Organoleptic properties of Harvey's 777 type developers

[Pixophrenic]

I am starting this as a merger of two recent threads, one on homebrew Microdol, and another on ripening and Harvey's 777.
By looking at the fomulas in what they <think> is Harvey's 777, I got to look closely into the family of Edwal 12, and Windisch 667. Which is, given the timeline, from a period when phenidone was out of the circle of comprehension. So, it is not unexpected that they basically mix up D-23, then <supplement> (it is an important word here) it with something that improves on its time-proven qualities. Now, Edwal 12, for one, is nothing but D-23 supplemented with PPD (p-phenylene diamine) and glycin. As I made myself some Edwal 12 (or what they think it is, anyway), I found that it retains the pH of D-23 (or very nearly so). Now it sits on the bench and after a few days I am going to develop the first film and continue watching what happens to it afterwards. An interesting thing is that both PPD and glycin are not supposed to be very active at pH 8. Typical developers for either used in isolation are very alkaline, pH 11 or so, and even then the times for PPD may be over half an hour with 10 g/L PPD. So in Edwal 12 they perform other function than that of a developing agent. My guess would be that one still acts as a halide solvent, and a more powerful one than sulfite, and the other is a padding in the prevention of oxidation of metol. You can see that the general idea behind homebrew Microdol is not that different. Now, Windisch 667 is a step in the right direction, as it uses o-phenylene diamine, now a rather scarse chemical ( which may hint to why Bluegrass may have a supply problem).
So, my question is, what are the organoleptic properties of commercial Harvey's 777? What's its color, how does it smell, and please don't taste it. Also, how color and smell change with time. Your impressions will be highly appreciated.

 

[Gerald C Koch]

PPD is a very weak developing agernt almost always used for its solvent nature to silver halide. Glycin is a slow but powerful developing agent. To increase its speed it benefits from a higher pH. Orthophenylenediamine has NO developing characteristics and is used a as solvent alone.

PPD has a distinctive odor that is usually described as pleasant or as medicinal ie the smell of an old time drugstore. Solid Glycin is easily oxidized but once in solution resists oxidation.The prence of PPD in Harveys is given away by its snell. Glycin is colorless while orthophenylenediamine is yellowish brown and PPD is dark purple. The presence of PPD in Harveys is given away by its small

 

[Pixophrenic]

PPD is a very weak developing agernt almost always used for its solvent nature to silver halide. Glycin is a slow but powerful developing agent. To increase its speed it benefits from a higher pH. Orthophenylenediamine has NO developing characteristics and is used a as solvent alone.

PPD has a distinctive odor that is usually described as pleasant or as medicinal ie the smell of an old time drugstore. Solid Glycin is easily oxidized but once in solution resists oxidation.The prence of PPD in Harveys is given away by its snell. Glycin is colorless while orthophenylenediamine is yellowish brown and PPD is dark purple. The presence of PPD in Harveys is given away by its small

So, Gerald, would you agree that in the Germain metol-PPD-glycin 777 combination only metol would work as developing agent, and the other two will develop only weakly if at all?
Also, PPD imparts distinctive odor and color, and glycin no odor but color, so what odor and color commercial Harvey's 777 has? My Edwal 12 solution now looks like a dilute Ceylon tea.

 

[Gerald C Koch]

So, Gerald, would you agree that in the Germain metol-PPD-glycin 777 combination only metol would work as developing agent, and the other two will develop only weakly if at all?
Also, PPD imparts distinctive odor and color, and glycin no odor but color, so what odor and color commercial Harvey's 777 has? My Edwal 12 solution now looks like a dilute Ceylon tea.

Probably metol does the majority of the work. The photographer Bob Schwalberg describes Hatveys odor as pleasant and aromatic.

 

[Pixophrenic]

Thank you, Gerald. Pleasant and aromatic hints that PPD or OPD is there. Catechol and pyrogallol are excluded, they are not stable in high sulfite. If PPD does not participate as a developer I suppose its concentration is rather arbitrary. What do you think?

 

[Lachlan Young]

Major problem with assuming that all these developers started as D-23 variants: wasn't D-23 disclosed in 1944 or thereabouts & 777 & Edwal 10/12 came into being in the late 1930's? Edmund Lowe seems to have published the Edwal formulae at least as early as 1939, and articles about 777 date to at least 1938. More importantly, they seem to have started as substitutions on D-76 with glycin for HQ (Edwal 10), then adding PPD ( Edwal 12). Also remember that things like DK-76 & other buffered variants etc of D-76 were disclosed in the later 1930's.

