Guidance on managing basic pH in homebrew chemistry

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Mr Bill

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Professional-grade and Kodak-recommended pH testing devices are somewhat unrealistic for my home use. That leaves me to: A) ignore the pH altogether, or B) do my best with what's available.

I understand. This is why I offer the solution: buy one known-good commercial developer package as your reference. Then when you mix your own developer from components you have a working reference to compare against. If you DO get a pH meter it won't be necessary to know the exact "true" pH value - you can simply compare your self-made developer against the known-good commercial developer.

Of course it's possible that your home brew may come in right on the money, and your inexpensive meter might read properly. But if they don't... you could be off on a wild goose chase. Or maybe not. My long history in photoprocessing has led me to become very conservative in testing, putting "controls" on everything. When you do this you seldom go on the wild goose chase, nor do you often have to retrace your steps. So... it's largely a matter of how you like to do things.
 
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Of course it's possible that your home brew may come in right on the money, and your inexpensive meter might read properly. But if they don't... you could be off on a wild goose chase. Or maybe not.
@Mr Bill Ahhhh, thank you! That makes sense now. I can likely ask my local lab if they have a control sample. If not, I'll get the kit. I get it now. Thanks for your patience.
 

Mr Bill

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I can likely ask my local lab if they have a control sample.

If you're on good terms with your lab you might even get them to supply ALL of your developer. If they replenish developer this means that they will always be discarding "overflow" from the machine; it's waste to them. But to you... it's exactly the same chemical that is in the developer tank, and is exactly what you need to process film. So if they are willing to tap out of the developer overflow line, and you are willing to deliver doughnuts periodically... well maybe you won't even need to mix developer.
 
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So if they are willing to tap out of the developer overflow line, and you are willing to deliver doughnuts periodically... well maybe you won't even need to mix developer.
Woa, genius. We are on good terms. thanks for the idea!
 

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Thank you for being patient with me. I assume the 5 minute wash is under running water? If so, will a clearing bath help reduce wash time? I'm fine skipping the clearing bath mixture and washing only, but also happy to save water where I can. Thanks a ton!
If you use the clearing bath I would use a minimum of 1 minute wash after the bleach, 1 minute clearing bath (10 grams/liter of sodium sulfite), and another wash of 1 minute before the fixer. All washes are running-water.

For stop/clear bath and second clear bath I would mix with distilled water. I also mix the ferricyanide bleach with distilled water. My fixer is made from regular Kodak C-41 fixer concentrate and I just mix with tap water.
 
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If you use the clearing bath I would use a minimum of 1 minute wash after the bleach, 1 minute clearing bath (10 grams/liter of sodium sulfite), and another wash of 1 minute before the fixer. All washes are running-water.

For stop/clear bath and second clear bath I would mix with distilled water. I also mix the ferricyanide bleach with distilled water. My fixer is made from regular Kodak C-41 fixer concentrate and I just mix with tap water.
This all makes 100% sense. Thanks a ton
 

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Brother, the pH meter is not that expensive,
What is the problem in purchasing a cheap class device,
I bought a $ 12 Chinese device (which is a wide pen) ,, and it was working fine ,, only the problem I had was that it fell several times over the tiles and it was not working disciplined and I bought another device like him and he kept working with me More than 6 months ago - it was only destroyed due to the oil stains caused by the developer (CD2), and that dilemma was later solved by using this method of cold pressing this developer in a separate cup before mixing.
This cheap device comes with a small package powder 4 and another 7.1.
You calibrate it before working once and then it becomes excellent for a long time and works successfully.
 

