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Leader Density: D-76 vs Rodinal and others

Xmas

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Some people in UK buy water in supermarkets take it home and put it in fridge, fizzy or still.

When I make up dev, fix and HCA I boil up faucet mix with cold for temperature and pour in powders.

Lots of people here have water softener plants in house that protect the water heaters from calcium carbonate but are not suitable for babies cause they can have a high salt content, they are ion exchange... you have a drinking water bypass for potable water.

Why are you using distilled water lots of it is
merely ion exchange suitable for steam irons and auto batteries...?
 

Bill Burk

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Hmmmm, where could I find some leaders of developed Tri-X?

Haaa of course, practically anywhere in my collection of negatives - since there is almost always a leader stuck next to shot 0.

D-76 1:1 ...

B+F ... Leader density above B+F ... description
0.27 ... 1.39 ... October 2005 Max and Nick
0.27 ... 1.92 ... 2005 LA Drive
0.39 ... 2.02 ... 2013 Hike and Rocket building

Dektol 1:9 ...
0.21 ... 1.82 ... Sensitometry seeking max grain
 
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Arvee

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Thanks, Bill, very helpful information. I consumed a gallon mixed with bottled drinking water and am starting into the second gallon. Excellent results so far. When I was in school we had to submit FB+F and highlight densities for any print submitted. If highlight density exceeded 1.5, we were instructed to not turn in the assignment and would get an 'F' for that week's assignment. Our instructor scrutinized each and every negative with his trusty densitometer. A hard task master he was, but those lessons are still with me some thirty years later!


 

Bill Burk

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As far as a sanity test though, like - darn my D-76 has gone bad, thin density of a developed leader is one very simple obvious sign of a problem.
 
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Arvee

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Michael, I would be very interested in your test results. I still don't understand what is happening but the problem appears to have disappeared with drinking water that has the higher pH (7.8). I did check to see that pH was normal when 76 was mixed with DW and it came to about 8.0 so I don't believe pH of the DW is a factor. The drinking water batch was somewhere around 8.5 to 9.0, not enough in my estimation to make a difference.

The only other factor to consider, IMO, is the dissolved oxygen. But I have no way of determining if this is a factor or not. Surely the lower pH of DW is caused by dissolved CO2 so perhaps there is an abnormal amount of DO in the DW.

One other thought: is there any practical difference between mixing 76 with tap water and then storing it in an HDPE gas permeable container versus mixing 76 with water that has been stored in an HDPE container and subsequently stored in a brown glass bottle? It seems to me that the developer will oxidize in either case. And, perhaps, there may be different levels of DO in DW depending on how fresh it is, that is, how long it has been sitting on the grocer's shelf since it was processed/packaged.

I have easily seen the difference between leader material that has been out for days and the portion of the leader that is exposed when loading the cameras. I haven't measured it precisely but there appears to be about a stop or two difference, the long exposure time portion of the leader has indeed gone into reversal. My observations have only been based on that portion of the leader that has been exposed to daylight for the few seconds during the loading process.

When I get the time, I may mix a batch with the DW and run some comparative tests as well. I may end up losing another gallon of 76 and I am not the least bit sure I will uncover anything more than I already know. Plus, I don't own a densitometer so my crude spotmeter approach would be insufficient in this analysis, however, Bill's clever test worked well when using the spotmeter. Also, I was able to detect 3 stops difference in leader density between Rodinal and 76 when using my crude tool.

Ideally, I would like to solve the problem, implement a solution and be able to use Xtol. I do prefer it over 76 but I have never been able to keep it alive. I even tried Suzuki's solution with brown wine bottles and a Vacu-Vin device but it still died on me and I ultimately attributed that failure to the bad water.

EDIT: I have mixed another batch with DW and will let it sit several days and try an A/B test with the batch that was mixed yesterday with water stored in a PETE container. Maybe we'll see a difference there.

 
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Arvee

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As promised, I ran some periodic tests with PX125 test strips: 6' in D76 @ 68F, stopped and fixed normally. The D76 was mixed with Kroger distilled water and decanted into brown glass bottles topped off and sealed with Saran wrap. I mixed the batch on 4/13 and created a reference test strip and then measured each strip with a Luna Pro meter as a crude transmission densitometer. The test strips were clipped from a bulk roll and exposed to daylight for a period of about 30 seconds then processed in a closed tank.

Here are the results:

[date] [meter reading] [net density difference]
[4/13] [15 1/3] [Reference]
[4/14] [16] [2/3 stop less density]
[4/25] [17] [1 2/3 stops less density]
[4/28] [17 1/3] [2 stops less density]

As indicated, 76 is steadily losing activity. Edit: I can't seem to get the data to tab correctly after posting. The numbers are 15 1/3, 16, 17 and 17 1/3.

