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sanking

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skahde said:
Recently I played a bit with the formula of Pyrocat-HD and modified the amount of metabisulfite: doubling it gets you more or less rid of the stain, at least when developing Delta 100. For me this was quite a surprise as with the usual 1+1+100 dilution you end up with just 200mg/L..

Stefan

Stefan,

Your observation is very consistent with all of my own testing. The amount of metabisulfite in the formula has been optimized to provide maximum staining with maximum synergism. Pyrocatechin is very sensitive to extra sulfite and at some point, and my figures are very similar to yours, the stain is lost entirely.

Sandy
 
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sanking

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sanking said:
I do not recommend mixing Pyrocat-HD in -TEA, at least at this time. My initial tests with Pyrocat-HD in TEA have shown that for the same amount of pyrocatechin in the working solution longer time of development are required to reach a given CI than if the stock solutions are mixed in water or glycol. It may be possible to adjust this by adding a little ascorbic acid to the mix but as yet I have not tested the concept.

Sandy

Well, I just tried adding some ascorbic acid to a Pyrocat-HD solution mixed in TEA and it did little or nothing to increase synergim.

The problem, as I see it, is that the working pH of a Pyrocat-HD solution mixed in TEA is around 9.4 or 9.5, while a regular working solutiion of this developer is around 10.9. And the threshhold of development of pyrocatechin is around 9.5. Pat wrote somewhere that when you have two or three developers in the soup the working pH is not as important as when working with any single one, but my experience with the Pyrocat-HD formula suggests otherwise.

Sandy
 

gainer

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pH is always an important consideration, but a certain pH may and usually will have a different effect with a suparadditive combination than with a single agent. I hear people say hydroquinone doesn't work below a certain pH, and therefore it isn't doing anything in D-76. If you take that to the extreme, a developer composed of 0.1 grams phenidone, 4 grams of hydroquinone and 100 grams of sulfite will act the same without the hydroquinone. T'aint so. In other words, the behavior of a given agent as pH changes is not an indication of its behavior in a superadditive mixture.

While metol is quite active in D-23, and will become more active if pH is increased, phenidone is not usually a desirable agent for most films. The example above is a useful substitute for D-23, even though the pH is far below what is considered the minimum for a hydroquinone developer, but without the hydroquinone it is nothing.

When you have a developer that works at a low pH, raising the pH will usually increase its activity, though it may also increase its fog level.

Adding ascorbate to Pyrocat-HD, even if it increased activity, probably causes loss of some or all tanning-staining properties. There is a trade off because with some processes, the stain is as important a contributor to printing contrast as some amount of silver. Certain methods of increasing activity may actually cause a net loss of printing contrast. That is why we hire people like Sandy to do the experiments. We should increase his stipend.
 
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sanking

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gainer said:
s nothing.

That is why we hire people like Sandy to do the experiments. We should increase his stipend.

Anyone who has been sending me a monthly stipend for my experimential work should plan to increase their monthly payments by 50% effective 1 January 2005. Direct bank transfers to my account can be arranged.

Some of this reminds me of a comment made by one of my professors in a class I took a long time ago on the great Spanish epic poem El Cantar de Mio Cid, or the Song of My Cid. The Cid, on being banished from Castiella, was accompanied in exile by many of his vassals. The Cid paid them little or nothing, of course, because at the beginning of his exile he himself had little or nothing. After one of the first important victories of the campaign of the Cid in the lands of the Moors in which his forces captured a lot of booty (that is, gold and silver and such, not "ass" as some today might first imagine booty), the Cid announced to his forces that he planned to double their salary, "doblaros he la soldada". I can remember to this day the reaction of my professor on reading those lines, “Ummmm, they were not being paid anything to begin with, so doubling their salary could not have cost him much.


Sandy
 
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Kirk Keyes

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sanking said:
Kirk,

I am using two pH measuring instruments at this time, both by Oaklon. One is the pH Testr 1, the other their pH Wand. Both provide very consistent readings from as low as pH 1.5 to as high as pH 15.0, but they are off (relative to each othe) by about pH 0.3 in the pH 8.0 to 12.0 range. I don't know which of the meters is most accurate, but at least they are consistent in readings within the range noted.

I would be very appreciative if you would send me the address/email/website of a company that can provide control samples/standards to verify pH measurements. I have use in the past pH strip indicators but these have almost always proven to be less accurate than my instruments.