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I found the pen type pH meters quite problematic and inaccurate at higher pH's around 10. I don't recommend them.
Nowadays I have a nice pH meter, but I've also used cheap ones. At around pH 10, the cheap one was quite good actually. Definitely not perfect, but usable and far better than nothing if that's all what your budget permits. It was at even higher pH values, like ~12 for E6 CD that the readings were iffy. Apart from that, the cheap meters may also have inconsistent quality control, making some units more accurate, durable, etc than others of the same model
 
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Brother, the pH meter is not that expensive,
What is the problem in purchasing a cheap class device,
I bought a $ 12 Chinese device (which is a wide pen) ,, and it was working fine ,, only the problem I had was that it fell several times over the tiles and it was not working disciplined and I bought another device like him and he kept working with me More than 6 months ago - it was only destroyed due to the oil stains caused by the developer (CD2), and that dilemma was later solved by using this method of cold pressing this developer in a separate cup before mixing.
This cheap device comes with a small package powder 4 and another 7.1.
You calibrate it before working once and then it becomes excellent for a long time and works successfully.
I have been looking for an inexpensive meter that comes with calibration option. It's a little more for that option, but I am still looking.
I found the pen type pH meters quite problematic and inaccurate at higher pH's around 10. I don't recommend them.
Thank you. I believe I'm left to decide if I should ignore the pH or do my best with what I can afford, taking into consideration the potential for inaccuracy. I believe this thread has been excellent for preparing me either way. Chances are: if the distilled water I use is good and I stick to the formula, whatever comes out will be great for my home use for the foreseeable future.

@Anon Ymous thanks for sharing your positive experience with inexpensive meters, and I appreciate the balance of caution with relying on it.
 

koraks

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if I should ignore the pH or do my best with what I can afford
While there are many technical and methodological issues involved in pH measurement, don't let yourself be discouraged from it altogether. There are pH meters in the $20-30 range (shipped from China) that seem to work quite OK. Maybe they're still off a bit in an absolute sense, but at least they will allow some degree of consistency in your work. Heck, even one of the $8-10 pen-type meters that I denounced may be helpful. I'd argue it's still better than nothing at all.
 
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While there are many technical and methodological issues involved in pH measurement, don't let yourself be discouraged from it altogether. There are pH meters in the $20-30 range (shipped from China) that seem to work quite OK. Maybe they're still off a bit in an absolute sense, but at least they will allow some degree of consistency in your work. Heck, even one of the $8-10 pen-type meters that I denounced may be helpful. I'd argue it's still better than nothing at all.
Cheers--thank you for following up! I'm sorry, my reply wasn't clear: I do plan to get an inexpensive meter, maybe not the cheapest. This thread has been incredibly helpful in teaching me about pH management with realistic resources and realistic expectations. Thank you.
 

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Concerning pH-meters, has none of you read what Serg spent on meters and probes? And still has uncertainties of what he actually is reading.
.And he is a seasoned guy. (To stay with our own vocabulary...)


A decent electronic thermometer (that can cope with a lab-grade stem thermometer) already costs about 100Euro.
And you are discussing far more complex ph-meters, below that...
The last pH-meter Serg used was in the 1000Euro range...
 
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koraks

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Yes AgX, I've read it and it's not the first discussion I've read on pH meters. But I don't have a 1k budget and I am taking a wild guess here and suspect neither has GBS. So then we can either go sit in a corner and cry our eyes out or try and do the best job we can at the budget we *can* afford.
 

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We have got some discussion on metrology at Apug and my impression is that only few have an understanding even concerning scales and thermometers. In the sense of "but it shows 3 digits".

Concerning "the best job", the question is how big a deviation from the pH tolerances of the manufacturer can we tolerate. Likely one does not know, moreover one likely does not even know what the tolerances of ones meter in the actual case are.
(Also taking over the aim-pH of commercial baths for homemade ones can at least be discussed.)

My question then is: Does pH-metering then make sense at all?
 