 

[Pixophrenic]

I am not an expert in photochemical history, but I recall that the "idea of D-23" predates the appearance of official Kodak D-76. It would not be expected to be accepted due to the quality of both metol and sulfite. You would agree, I hope, that Edmund Lowe's idea of using PPD under conditions where it would display negligible developing activity was not in either D-76 or D-23, even though the use of PPD as a developer (under highly alkaline conditions) predates both of them. All I am saying is that from today's perspective Edwal 10 and 12 are substituted D-23, not D-76, because extraneous alkali is absent. Edwal 10 or 12 are not "buffered" in the common sense of this word in the area of developers. An additional argument for metol being the main driver in 777 is that only metol works reasonably well at low pH and also has low temperature dependence, aka "panthermic" quality. Since 777 went though a number of revolutions, such as going to Dupont and then back, if I am not mistaken, it may have undergone some modernization, wherein PPD may be expected to have been replaced with something less toxic, and glycin dumped altogether and replaced with another "padding" for metol such as a weak but stable derivative of hydroquinone. It could be expected that Bluegrass is facing a cost/sourcing dilemma, which makes me think that PPD was replaced with OPD in their formula, as it is readily "available" just not in a photographic market.

Oddly, no one is willing to contribute to the issue of organoleptic qualities so far.

 

[Lachlan Young]

I think that there's probably a good chance one of the CD's has been used to replace the PPD, perhaps compare it to C-41 developer, E6 colour developer, RA-4 developer or Adox Atomal & that might narrow down things somewhat, given that they all use specific (and different) CD variants. They do have distinguishable smells, but describing them is probably harder than experiencing them. Furthermore, I have no great desire to sniff unsubstituted PPD if I can avoid it...

More to the point, I think that Henn et al probably had a pretty good idea of what was going on in 777 (and Edwal 12) & realised that you could probably eliminate everything apart from the metol & sulphite at that pH without significant downsides. If you wanted finer grain still, add a chloride salt (and an antifoggant if needed). KRL would have been deep in work on PPD & its substituted derivatives at the time & I'd be inclined to say that they probably had a clearer idea of their usefulness & effects in the pH ranges in question than either Harvey or Lowe. If they had the claimed effects of E12 or 777, I have little doubt Kodak would have offered an equivalent developer. I'd be interested to see a well controlled comparison between replenished D-23, E12, E10 & 777 (preferably accompanied by photomicrographs & microdensitometric studies), but the difficulty of carrying out the latter essentially puts it out of reach of pretty much anyone outside a manufacturer's R&D lab.

 

[Rudeofus]

Just to clear up some confusion:

1. yes, PPD is slow at pH 8, because its oxidation product still sticks to silver and silver halide and effectively prevents fresh PPD from reaching the grain. Oxidized PPD reacts with sulfite only slowly, which makes PPD only developers slower than Metol+sulfite type developers.
   
2. Yes, Glycin alone is quite a slow developer at pH 8, because it is negatively charged and has only weak tendency to adsorb to silver and silver halide grains. On its own it just doesn't reach the development center quick enough to facilitate quick development action
3. No, together they don't perform random miracles, they just work as superadditive combo. PPD does the initial reduction of silver ion to silver, and Glycin happily passes its own electron to oxidized PPD, thereby restoring it to original condition. It's pretty much the same situation as with MQ, PQ or PC type developers.

Whatever may be in Harvey's 777, lots of people have already speculated, some even claimed to possess the formula, with neither the speculation nor the claimed formulas having much credibility.

I guess if anyone really wanted to know what's in Harvey's 777, one would have plunked down real hard cash for a mass spectrometric analysis and been done with it.

 

[removed account4]

I guess if anyone really wanted to know what's in Harvey's 777, one would have plunked down real hard cash for a mass spectrometric analysis and been done with it.

LOL exactly .. but that's too easy ..
and it is much fun-er to go by what others imagine it might be

 

[Lachlan Young]

I guess if anyone really wanted to know what's in Harvey's 777, one would have plunked down real hard cash for a mass spectrometric analysis and been done with it.

Indeed - and it's probably a whole lot less exotic than people want it to be...

 

[Rudeofus]

And it's concrete evidence that people don't care about Harvey 777 nearly as much as they claim.

I still remember all these page long threads about Microdol-X - now that PE has revealed the formula, I still haven't read a single report "I mixed it with these ingredients and it did ...". Note: PE has also claimed that Formulary offers ALL the required ingredients, even if some may not be publicly listed on their web page. "I can't get 4-CR" is not a valid excuse.