Sandy

Sandy, while I don't have any experience with Oakton pH meters, I found some instructions for the Tester 1 online - it looks like it can be calibrated at 1 point and it has no Automatic Temperature Control (ATC). (I didn't find any info on the pH Wand in the time I looked.) The Tester 1 a very minimal design for a pH meter and it may not be accurate enough for what you are hoping to do. There is no way any pH meter is going to be accurate over a wide range with only one calibration point and no ATC. The manual for your pH Tester 1 says that it is accurate to +/- 0.2 pH. If you like the Oakton line, it looks like the pH Tester 2 (among other meters) will give you 3 point calibrations and ATC. Either way, these will be much better than using the multistrip pH papers!

But anyway, for what you have now, I suggest that you get a pH 10 standard, and using that standard, make a reading of it. I recommend that the solution be stirring gently while making pH readings. Your meter should have an adjustment screw with which you can make any changes to the meter if there is an offset from the nominal value of the buffer. Remember that pH changes with temperature, and the buffer bottle may have a table on it that will list the pH of that buffer at various temperatures - you can interpolate the actual pH of the solution by measuring the temp and then using the table. So once you have done that, you could use a pH 7, 8, 9, 11 or 12.5 pH buffer to check the linearity of your meter of the range of interest. You may find that your meter is fairly accurate over the narrow range of interest. And by narrow, I mean maybe 1.5-2 pH on either side. (Even though your meter manual says it can make readings from -1 to 15, that really just reflects the error and difficulty associated with making pH measurements at the ends of the pH scale, which in water ranges from pH 0 to 14. While your meter may read numbers outside of that range, they are undefined (i.e. non-sense) and they just mean you've exceeded the actual practical range of the meter. Also, try to have the solution you want to measure as close in temperature to the temp of the calibration standard.

AS far as where to get pH standards, check with you favorite chemistry supply place. Here's my local favorite - they will ship: http://www.nurnberg.com/ Looking at their online catalog, they list 4,7, and 10 pH buffers, and I am pretty sure they can get more values if you want. As far as brands, I have had good luck with Fisher, Ricca, and Orion buffers. Remember that pH buffers do not last forever, so buy small amounts, like 500 mls (about $15-20 each). Find some small resealable bottles of a few ounces and pour out some buffer into them for daily use, and reseal them to keep them from changing when not in use. You don't need some sort of special control samples for this, just look "pH buffers".

Other things to think about about are that the electrode will age and become sluggish and less accurate with age. You will want to be storing the electrode in a storage solution as recommended by your manufacturer to increase the life of the electrode.

Sandy, since you are at Clemson, swing by the Chemistry department and someone there could let you check your meter. If been to there in the past for mass spectrometry training several years ago and it's pretty nice! They may also have some recommendations on local places to get some buffers.

Also, remember that unless you are taking extra care with higher quality meters with ATC and better designed electrodes, you probably cannot put a lot of faith in making really precise pH measurements, especially when comparing numbers over time. For environmental laboratory work, I put a lot of faith in the whole number portion of a pH measurement, pretty good faith in the first decimal place, not much faith in the second decimal, and as far as I'm concerned, for that type of testing, the 3rd decimal place could be used as a random number generator.

So for using your meter, you may want to consider readings right around the pH buffer used for calibration to be +/- 0.1, one or two units away may be +/- 0.2, 3 or more units away will probably be greater in error. It all depends on the slope of the response of your electrode, which changes with time and age. If you have a meter that you can calibrate with more than one point, you may expect to be within 0.1 or better pH units between the two calibration points. THis is because the meter can measure the slope of the pH electrode response and then use that in the calibration. But even then, the only way to be certain is to get a buffer to measure in the range of interest to be certain.

As an example of how hard it is to measure water samples for pH precisely, in a recent national water pollution proficiany test, with a pH test sample that had an assigned pH value of 8.50, the labs in the test had to get a measurement between 8.25 to 8.75 to get an acceptable result. That +/- 0.25 pH acceptance range was not just a made up number, it was determined by doing a statistical analysis of the results submitted by the labs and it reflects the calibration and performance of all the equipment used in the study.

It's good that your meters are consistent, but with a little work with calibration, you should be able to get them more accurate for small ranges near the calibration point.

If you have any other questions, let me know.

Kirk - www.keyesphoto.com
 

Kirk Keyes

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sanking said:
But to reach your goal will require first and foremost definining rather precisely what it is that you want to achieve, and then devising an efficient testing methodology for taking you there.
Sandy

Sandy, Jay - are you guys familiar with what is sometimes called a "Youden Testing", "Youden Analysis", or "Ruggedness Test"? W.J. Youden was a student a chem engineer and later became one of founders of process control and quality control/assurance.