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Anon Ymous

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... My question then is: Does pH-metering then make sense at all?
Yes, it does, even considering all the limitations. By the same token, I'm not entirely sure what the precision (not resolution) of my thermometer is, I don't precisely know what difference half a degree might have, but I don't start developing anything without taking a measurement. Sure, there's a margin of error in the readings, some tolerances, but they're still useful. If I had exactly the same chemicals that the formula creator uses, I'd likely not be very worried about pH. But I don't have exactly the same chemicals, mine might be slightly less pure, so I have to check. Besides, when using a formula, some ingredients may not be available. Chelating agents aren't always widely available, some are basically unobtainable in small quantities. You'd be surprised how much excluding, or substituting such an agent affects pH. And since I've already mentioned E6 CD, and the difficulty getting a correct reading with a cheap meter at this pH level (~12), it still helped me find out that something is wrong with my chemicals. The reading was way below what it should be, even considering questionable precision. The colour balance of the slides confirmed this. Using a pH meter, even one that gives faulty readings, but consistently so can help.
 

Mr Bill

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Concerning pH-meters, has none of you read what Serg spent on meters and probes? And still has uncertainties of what he actually is reading.
.And he is a seasoned guy. (To stay with our own vocabulary...)

There are a few things that Serge said that may not be clear to people. In his item #1 he found a "ground glass sleeve type junction," and this is how he was able to be successful in reading seasoned chemicals. Now earlier in that thread I had mentioned my own (via employer) success with either annular ring or sleeve junctions. This probably needs some explanation for people not familiar with pH reading methods. First, it is necessary to have two electrodes - the pH sensing electrode itself, plus a "reference" electrode. Together they form a cell and generate a small voltage which the meter reads.

People who use an inexpensive meter might say, "wait! I only have one electrode." This is because they have what is known as a "combination electrode," which has the two built into one housing. And you can also buy combination electrodes for any other meter if you wish.

Back to the reference electrode... the usual reference electrode uses a "filling solution," commonly about 3.5 M KCl, which is in contact with, and slowly "leaks" into the test solution. It's called a "filling solution" because you have to periodically refill the electrode. (You must always keep the level of the filling solution higher than the sample level, else some of the sample might leak backwards in side of the electrode.) The point where the filling solution contacts the sample is called the junction. Most reference electrodes will use a junction that flows very slowly; this is useful because there is very little contamination of the sample with the filling solution. But... in difficult samples it is very easy for the small junction to get clogged, and you will not be able to get a stable reading.

Ok, finally we come to the topic of this post - Serge's "ground glass sleeve type junction." You know by now that this is in the reference electrode, and this is where the electrode's filling solution contacts the sample, right? Okay, the sleeve fits around the (cylindrical) body of the electrode, and the junction is the entire perimeter of the sleeve. This gives something like about a hundred or so times the junction area, and consequently it is very resistant to clogging. And if it does clog, it's very easy to clean - you simply slide the sleeve up a bit and the filling solution runs out, flushing out the junction. Of course you have to refill the electrode which takes about two seconds.

So, for photo solutions a high-flow junction, such as an annular ring or sleeve junction can be useful.

Here's the bad news for the user of a cheap meter - you don't have any choice of the electrodes; whatever it comes with is what you get. Most of the time they seem to come with a so-called gel electrode, where the reference junction is some sort of a permanent gel material, which I really don't understand how they work. If I had such a meter I would probably keep it out of seasoned solutions.
 

Mr Bill

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My question then is: Does pH-metering then make sense at all?

Hi, I think that if someone is mixing from some formula with possibly marginal chemicals, maybe different purities than what the formulator used, then result will likely be a little different. So the problem is, how does the user deal with this?

Now the original formulator probably had to experiment by processing film, etc., while tweaking the formula, and ideally they can report an aim pH. Now if they had an inadequate meter reading then it sorta leaves another user with not many options - they'll have to tweak the formula by trial and error. Probably the most useful modification would be pH adjustments. So once they find a good working formula, they could use their own meter to find an aim pH value for their own use. (It might not be a "correct" pH, but it should be repeatable for them.)

With respect to a "proper" C-41 formula, one that closely approximates the "real" formula, this is more than likely gonna need to operate at the pH spec given by Kodak. (I've looked at more than a couple of these over the years; they're close to the Kodak pH spec.) Ok, now the user has a problem; they should ideally adjust pH to spec, but they're not sure their meter is accurate. This gets back to what I suggested previously - if they buy an actual Kodak mix (or other mainstream mix) they can use their own meter to measure the Kodak mix. This then becomes the aim pH value for their self-mix.

