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Two bath Selenium Suphide toner to Kodak Rapid Selenium Toner

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TMZ

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Hi,

This is a fairly advanced question.

I am a professional photographer and have been printing fine art BW prints for 27 or so years.

In the past I have used my standard Kodak Rapid Selenium Toner, replenishing and filtering an old bottle (from late 1980s?) for years. Sadly, I have now run out of my reserve stocks of the Kodak and will have to shift to a new brand. I can now get the Adox or the Fotospeed SLT20.

However, my question is this: I have 3 full packs of Photochem's Selenium Toner, which is actually a 2 bath version, with a bleach (ferricynide one, like for sepia), then a Selenium Sulphide toner. More like a Flemish toner really. I prefer the "normal" one bath system. Is there any additives(chemicals) I can add to the Toner part of this kit (2nd bath) to make it close to the Kodak. I cannot find info on the Photochem anywhere about it's formula, so a bit of guesswork.

I've been told this style of 2 bath selenium toner has a very short working life, whereas the old Kodak(KRST) had almost an indefinite life. So if I can mix anything into it to make it closer to the Kodak, it'd be great.

From what I can gather, the main difference from published formulae of the 2 bath Selenium to the standard one bath Selenium toner, is that there is much more Sodium Sulphide in the latter ( for 1 litre, it was 25g in the former and 250g in the latter, both with approx 5g of powdered selenium.) Is this the secret to a non bleach bath selenium toning process with extended working life?

I have a darkrrom full of chemistry, from Metol to Thiosulfite to Sodium Sulphide by the kilo, so all I need is a recipe, or even a hint of one.

Thanks in advance.
 

Rudeofus

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The toner you describe is not a standard selenium toner. It is a mixed toner that does both selenium and sulfur toning in order to achieve a certain image tone. I think Moersch's Carbon toner does the same thing.

For a long time I had the impression that all selenium toners were created equal, until I ran into big problems with Rollei selenium toner. I had to use it at much higher concentration than Kodak KRST to really protect my images. Rumors have it that EU rules were imposed because selenium is toxic, and this forced many vendors to either go up in price or lean down their soups. Do yourself a favor and get the real thing, AFAIK you can still get it in Europe.
 

David Allen

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The formula that I have in my notes is

destilliertes Wasser (Distilled water) 560 ml
Ammoniumthiosulfat (Ammoniumthiosulfate, sicc). 270 g
Natriumsulfit (Sodiumsulfite, sicc). 150 g
Natriumselenit (Sodiumselenite) [Na2SeO3] 20 g

Please remember that Sodiumselenite (Na2SeO3) is very toxic!! and that this formula should only be made if you have access to a fully efficient fume hood.

Personally, I have been happy with ADOX Selenium Toner 500ml which can be ordered from Fotoimpex in Berlin and Moersch also sells Selenium and Carbon toners.

Bests,

David.
www.dsallen.de
 

john_s

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There are recipes for making sodium selenite from sodium sulphite and elemental selenium if you do a search on the internet. Below is a collage of posts I've copied from the web over the years in case Kodak RST becomes unavailable in my country (looking increasingly likely).

<start of copied posts>
Selenium is extremely nasty stuff that many photographers won't even touch;
I believe it's safe enough at room temperature (with skin contact avoided),
but a boiling solution does give off toxic fumes. I make mine in the open
air, usually 25 litres at a time, in an aluminium "Burco" boiler (which, I
understand, was used in the old days for cleaning dirty nappies/diapers).
The toning solution attacks other metals, so I've had to replace the tap
with a nylon one from a home-brew shop.

The published Kodak recipe (T-55 or T-56, I forget which) contains about 6g
of selenium per litre, but I could never get it to dissolve completely, even
with boiling for an hour. I don't remember the Kodak formula exactly, but
I've modified its quantities as follows. so that the selenium should
dissolve fully in less than 30 minutes:

Sodium sulphite 140g
Selenium powder 5g
Ammonium chloride 140g
Water to 1000ml

Dissolve the sulphite in hot water, bring to the boil and add the selenium.
Boil for as long as necessary, then stir in the amm. chloride. Kodak said,
I think, that the solution should be cool before adding the amm. chloride,
but it dissolves much easier in warm/hot and does not seem to make any
difference. The toner is then diluted 1+5 for use, at which strength its
action is roughly equivalent to Kodak Rapid Selenium at the 1+3 dilution.

Maybe selenium came in a different form in the 60s and further back (which
Clerc appears to confirm), but you're not alone in finding that specified
quantities do not always dissolve completely. I once tried to speak to
someone at Kodak about their selenium recipe, but they knew nothing about it
and denied it was one of theirs. If I got that in writing, maybe I could
patent it...