Update: just ran another snip test with a batch of 76 (approx. two weeks older and mixed with bottled drinking water); registered a 15 2/3 reading. Clearly, my Kroger DW comes fortified with developer killer! Dumped yet another gallon of 76! I'm done!
 
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That Kroger water is very suspect. Be interesting to do a water analysis on it to see just what's in it. That costs a bit of money, though.

Anyway, seems like whatever is causing the failures with the Kroger water is the culprit, and that you have found a way of avoiding this problem.

I'll drink to that later tonight when I have a beer.

 
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Arvee

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Interested to hear your results, Michael, but I'm going to bet a beer that it's something with the Kroger water, not distilled water in general. Congratulations on using Tri-X but it's nothing like the Tri-X I used back in the 70s! Today's Tri-X is pretty mundane in comparison with the original product. I do miss it!

PE raised a flag on DW pH a while back and the Kroger product was at the low end of that range. I also read in Anchell Cookbook that Borax isn't the best as far as buffering goes. Perhaps a pH of five-ish and mild buffering isn't a good combination?


Thanks, Thomas, enjoy that beer! I am going to stick with TMax and Rodinal for the time being and maybe come back to 76 when I run out of developer.
 
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Gerald C Koch

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Every time I visit this thread the famous Tallulah Bankhead quote keeps popping into my head. "There is less to this than meets the eye."
 
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Arvee

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Every time I visit this thread the famous Tallulah Bankhead quote keeps popping into my head. "There is less to this than meets the eye."

Every time I read a comment such as this it reminds me of the saying, "If you don't have anything constructive to offer, then...."

I'm trying to resolve a frustrating issue here.
 
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Gerald C Koch

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Every time I read a comment such as this it reminds me of the saying, "If you don't have anything constructive to offer, then...."

I'm trying to resolve a frustrating issue here.

I was attempting to humorously point out that this is really a non-issue. Nobody does anything with leaders. You are worried about an observation made from a group of non-reproducible results. People including myself have offered constructive ideas. Suggestions are either ignored or don't fit your observation. If you are concerned then do a series of controlled experiments. I am sure that people will be able to offer you suggestions on how to design these experiments. Then do you see any difference in your negatives? They are the only things that matter.

BTW neither Rodinal nor D-76 produce full emulsion speed. You need a developer containing either Phenidone or a phenidone derivative.
 
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baachitraka

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Only matters is how they print.
 
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I think Fred has a good point, and it is evident that his D76 has been steadily tapering off in activity with one particular kind of water.

Now, in my book to identify that the specific Kroger water is the culprit = problem solved. Don't use the Kroger water. The end. Shoot and develop film and be happy.
 
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Arvee

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Gerald, unfortunately, your feeble attempt at humor was lost on me.

I am simply using the leader as a yardstick of developer activity. My D76/PX negs are flat with weak highlights; they produce terrible, muddy prints. Since I don't have a densitometer I used the leader material as a yardstick (I use a luna pro meter to measure density with sunlight as a source)and need a large area to measure. Since the negs are weak and print terribly, I started measuring Dmax on the leader suspecting weak developer. When my 76 was mixed with DW I couldn't reach leader Dmax; leaders look like they were dipped in strong coffee. Kodak states any film exposed to daylight should reach Dmax with any developer (unless, of course, the developer is defective).

With Rodinal, Tmax, HC110, (note all liquid, mixed just before needed, never stored) the leaders look as though they were painted with opaque black paint. After fussing about, I concluded that the 76 was in precipitous activity decline shortly after mixing with DW(see above post with density numbers).

Since you missed the underlying question in the thread, let me say it again: the issue is not leader density (the leader is my yardstick); it is the rapid and steady decline in developer activity when mixed with Kroger distilled water. I haven't a clue why the water is killing the developer and that is why I brought the question to the forum for possible help.

Not receiving any help other than PE's past posting on the pH of DW being measured in the fives (mine is about 5.2), I have dumped my 76 and will proceed with liquid developers that do not exhibit the problem.

FYI, I have been formally trained in DOE techniques and the Shainin Methods/Tools.

Note to moderator: Please close this thread. Thanks!

 

Gerald C Koch

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As I said there were a lot of people making suggestions (ten pages of suggestions) but I think the consensus is that we are all stumped. I did understand the use of the leader but it is far from a meaningful test. Good luck solving your problem. Do run your own experiments. Try to borrow a densitometer or enlarging meter. This would help.

Packaged D-76 contains a sequestering agent and you really don't need to use distilled water. So just avoid the Kroger water.
 
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pdeeh

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I have been formally trained in DOE techniques and the Shainin Methods/Tools.

is that like Tiger Crane or is it more Eagle's Claw?
 

Bill Burk

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Hey Michael,

How do you test such a wide log-E? It's great that you get to see the shoulder I hardly ever see with only a 3.0 test.

