps.

 

[Samu]

Some people are suggesting that using inaccurate beakers for measuring is the problem. This is not true. In order to get any noticeable difference in process, the amounts mixed must be significantly incorrect. Either the developer concentrate is spoiled (broken seal in bottle, frozen, etc,), there has been a mistake when mixing, or there is a serious contamination with some other substances, suxh as fixer.

 

[dcy]

Some people are suggesting that using inaccurate beakers for measuring is the problem. This is not true. In order to get any noticeable difference in process, the amounts mixed must be significantly incorrect. Either the developer concentrate is spoiled (broken seal in bottle, frozen, etc,), there has been a mistake when mixing, or there is a serious contamination with some other substances, suxh as fixer.

Thanks. That's good to know.

I think the consensus is that indeed the mixing is the culprit. Importantly, @koraks gave a very informative explanation that clearly shows how the symptoms I observed when mixing point to some of the CD4 turning into oily globules, effectively giving me a developer with too little CD4, which perfectly explains the badly underdeveloped negatives.

 

[koraks]

The table shows water in the first column, so it kind of implies it goes in first.

That's how the mixing order is often specified for color chemistry. You didn't realize; no biggie. PhotoSys should consider adding pictorial instructions like Fuji does so that inexperienced users are less likely to make the same mistake.

In general, when mixing chemistry, the following workflow is virtually guaranteed to work well:
1: Measure out 60-80% of the volume of solvent (often water) needed for the mix. When mixing chemistry from dry ingredients, you can use warm water (ca. 50C) to facilitate the process.
2: Add the ingredients one by one, in the order listed in the formula/by the manufacturer. Ensure that each ingredient is fully dissolved/incorporated before the next ingredient is added.
3: Make up the solution to the target, final volume using the solvent.

So for instance, for this particular color developer, if you were to make the full 2.5L volume at once, you could do the following:
1: Take 1.5L of water.
2: Add contents of bottle A. Stir until completely incorporated. Repeated with B, then C.
3: Top up to 2.5L with water.

As said, this approach works virtually always, regardless of what kind of (photo)chemistry you're preparing.
It's a pity that PhotoSys didn't specify the mixing procedure; they likely acted on the erroneous belief that everyone's aware of the kind of procedure outlined above. Of course, we all have to learn for a first time!

 

[dcy]

In general, when mixing chemistry, the following workflow is virtually guaranteed to work well:
1: Measure out 60-80% of the volume of solvent (often water) needed for the mix. When mixing chemistry from dry ingredients, you can use warm water (ca. 50C) to facilitate the process.
2: Add the ingredients one by one, in the order listed in the formula/by the manufacturer. Ensure that each ingredient is fully dissolved/incorporated before the next ingredient is added.
3: Make up the solution to the target, final volume using the solvent.

Yeah. That is what I normally do. I understand that the sequence is important. For example, often the key active ingredient is not anything you directly pour into the solution, but something that is produced as part of the sequence of steps. So if you alter the order, or don't wait for one ingredient to fully dissolve, you might interrupt or prevent the production of something that you needed.

But it didn't occur to me that the concentration can also alter the reaction byproducts (which makes me feel dumb, since it sounds kind of obvious in hindsight). The issue never came up before because I'd never mixed a volume of chemistry that I couldn't fit in my largest beaker before.

I used the link @MattKing gave me to reach out to PhotoSystems / CineStill, with what I hope was a clear and detailed explanation of where I went wrong, and a request that they update the instructions to make the mixing steps more explicit.

 

[koraks]

often the key active ingredient is not anything you directly pour into the solution, but something that is produced as part of the sequence of steps.

This is possible, but very often not the case. In the case of C41 developer, the CD4 in the form supplied may react with the alkaline activator, but it depends on the kind of CD4 that's used by PhotoSys. In the end, it doesn't matter as it's the part of the molecule that's not involved in this acid/base reaction that does the actual color development.

So if we were to get this just right at the theoretical level, we would need to distinguish between situations where e.g. a buffer is formed or the pH is affected by the final mix of ingredients, vs. the situation where actual functional groups of molecules are affected in order to end up with the desired chemistry. An AFAIK rare example of the latter is DIY parodinal.

the concentration can also alter the reaction byproducts

I'm not sure what this means, exactly. All I do know is that Photo Engineer once explained to me in a private message that hydroxylamine sulfate and CD4 cannot be part of the same concentrate. I guess you've demonstrated accidentally that this is indeed correct!

 

[Willyekerslike]

.

 

[dcy]

I'm not sure what this means, exactly.

By concentration I just mean I didn't have enough water in the mix.

All I do know is that Photo Engineer once explained to me in a private message that hydroxylamine sulfate and CD4 cannot be part of the same concentrate. I guess you've demonstrated accidentally that this is indeed correct!

Indeed. Looking back, I had noticed a couple of oddities in C-41 kits:

• The Bellini kit, which is a single developer concentrate, is the only one that doesn't list Hydroxylamine as far as I've been able to tell from the MSDS.
• The Flic Film kit, which is the only one that doesn't list CD4, is also the only one that comes in only 2 parts, and according to the MSDS, part B has Hydroxylamine and p-Phenylenediamine replacing CD4.

Every other kit is the classic formula --- one part is hydroxylamine, one part is CD4, sometimes with an antioxidant (I think), an one part is everything else. But you never see CD4 and hydroxylamine together.

 

[Craig]

The old Kodak Flexcolor instructions give the acceptable range of specific gravity for each chemical and the processing temperature is 37.8 ± 0.15 °C. I've not done C41 processing, but my understanding is that both time and agitation are critical.

Look for publication Z-131, I have attached it. Section 3 on sink line is what means small tank processing.

 

[Craig]

While I'm on this topic, I thought that the color of the developer was odd when I was mixing it. As I poured part C into the A+B mix, the solution quickly turned milk white. It felt like pouring milk in coffee. As I stirred, the solution became clearer, but developed some weird blotches, similar to drops of oil floating on water. I used a magnetic stirrer to do the mixing, and after a little while the entire solution turned clear, with no blotches. Just a very slight brownish tint, like very diluted tea.

Hmm, that doesn't sound right. Kodak mixing instructions:

Mix the developer solution at 21 to 38°C (70 to 100°F). The mixing order is important with developers and developer replenishers because Parts A and B contain the preservatives. Therefore, add Part C only after you have mixed Parts A
and B. It is not necessary to mix each part for a long time. You can add the parts in fairly rapid succession without causing a
problem. Agitate enough to mix the developer completely in less than 5 minutes without introducing a lot of air into the developer solution. The solution will be clear and colorless after you add Parts A and B; it will be amber after you add Part C.

Developer Replenisher
Developer Replenisher LORR

Part A Clear, colorless to
very pale yellow;
odorless:

A crystalline precipitate may appear in parts that are kept too long (more
than 2 years) and/or exposed to cold temperatures. If color and odor are
normal, Part A is usable if the crystalline material dissolves upon mixing.
Extended mixing and heat may be needed before adding Parts B and C.
However, be sure mixture is no warmer than 38°C (100°F) when Part C
is added.


Part B Clear, colorless;
odorless



Part C Clear; color varies
from light yellow to
yellow

The color range is due to different levels of sulfite. Absence of sulfur
dioxide odor means the preservative is exhausted. If the solution turns
color or becomes opaque, or if there is a precipitate, do not use it.