Finally, a bit of info from Clerc:

The use of selenium in the form of seleno-sulphate* (with ammonium chloride
added) for toning print-out papers was suggested in 1912 by P. Rehlander as
being more economical than toning with gold and platinum. [Clerc says
elsewhere that the same solution is fine for development papers.] Even with
papers that have been well washed to remove the soluble silver salts, toning
with sodium selenosulphate tends to stain the whites of the image very
strongly. This trouble can be obviated, when toning is done after fixing
and washing, by adding a small quantity of sodium hyposulphite [what they
then called sod. thiosulphate, or hypo] to the toning solution (Lumiere and
Seyewetz, 1924). This procedure greatly increases the speed of toning. The
tones obtained vary from dark brown to red**, according as the image is
coarse or fine grained; this toning gives (with certain papers) an
appearance of platinum toning when used on a print which has been toned with
gold and fixed.

Sodium selenosulphate may be obtained by dissolving 260 gr. of powdered
selenium in 20 oz. (30 grm. in 1,000 c.c.) of a warm 20 per cent solution of
anhydrous sodium sulphite. [No way!! But see first footnote - doesn't
sound like the selenium I buy. Liam.]

Twenty to 50 minims of this solution are added to 20 oz. of a 30 per cent
solution of hypo (2 to 5 c.c. per litre of hypo solution). The smaller
quantity is used for toning albumen papers and the larger for emulsion
papers (gelatine or collodion P.O.P.). The bath is limpid, colourless, and
keeps well.

Toning is very rapid, taking from 2 to 5 minutes, according to the degree of
exhaustion of the bath. This toning solution is very economical; 35 oz.
(1,000 c.c.) will tone 80 prints 7 X 5 in. in size, and the results are
highly permanent if washing is properly done.

* Selenium, which in many of its properties resembles sulphur, appears
usually as grey crystalline masses; in a fine state of subdivision it is
generally red. The alkaline selenosulphates, and particularly the sodium
salt (Na2SSeO3), have a constitution which is closely analogous to that of
the hyposulphites (Na2S2O3), the selenium replacing a portion of the
sulphur. Just as thiosulphate is obtained by dissolving sulphur in a hot
solution of sulphite, so selenosulphate is obtained by dissolving selenium
in hot sulphite solution. As selenosulphate is not made commercially it
must be prepared as required by dissolving selenium. Solutions of
selenosulphates should be kept in full bottles, well stoppered to avoid
conversion into inactive selenotrithionates by oxidation; they are more
stable in presence of sodium sulphite or hyposulphites. Analogous compounds
of tellurium have also been used for the toning of silver prints.

** The ratio (1:0.88) in a long while toned print is greater than that for
silver selenide (Lumiere and Seyewwtz). The selenium is deposited on the
silver without combining with it until each grain of silver is completely
enclosed in selenium.

[In recent times, there have arisen serious doubts about the ability of
selenium to protect silver images against oxidation, which others on this
list can probably say more about.]

Liam
===============================
Tan, you asked if anyone had done it.... I did and seemed not to have any
problems, other than fear for my life, since so much is made of the danger
of selenium. I boiled it in a narrow-mouthed flask, and it went into
solution in a minute or two. One difference I suspect is that my formula
has much less selenium. I suspect yours may have too much.

Here are the formulas I have, and which, incidentally were reprinted on
page 27 of Post-Factory Issue #3 (along with a dozens of others!).

T-55 is a DIRECT TONER

Dissolve 25 g sodium sulfite anydrous in 100 ml hot water. Add 1 (ONE) g
selenium powder and boil til dissolved. Cool
Add 31 g ammonium chloride, stir.
Add 67 ml water.
For use, dilute from 1 to 5 to 1 to 9 with water.

T-56 is bleach & redevelop, AND has sodium sulfide (with a d,) instead of
the sulfite), and the sulfide (I have read) aids dissolving of the
selenium, maybe it's that powerful smell.

Dissolve 25 g sodium sulfide in 100 ml water. Warm solution. Add 5 g
selenium powder, boil til selenium is dissoved. For use dilute 1:20 in
water. Use as redeveloper after ferricyanide bleach. Etc. Etc., Etc, with
various variations. If whites stain, a few drops of ammonia in working
solution is said to clear. I didn't have any staining. (Probably the
exquisite NYC water, or possibly the lesser amount of selenium.)

Apparently this disagrees with Liam's notes from very authoritative
sources, sorry I don't remember where mine are from. If it matters I might
be able to look them up -- but they surely toned & beautifully. It's also
possible that my selenium is a different sort -- bought it 20 years ago...
and who knows if it's still any good. But it was already very dark brown,
nearly black.

cheers,

Judy
======================================
Oh one more thing, Tan

When I prepaired the T55 I used a magnetic stirrer/heater, and the
solution was in a erlenmeyer, so during boiling the solution was cont.
stirred, maybe that is why I had more luck in soluting the selenium (which
was a very old jar, the powder was deep black)

A ps.

I have been wondering why there is fixer in the Kodak selenium toner for a
long time. I think Liam gave the clue by the quote from Clerc where it is
mentioned that adding hypo to the selenium toner can prevent highlight
stain of this toner on prints (POP?).