Did you hold some chemistry for an elapsed time (say weeks) test for lost activity due to issues Fred Aspen was seeing?
 
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Arvee

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Thanks, all; results as expected.

Brita filtered water has replaced the Kroger distilled water and no developer failures have occurred; normal dense leaders are now the rule.
 
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Sal Santamaura

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Out of curiosity, I purchased these pH test strips specifically designed for use in water


and checked two gallon bottles of the steam-distilled water I've always used to mix and dilute XTOL. One bottle was in my home for quite a few months and almost empty. The second gallon was newly purchased and full. In both cases, pH tested as 4.

I'm curious. What would the chemists here suggest for adjusting pH to 7 before using the water? Might that buffer cause issues with XTOL? I've had no problems using the acidic distilled water, but am academically interested whether any sensitometric changes could be seen if it were first brought to neutral pH.
 
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Arvee

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It's interesting that an 'ideal fixer' has a pH of approximately 4.5 and will easily kill developer. My distilled water was about 5.0 and killed my XTOL in a week or so and the D76 just sorta gradually petered out over a period of a several weeks. I read that adding a pinch of bicarbonate of soda would bring the pH of DW closer to 7. For me, I've gone to Brita filtered water that has a pH of about 7.5 and I've not had any further troubles.

Like you, I sure would like to know what the heck is going on with distilled water. Theoretically, I read the absorption of CO2 through the plastic walls of the bottles would supposedly only drop the pH to about 6.5 through the formation of carbonic acid. There has to be something more going on with distilled water ranging from 4.0 to 5.0.

Haven't heard a peep out of PE; he brought the issue to the fore sometime back as a result of a nationwide survey.
 

Gerald C Koch

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Distilled water has no buffer capacity. A VERY, VERY SMALL amount of an acid such as carbonic acid from dissolved carbon dioxide can cause a large deviation from a neutral pH. Once the developer is added to the water the pH becomes what is expected from the developers constitution. So testing the pH of distilled water really has no practical meaning.

The concept of buffer capacity is responsible for seemingly endless misunderstanding on APUG. Whatever is causing the OP's observation is not caused by the pH of the water unless it is seriously contaminated.
 
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Sal Santamaura

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Distilled water has no buffer capacity. A VERY, VERY SMALL amount of an acid or base can cause a large deviation from a neutral pH...
Does that mean that, if I add a very, very small amount of baking soda to the new gallon of steam-distilled water, its pH will rise to 7? If so, roughly how much baking soda?
 

Gerald C Koch

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My distilled water was about 5.0 and killed my XTOL in a week or so

Most probably caused by the Fenton reaction and certainly not by the acidity of the water.
 

Gerald C Koch

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Does that mean that, if I add a very, very small amount of baking soda to the new gallon of steam-distilled water, its pH will rise to 7? If so, roughly how much baking soda?

The same argument also applies to very small amounts of bases. There is no buffer capacity so don't worry about the pH of the water. No matter what the pH is it will have no effect on the developer unless the water is contaminated. Of course in this case all bets are off.
 

Sal Santamaura

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As this thread died down, I couldn't resist contacting Dick Dickerson and Silvia Zawadzki, the Kodak engineers who invented XTOL. Although retired, Dick and Silvia still get together regularly, and said they'd discuss my question on implications, if any, of pH and water used to mix stock solutions, at their next meeting. I included a link to the thread, which they reviewed.

After considering my distilled water measurements, their response echoed Gerald's comments; it absorbs CO2 from the atmosphere, causing pH to tumble, and offers miniscule buffering capacity. They indicated bringing the water to neutral would be tedious to do and gain me nothing, adding that the amount of CO2 absorbed by the water is likely no different than what perfectly neutral water would absorb while stirring to mix a developer.

Dick and Silvia went on to discuss the sequestrants, buffers and other addenda found in XTOL (as well as other packaged developers) which enable mixing stock solutions with all but the most foul local water. They noted that there could be a small difference in optimum development time for a given film based on one's particular water supply, but, once dialed in, that time would be consistent. The only photographers they suggest might benefit from mixing XTOL with distilled water are photojournalists who travel the world, encountering varying water supplies in different locations. I replied that, since my local municipal system alternates between water sources of substantially different quality, I'll continue to mix XTOL with distilled, since less than $2 every six months or so seems a small price to pay for consistent contrast index results.

I had mentioned to Dick and Silvia that there have been reports lately of XTOL packages being received in breached envelopes that were open to the atmosphere, which seemed to coincide with a change in supplier from Champion to (reportedly) Tetenal. This is a verbatim quote -- with permission -- of their response's final paragraph:

"Of course all of this is predicated on XTOL still being properly manufactured. No reason to think it isn't, but that is something we can no longer vouch for!"​