Anyway, Youden came up with a "ruggedness test" - one can measure the stability (i.e. the change) in results produced when steps in a method (procedure) are varied. These steps can be amounts of materials, times, temps, concentrations, reagents. The beauty of this testing scheme is that one can measure the effects of 7 different variations in procedure in only 8 different tests. You make a list of the 7 variables you want to test, and then (with the help of a matrix) you come up with the 8 tests and you run them. Those 8 tests have all the combinations of each of the 7 variables. Then, and here's where Sandy's recommendation to define what you want to design for comes in - whether it is density, stain, graininess, speed, resolution, whatever - you need to be able to measure what you want and then make the measurements. Once the measurements are made, you pair up a certain set of 4 tests and compare the results with the remaining set of 4 tests to see if you maximized or minimized the property your were testing by making the changes in each of the 7 variables you defined above. It also can tell you which variable has the greatest or least effect, and by how much.

I hope that made sense...

The other thing that is cool about this is that the matrix can be scaled - we are all familiar with being able to test for one thing by making two tests. Well, it can be scaled so that n tests can be used to measure n-1 variables. So if you have 3 variables you want to test for, you can measure the effect with 4 tests, and so on... You just need to figure out a matrix that allows you to do it.

It's a really powerful tool and if you aren't familiar with it I suggest that you read up on it some. Every so often, Robert Chapman in PhotoTechniques covers this subject. I suggest going to the library and finding a book of quality control and statistics, but here's a link that covers it in more detail than I can give here. Go to section 7.5.7 Ruggedness, Robustness: http://www.fao.org/docrep/W7295E/w7295e09.htm

If you have any questions, feel free to ask.

Kirk
 

Kirk Keyes

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Jay (or is it "Homestar"?) -

That's a lot of things that you could be using a testing scheme like Youden's to work with. And remember, you can probably measure the effect of all your test variables for all of the things you are currently measuring using the Youden test. Simply recalculate your results using the different properties that you have measured.

Kirk
 
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sanking

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Kirk Keyes said:
It's good that your meters are consistent, but with a little work with calibration, you should be able to get them more accurate for small ranges near the calibration point.

If you have any other questions, let me know.

Kirk - www.keyesphoto.com

Kirk,

Thanks for all of the useful information in your last post. What with the holiday season upon us and a trip to Mexico in January I am not going to be doing much testing for a while, but I will definitely plan to take advantage of your advice and sources when I return.

Sandy
 

craigclu

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As I'm narrowing down some very long term and sporadic testing, I was cleaning up some of my formula records and thought I'd ask some things that I've been meaning to clear up regarding Rollo-TEA. This was one of the first Pyro/TEA solutions that I tried back when Sandy was first discussing it and I've got conflicting formulas in my file.

Sandy, have you settled on Sodium Metabisulfite vs bisulfite? One of my formulas lists 50% more KBr (my one old batch of this has the lesser amount). What is the pattern of film speed results you are seeing? I hadn't done any tightly controlled testing on the Rollo-TEA yet, but I seemed to be in the 240-320 range with HP5+. What sort of pH did your final version seem to measure at? Thanks in advance.
 
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sanking

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Craig,

Sodium metabisulfite is what you want to use. Fact is, most sodium bisulfite sold for photographic purposes is really sodium metabisulfite. Morever, the two give very similar results in this forumula, except in the most critical operation.

I have found that effective film speed with the Rollo-TEA formula to be very similar to what you get with the original Rollo-Pyro formula.

As for pH, I am on the road at this time and don't have the data on hand, but as best I recall the pH of a working solution of Rollo-TEA is about 9.2. And the working solution is well-buffered.

Sandy


craigclu said:
As I'm narrowing down some very long term and sporadic testing, I was cleaning up some of my formula records and thought I'd ask some things that I've been meaning to clear up regarding Rollo-TEA. This was one of the first Pyro/TEA solutions that I tried back when Sandy was first discussing it and I've got conflicting formulas in my file.

Sandy, have you settled on Sodium Metabisulfite vs bisulfite? One of my formulas lists 50% more KBr (my one old batch of this has the lesser amount). What is the pattern of film speed results you are seeing? I hadn't done any tightly controlled testing on the Rollo-TEA yet, but I seemed to be in the 240-320 range with HP5+. What sort of pH did your final version seem to measure at? Thanks in advance.
 
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