 

[Raghu Kuvempunagar]

What’s the USP of Harvey’s 777 developer?

 

[Pixophrenic]

Just to clear up some confusion:

1. yes, PPD is slow at pH 8, because its oxidation product still sticks to silver and silver halide and effectively prevents fresh PPD from reaching the grain. Oxidized PPD reacts with sulfite only slowly, which makes PPD only developers slower than Metol+sulfite type developers.
   
2. Yes, Glycin alone is quite a slow developer at pH 8, because it is negatively charged and has only weak tendency to adsorb to silver and silver halide grains. On its own it just doesn't reach the development center quick enough to facilitate quick development action
3. No, together they don't perform random miracles, they just work as superadditive combo. PPD does the initial reduction of silver ion to silver, and Glycin happily passes its own electron to oxidized PPD, thereby restoring it to original condition. It's pretty much the same situation as with MQ, PQ or PC type developers.

Whatever may be in Harvey's 777, lots of people have already speculated, some even claimed to possess the formula, with neither the speculation nor the claimed formulas having much credibility.

I guess if anyone really wanted to know what's in Harvey's 777, one would have plunked down real hard cash for a mass spectrometric analysis and been done with it.

The lore goes on that a} it works especially well at higher than usual temperatures b) it keeps well in large volumes protected from air. Both properties are supplemental to a D-23 used under the same conditions, except that if someone valued stability and compensating action occurring at the same time, this is it. 777 value is clearly limited outside these two constraints, which explains why there is limited incentive to find out what it is. In addition, the reported dependence on the kind of agitation in use, addressed at length in the online article is characteristic of PPD or derivative. Color films are indeed processed with constant agitation.

 

[Pixophrenic]

LOL exactly .. but that's too easy ..
and it is much fun-er to go by what others imagine it might be

One possibility is that someone did that and was disappointed with the results. The other is what I suggested, that the magic component, the ripening, is not initially in the formula.

 

[Pixophrenic]

I think that there's probably a good chance one of the CD's has been used to replace the PPD, perhaps compare it to C-41 developer, E6 colour developer, RA-4 developer or Adox Atomal & that might narrow down things somewhat, given that they all use specific (and different) CD variants. They do have distinguishable smells, but describing them is probably harder than experiencing them. Furthermore, I have no great desire to sniff unsubstituted PPD if I can avoid it...

More to the point, I think that Henn et al probably had a pretty good idea of what was going on in 777 (and Edwal 12) & realised that you could probably eliminate everything apart from the metol & sulphite at that pH without significant downsides. If you wanted finer grain still, add a chloride salt (and an antifoggant if needed). KRL would have been deep in work on PPD & its substituted derivatives at the time & I'd be inclined to say that they probably had a clearer idea of their usefulness & effects in the pH ranges in question than either Harvey or Lowe. If they had the claimed effects of E12 or 777, I have little doubt Kodak would have offered an equivalent developer. I'd be interested to see a well controlled comparison between replenished D-23, E12, E10 & 777 (preferably accompanied by photomicrographs & microdensitometric studies), but the difficulty of carrying out the latter essentially puts it out of reach of pretty much anyone outside a manufacturer's R&D lab.

The problem with that supposition is that as film formulation changed, the chloride trick was no longer working. On another of your impressions, when I first experienced catechol, my first thought was "why anybody on earth want to use that?", but after a a few films I think that Pyrocat/Tanol is something any serious analog photographer should experience personally. Just be careful with the waste.

 

[Pixophrenic]

Major problem with assuming that all these developers started as D-23 variants: wasn't D-23 disclosed in 1944 or thereabouts & 777 & Edwal 10/12 came into being in the late 1930's? Edmund Lowe seems to have published the Edwal formulae at least as early as 1939, and articles about 777 date to at least 1938. More importantly, they seem to have started as substitutions on D-76 with glycin for HQ (Edwal 10), then adding PPD ( Edwal 12). Also remember that things like DK-76 & other buffered variants etc of D-76 were disclosed in the later 1930's.

Now that I dug up some literature, I could answer this properly. Lowe's patent US2164280 of 1939 is cited in Henn and Crabtree patent of 1945. The point in the former was that the developer was made up of metol, glycin, sulfite and ammonium chloride, so that the resultant pH was preferably between 7.3 and 7.5. As I mentioned, such developers are extremely slow at 20 degrees Celsius and also that glycin does not really do any developing. An interesting revelation of Lowe is that 10% solution of his sulfite had a pH of 9.7, while currently available reagent grade sulfite would make a solution with pH of 8 to 8.2.That's quite a difference. It means that any current user trying to reproduce Lowe's recipes with high quality reagents would end up with a different developer than the originally intended. Also of note, Henn and Crabtree make a point that their invention is supposed to address the stability of ammonium chloride containing developers, replacing ammonium chloride with a mixture of amine and sodium chloride. Edwals, on the other hand, are clearly coming out of Lowe's work looking for an alternative silver complexing agent in place of ammonium chloride that would also provide better keeping properties. At this point in time, enter the 777.