Some people may think the meter will be accurate, but this is not necessarily so. Kodak has a specific pH electrode that they recommend, and they caution that any other electrode should be verified by the user.

Now I have personally observed a pH difference in other meters/electrodes, albeit back in 1990s or so. Previously user Anon Ymous advised me to calibrate the meter with pH buffers (as though I didn't know this). So let me clarify the methods used. First, the pH reading will vary by temperature. So you must always take a pH value at a specific temperature. For Kodak this is usually 25 deg C. Now to calibrate a meter you must do two things - zero the meter and then set a slope (this is probably semi-automatic with modern meters). Here's how it works, sort of: a pH value of 7 is a "neutral" pH value, and this is where you zero the meter. The electrode pair is gonna have a certain theoretical response characteristic to changes in the pH , but they vary slightly. So to calibrate your meter/electrode combination, here's what you do. First obtain a reference pH buffer solution for pH 7 ( the exact values will be listed on the buffer package). Now, to set a slope value you ideally use another reference pH buffer with a value similar to your sample. Since the color developer is near pH 10, you would normally use a pH 10 buffer. So obtain a pH 10 (approximately) buffer. Ok, for the calibration: note the specified temperature for the developer pH; also note the exact pH values of your buffers at that temperature. You ideally want your sample AND the buffers at that same temperature. Ok, use the pH 7 buffer to zero your meter for the exact value for the temperature. Next, use the pH 10 buffer to set the meter slope for the exact value for the temperature. (Note: follow standard procedures while doing this, rinsing electrodes with distilled water when changing solutions, blot off excess water, never ever wipe, etc. pH 10 buffers are subject to changing when exposed to air, so it should be fresh from the container for critical work.)

Ok, finally, read the developer sample. As a note, you will typically find that the buffers give a stable pH value very quickly, meaning in perhaps 5 or 10 seconds (? I don't recall clearly). But the developer samples will probably take quite a bit longer.

When we read seasoned developer samples it would typically take between 1 and 2 minutes. This is with a 3-decimal research-grade pH meter, a high-flow reference electrode, and the Kodak-standard pH electrode. We watched the third decimal digit to judge the rate of drift. If only two decimal places are shown one might judge the drift to have stopped earlier. I believe that more modern meters are calculating the rate of drift internally, and possibly predicting how far it will go, so they might obtain readings much quicker - I dunno.

With respect to different pH electrodes, we would get different values for the developer with some electrodes. So we take the Kodak-standard electrode as "correct," and reject other electrodes as not useful. The values we got would (typically) concur with the published Kodak spec.

With all this out of the way, I'll repeat: I think that the user of a non-Kodak-standard meter can probably get an aim pH reference value, FOR THEIR METER, by mixing a packaged Kodak developer, then measuring it. (Congratulations if you get the "correct" value.)

Ps, I DO have a question for the other proponents of the low-priced meters: how did YOU know if your meter was accurate or not? I mean, if you think your meter was useful in measuring pH, you must have had some idea how close it was, right? (Presumably you are then adjusting the developer to some pH value? If not, what was the use of the meter?)

With that I'm gonna try to step out of this thread; I don't really have much else to say)
 
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Anon Ymous

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... Previously user Anon Ymous advised me to calibrate the meter with pH buffers (as though I didn't know this)...
I didn't advise you about anything. The OP is interested in scratch mixing his chemicals. You proposed him to try taking a reading from ready made chemicals. While this idea may have merit, it's an added expense to a possibly already tight budget. And since the OP has stated that he needs some guidance, I mentioned that a buffer solution could provide a good reference point, especially considering that a pH 10 buffer is basically at the same pH level C41 developer would be. And these buffers would be essential and it wouldn't be wise to take any readings without calibrating his meter. So, I'm not advising you, I'm trying to help the OP, as someone who must scratch mix everything, because I don't really have an alternative.
 