==================================================================
FWIW, elemental Selenium, sometimes called Selenium dust is a dark brown
to black color. Sodium Selenite, the substance used in Kodak Rapid Selenium
Toner is a white or off-white crystaline or powder. It comes as in both a
pentahydrate or anhydrous form.
Selenium and its compounds are very toxic. Chronic exposure is more
dangerous than acute exposure. The powder is easily airborne and is
dangerous to breathe.
In liquid form, as in a mixed toner, its a lot less dangerous.
Somewhere Mees mentions a couple of patents for Selenium toner with
ammonium thiosulfate in them. That sounds like the basis for KRST, which
contains Ammonium thiosulfate, sodium sulfite, and sodium selenite.
You can find MSDS for all this stuff on the SIRI web page at
http://hazard.com

----
Richard Knoppow
Los Angeles,Ca.
 

MartinP

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Kodak rapid Selenium Toner is still made so should be available one way or the other. Functionally, the Ilford selenium toner works very similarly and, by repute (as I haven't used them myself), the Adox and Moersch products are fine too. Other brands also exist.

Very often photographic chemicals cause lots of FUD (Fear, Uncertainty and Doubt) in the general public due to misinformation and ignorance. However in this case, don't make up selenium compounds outside of a chemistry lab with a perfectly working fume hood and lots of expertise. The metal gradually and insidiously destroys your nervous system. There was a printer in London who made amazingly toned prints with homemade selenium toners, but died from it very unpleasantly after some decades. (What was his name? His darkroom was in a cellar and he boiled up his toners in a saucepan, thirty years ago or more?)
 

MattKing

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TMZ

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Thanks for all the replies.

I'm in Australia, so sadly we have lost quite alot of Kodak products over the years. But that's fine, as, in terms of Selenium toner we have readily available the Adox and the Fotospeed.

While I am quite adept at mixing up formulae and have done so for quite a long time, I am not expert or game enough to do selenium from powder. So I don't want to actually mix it from scratch.

I was more interested in "augmenting" the Selenium Sulfide solution that I already have from this kit. So the selenium part of it is already in solution. I know that the Kodak (KRST) has ammonium thiosulfate in it for example. So perhaps with a bit of that and more Sodium Sulfite I can get it closer to the KRST.

My question(s) to the more "specialist" chemists and mixer-upperers out there is:

1. Is this possible? or is there a trick I'm missing?

2. What measures should I start with? say an extra 100g of the Sodium Sulfite and ?g of the Ammonium ThioSulfate?

I know it's a bit "round-the-houses", but I have 3 bottles of the other (2 bath) selenium and would be great to be able to use it as I like rather than leave it on the shelf.

While I'm not against the style of the 2 bath selenium toner, I prefer working with the single solution way, as I have developed a long term affinity with it.

And thanks again for all the replies!
 

Rudeofus

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Of course you can omit the first bath, which is a Ferricyanide bleach, and use the second bath as selenium toner, the Sulfide component won't do much to unbleached silver. You should be very careful with mixing other compounds into the second bath. The second bath most likely contains Sodium Sulfide, which releases a very toxic gas (Hydrogen Sulfide) whenever its pH goes too low, and mixing it with Rapid Fixer may do just that. If you mix it with Rapid Fixer and keep its pH high, it will release Ammonia, which is less toxic but still not good.

The best you can do is mix in 100-200 g/l Sodium Sulfite and make sure (e.g. with Sodium Hydroxide), that pH stays high. If the bath smells like rotten eggs, pH is too low. Be careful with that smell, above some concentration it paralyzes your sense of smell and you won't notice its dangerous presence! Make sure you have proper ventilation and experience before you do this. If you are unsure, make a tiny trial batch first and see whether it is safe (i.e. at least as odorless as the original bath) and effective (i.e. selenium tones small test clips).

Since there is no Sulfite in this soup, you won't be able to store this soup between sessions. Adding Sulfite won't help, because it will react with Sulfide to form more Thiosulfate, which is nice but won't protect the other Thiosulfate.
 
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TMZ

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Thank you very much Rudeofus,

that's a very knowledgeable and detailed response.

I see the problem now with the sulphide and my pH with the Thiosulfate. Rapid Fix is way too acidic.

Also the issue of the short life will be a real issue, as i use my darkroom professionally and the reuseable quality of the KRST and the long life definitely was a big plus. I think I'll give the Adox Selenium a trial for my new working toner, but will be fun to experiment with this.

I won't be able to get into the darkroom till tomorrow, as today is post on digital pics, but will try out some of the ideas you have suggested. I'll have my full chem protection on and do it outside, just in case! Thanks for the precautionary notes.
 

Rudeofus

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BTW I just noticed that there is a bad error in my previous posting: of course there is no need for Sodium Sulfite, you need Sodium Thiosulfate.
 
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