 

[Rudeofus]

An interesting revelation of Lowe is that 10% solution of his sulfite had a pH of 9.7, while currently available reagent grade sulfite would make a solution with pH of 8 to 8.2.That's quite a difference.

The difference is insignificant, since Sodium Sulfite is an extremely weak buffer at pH 9.7. Once you add Metol, pH will come down towards a range where buffering is strong, i.e. around pH 8.0 - 8.5.

Note, that if you mix 100 g/l Sodium Sulfite solution fresh from powder, initial pH will be above 9, and you can observe how pH drops as aerial Carbon Dioxide is dissolved. This happens within the first hour. I would therefore be extremely hesitant to trust any "pH of 10% Sodium Sulfite" number you see. There is some discussion about this here (post 486ff)

 

[Pixophrenic]

The difference is insignificant, since Sodium Sulfite is an extremely weak buffer at pH 9.7. Once you add Metol, pH will come down towards a range where buffering is strong, i.e. around pH 8.0 - 8.5.

Note, that if you mix 100 g/l Sodium Sulfite solution fresh from powder, initial pH will be above 9, and you can observe how pH drops as aerial Carbon Dioxide is dissolved. This happens within the first hour. I would therefore be extremely hesitant to trust any "pH of 10% Sodium Sulfite" number you see. There is some discussion about this here (post 486ff)

Thank you for the link, rudeofus, but in my opinion this discussion is not all correct. It is also quite surprising that a professional like PE did not object to some things that were said. It cannot be assumed that they had the same sulfite quality in mid-1930s relative to today, and that even today we all have the same purity sulfite on hand, and that it is reagent grade or better. It is true that sulfite is a poor buffer at pH 10, but that's assuming is it 99.9% pure. Sodium sulfite is made industrially by reacting sulfur dioxide with a solution of sodium carbonate, and then sodium hydroxide, so its prime impurities are going to be sodium carbonate and sodium bisulfite. I read somewhere there is a special procedure to get rid of carbonate impurity in actual sulfite on hand for critical applications. Unfortunately cannot place where it was. Also, pH drift in solution from dissolving carbon dioxide from air relative from that of oxidation to sulfate is at least 100-fold speed difference. And that's again assuming that we are dealing with a pure chemical in pure water. Finally, when you add metol which is a hemisulfate, what you see is a relatively fast equillibration of the two anions competing for the metol cation, not dissolution of carbon dioxide.

 

[Rudeofus]

If you make Sodium Sulfite from Sulfur Dioxide and Sodium Carbonate, I am quite sure it is done in a way that avoids significant left over carbonate in the final product. Even if you start with 99.999999% Sodium Sulfite, aerial Carbon Dioxide will add some carbonate very quickly. It doesn't matter, though: some fraction of percent carbonate is not going to turn a 100 g/l Sodium Sulfite solution into a decent buffer at pH above 9.

If you look at Metol in alkaline solution, it is not just some cation with half a sulfate anion: the -OH group of the cation itself is weakly acidic. This will form a neat buffer with Sulfite at a pH around 8.0 - 8.5.

 

[Pixophrenic]

The difference is insignificant, since Sodium Sulfite is an extremely weak buffer at pH 9.7. Once you add Metol, pH will come down towards a range where buffering is strong, i.e. around pH 8.0 - 8.5.

Note, that if you mix 100 g/l Sodium Sulfite solution fresh from powder, initial pH will be above 9, and you can observe how pH drops as aerial Carbon Dioxide is dissolved. This happens within the first hour. I would therefore be extremely hesitant to trust any "pH of 10% Sodium Sulfite" number you see. There is some discussion about this here (post 486ff)

The truly interesting thing happens in this discussion later on. I also considered a concoction with minimal sulfite, phenidone and sodium ascorbate, without knowing about this massive thread. It was stimulated by Crawley's FX-55. I cut it down to a bare minimum (same concentrations of developing agents, same pH) and observed the same phenomenon when a test strip developed properly (5 frames) and 24-frame film developed in the same portion only two hours later had this Dmax limitation. The same thing was observed when a tiny amount of HQ in the H&W Control developer was replaced by sodium ascorbate. I think, however, that this had something to do with the film formulation than with the developer. But the result was that I dropped ascorbate from consideration altogether.