Mr Bill

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I didn't advise you about anything.


Here's exactly what you said earlier:

@Mr Bill Instead of buying commercial chemical and see what the pH meter reads, it would be better to use the buffer solutions that you need anyway with a pH meter. Usual buffer solutions are at pH 4, 7 and 10, the last one being very close to C41 developer pH. Using a pH meter without calibration with a buffer solution isn't very wise anyway.


Now on to the current post...

... I mentioned that a buffer solution could provide a good reference point, especially considering that a pH 10 buffer is basically at the same pH level C41 developer would be.

My whole point is that even though the pH meter reads the pH 10 buffer perfectly, it can be largely in error with a nominal pH 10 color developer. This is exactly why Kodak specified use of a specific pH electrode by part number, and cautioned that other pH electrodes may not give the same pH value.

I have personally seen electrodes perform this way, so it is not just a hypothetical situation to me.

I realize that this is an additional expense to the OP, and it would be a pain in the backside, but... without such verification the OP MIGHT be unknowingly adjusting developer pH to the wrong value while believing it to be correct. The only other alternative I see, assuming that one wants "proper" development, is to do trial development tests vs some known-good reference (perhaps commercially processed?).

My experience has primarily been with optical printing, where the requirements are more stringent than with scanning. And I'm a long-time QC guy from an outfit where the process variation was necessarily held very tight. So this is the viewpoint where I'm coming from.
 

Anon Ymous

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@Mr Bill For the last time, since it is getting way off topic and doesn't contribute anything to this thread, I never said you didn't calibrate your pH meter, nor that you don't know how to do, or whatever.

Yes, I get that different electrodes may give different readings, this is a valid point. But there comes a point where the costs involved for this kind of top notch electrode and meter defeats the purpose of taking this path. As for the lab processed film being a point of reference in theory it is, but at this point, with very low throughput being the norm rather than the exception, it can be of questionable quality. I even have the curve to prove it. Obviously, not all labs have this problem, but one needs to find a lab that uses fresh chemicals and has quality control a top priority. Not necessarily an easy task.
 

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@Mr Bill For the last time, since it is getting way off topic and doesn't contribute anything to this thread, I never said you didn't calibrate your pH meter, nor that you don't know how to do, or whatever.

Yes, I get that different electrodes may give different readings, this is a valid point. But there comes a point where the costs involved for this kind of top notch electrode and meter defeats the purpose of taking this path. As for the lab processed film being a point of reference in theory it is, but at this point, with very low throughput being the norm rather than the exception, it can be of questionable quality. I even have the curve to prove it. Obviously, not all labs have this problem, but one needs to find a lab that uses fresh chemicals and has quality control a top priority. Not necessarily an easy task.

Ok, I accept that I interpreted differently than what you meant; fair enough.

Back on the topic: we're gonna probably just have to be in disagreement on this.

I agree that your points ARE valid, if the resources are not available to you, which sounds like the case. But... this does not apply to the OP. The OP lives in a place where the chems should be readily available, and is even on friendly terms with a local processing lab.

From your past posts it appears that you have considerable experience working with photo chemicals, including testing, etc. If your pH meter were to read significantly in error, I'd guess that you could figure a way to work through it.

But the OP seems to be a relative novice, ready to jump into the deep end of the pool, so to speak, and may not recognize what is, or is not, a problem. The pH meter can be something of an insidious problem - it confidently displays a value, perhaps to two decimal places, and who would doubt such a value? Well, I happen to know that such a value for a color developer is very likely to be wrong. So I want to make sure the OP recognizes this possibility, and does not blindly adjust pH to what seems like the correct value.