Anyways. the lack of straight answer to my initial question is surprising, to say the least. 777's color, anyone? What are you afraid of?

 

[removed account4]

One possibility is that someone did that and was disappointed with the results. The other is what I suggested, that the magic component, the ripening, is not initially in the formula.

if someone did a spectral analysis of the developer and figured out the ingredients
and had the mix ..
and they had some of the original mixture from bluegrass left ( they give you 2 > 2 gallon sacks from what
i remember )
maybe i am totally wrong, but as a layman not a chemist,
i am guessing that both fresh developers made with water
would yield the same results whether they were ripened or not.
( if they were in fact the same developer ) .. right?

its not the dry chemicals that are ripened but the mixed stuff.

photography companies have a long history of not giving information out to people who ask
emulsion recipes purposefully leave out steps or give wrong amounts of ingredients
and even today when people post "results" some aren't really up front with
what they did and how they got their results so things need to be taken with a huge grain of salt ..

if you like the results, why not just use the unblinking eye formula
and call it a day ... isn't that what it is all about, using a developer and liking the results?

 

[Pixophrenic]

If you make Sodium Sulfite from Sulfur Dioxide and Sodium Carbonate, I am quite sure it is done in a way that avoids significant left over carbonate in the final product. Even if you start with 99.999999% Sodium Sulfite, aerial Carbon Dioxide will add some carbonate very quickly. It doesn't matter, though: some fraction of percent carbonate is not going to turn a 100 g/l Sodium Sulfite solution into a decent buffer at pH above 9.

If you look at Metol in alkaline solution, it is not just some cation with half a sulfate anion: the -OH group of the cation itself is weakly acidic. This will form a neat buffer with Sulfite at a pH around 8.0 - 8.5.

Frankly, Rudeofus, I do not understand what you are trying to achieve here. We were talking about sodium sulfite quality then and now. Do you have doubts that it has vastly improved in 60+ years?

if someone did a spectral analysis of the developer and figured out the ingredients
and had the mix ..
and they had some of the original mixture from bluegrass left ( they give you 2 > 2 gallon sacks from what
i remember )
maybe i am totally wrong, but as a layman not a chemist,
i am guessing that both fresh developers made with water
would yield the same results whether they were ripened or not.
( if they were in fact the same developer ) .. right?

its not the dry chemicals that are ripened but the mixed stuff.

photography companies have a long history of not giving information out to people who ask
emulsion recipes purposefully leave out steps or give wrong amounts of ingredients
and even today when people post "results" some aren't really up front with
what they did and how they got their results so things need to be taken with a huge grain of salt ..

if you like the results, why not just use the unblinking eye formula
and call it a day ... isn't that what it is all about, using a developer and liking the results?

Do you think it wrong to "desclassify" it after so many years? Especially as it is no longer available for purchase? What if it contained an idea worth using today in other formulas?

 

[removed account4]

Anyways. the lack of straight answer to my initial question is surprising, to say the least. 777's color, anyone? What are you afraid of?

i had some given to me but never mixed it, i shipped it to a friend. i think the powder was off white but sorry
i don't remember, it was in a bag so i don't know what it smelled like.

Do you think it wrong to "desclassify" it after so many years? Especially as it is no longer available for purchase? What if it contained an idea worth using today in other formulas?

yup i do i think they should keep the formula secret if they want.
the ziljian family keeps their alloy secret, and even bought out splinter family members
and the cocacola formula is secret, and rockland colloid keeps their
liquid silver emulsion ferrotype developer formula secret.
and while some folks think the "secret sauce" of a big mac is 1000island dressing
its not, its still a secret too, not to mention my grandmothers paklava recipe, when i made it in college
i made all my friends leave the room when i did the secret part ...
i see nothing wrong with keeping the 777 secret, especially since they still make it and sell it ...
absense makes the heart grow fonder, AND threads like this tend to boost sales when they do
offer it for sale ... speaking of which why not buy 50gallons worth

OR

if you like the unblinking eye recipe why not use that
if you like the way it makes your film look, ...
there really aren't any silver bullets ..

OR

you could always offer to BUY the formula from them.
and then post what the formula actually is
(instead of hopeful rumors, and hearsay formulae )

 

[Anon Ymous]

Anyways. the lack of straight answer to my initial question is surprising, to say the least. 777's color, anyone? What are you afraid of?

I don't think they're afraid of anything, I'd assume they don't exist.