As a note, I've trained probably a half-dozen people to take such readings, and I'd say, offhand, that this took perhaps 3 to 5 hours spread out over several days. This is with the high-grade equipment prior to micro-processor-controlled meters. They would be reading perhaps 50 samples of a mixed assortment - some C-41 developers, some RA4 developers, bleach, fix, and paper blix. In the process they would learn to recognize good readings from problematic, and learn how to troubleshoot the instrument and electrodes. At this point I'd feel mostly comfortable with their testing. But if they had a question, someone could walk them through things over the phone.

If it were a brand new person, learning on their own, it's a different situation. If they don't have a way to somehow qualify the "correctness" of their readings, well, now I think that they might be better off without a meter.
 

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Thanks for your time.

Yes, I have values and tolerances.

For example, one developer is 10.00 +/- 0.03, another is 10.25 +/- 0.05. Bleach is 6.5 +/- 0.5. I'm testing a few mixes, so I won't list all the values, but save for 1 or 2, I have them all.

I will be starting with distilled water (checking for 7.0 pH however possible), but cannot fully rely on distilled water for every instance in the future.

I'm asking

1) how to adjust: developer pH up or down
2) How crucial is the stop bath pH and how to adjust?
ECN stop - sulfuric acid based
C41 stop - acetic based (can I use vinegar or Kodak indicator? I don't have a "value" for this, only the recipe)
3) How crucial is the bleach pH and how to adjust:
Potassium Ferricyanide + Sodium Bromide
4) how crucial is the fix pH and how to adjust?

5) Tangential question: do you have a recommendation for a clearing wash other than water, and if so, does it have critical pH to adjust?

Thanks again

The developer has a carbonate that buffers it to the right pH, so you can adjust that, but the pH measurement is just a check that you did things right. It should be right if you did the formula right.
Stop bath is non-critical and no buffering is needed. Its just an acid to get the pH low in a hurry. The meter could be used to see when you are losing acidity if you reuse it, but I wouldn't re-use it much.
You can use acetic acid to adjust the bleach bath to 6.5 (or just replenish it per the schedule and check). It will get basic with use. It isn't real critical as your tolerances show.
I wouldn't use black and white Ilford Rapid Fixer for color. Use a color fixer that is designed to be around 6.5, and you don't need to adjust it, just re-use it a limited amount of times.
I had pretty good luck with cheap pen style meters. They are not temp. compensated even if they show the temp. It is important to use fresh buffer solutions to calibrate, and the pH 10 solution will go acid on you in a few days. You might be able to get a week or more if the bottle is glass and filled to the top.
 
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The OP lives in a place where the chems should be readily available, and is even on friendly terms with a local processing lab.
I asked my lab about checking pH as a control, but he doesn't have a meter, either. I forget the name of his processing machine, but he does have a densiometer and uses control strips religiously which always check out. He said we could erad his pH anytime, but I won't know the exact read.
So I want to make sure the OP recognizes this possibility, and does not blindly adjust pH to what seems like the correct value.
Novice to home color developing, yes. Otherwise, I've been shooting still and motion for decades and processing my own B&W just as long. I'm very mechanically and technically minded and competent. If you need your engine rebuilt or home remodeled, I got you. Same with video editing. I know those skills aren't directly corollary to mastering C-41 chemistry, but I do have what it takes to understand the realities with a little guidance. You've been very helpful in instilling caution with regards to cheap meters and willy-nilly adjustments with said meters. Thank you.
The developer has a carbonate that buffers it to the right pH, so you can adjust that, but the pH measurement is just a check that you did things right. It should be right if you did the formula right.
This is new information to me. Thanks a ton for sharing it. Your whole comment is concise and informative. Thank you.
I wouldn't use black and white Ilford Rapid Fixer for color.
Wow, this is the first time I've read definitively: 'don't use B&W rapid fix.' I hate to open a can of worms, but why not? Is it pH alone? My initial research led me to believe the fix pH isn't crucial to the final image.
It is important to use fresh buffer solutions to calibrate, and the pH 10 solution will go acid on you in a few days.
Thanks - I plan to order pH 10 buffers. Are you saying I should also heat it to development temp? Thanks a lot!
 
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