Liver of Sulphur

Mr Man · Oct 1, 2012

I would like to make some polysulfide toner but the main ingredient Liver of Sulphur appears to be imposable to obtain in solid form here in the UK now. Does anyone know where to get solid liver of sulphur in the UK or has anyone made polysulfide toners using the liver of sulphur gels that are available if so how much are you using. I know Photographers Formulary sell a polysulfide toner, and I will probably order some when I do my next bulk order to them, but shipping to the UK is expensive. I also know that Moersch sienna toner is a polysulfide toner but again it is very expensive. I also here that sodium polysulfide can be used in place of liver of sulphur, has any one tried this? And does it work.

BMbikerider · Oct 1, 2012

Have you tried a company called 'Speedybrews' based in Surrey (I think). It is a small independent company making all sorts of specialist developers both colour and B&W. Just Google the name.

Update

I have just done it for you. They do list some of the things they say can supply but they no longer supply chemicals direct to the public but give an E mail address where you can get them

sales@silverprint.co.uk

Good luck

bdial · Oct 1, 2012

On this side of the pond I bought some online from Dick Blick art supplies. It's also used for putting a patina on brass. If you have no joy with photochemistry suppliers, you may want to check an artist supply house.

kevs · Oct 1, 2012

'Liver of sulphur' = potassium sulphide. Try Rose Chemicals: http://www.rose-chemicals.co.uk

Cheers,
kevs

Mr Man · Oct 2, 2012

BMbikerider said:
Have you tried a company called 'Speedybrews'

I have looked at the Speedybrews site and have never seen Liver of Sulphur listed. Also as you point out they do not supply direct to the public. As for Silverprint I have never seen liver of sulphur, potassium polysulphide or potassium sulphide listed on their site. I have also asked in store for potassium sulphide before and been told they do not stock it.

kevs, thanks for your reply. I did not realize liver of sulphur was potassium sulphide I thought it was a more messy mixture of chemicals. I'm sure I have googled potassium sulphide before and not turned up anything useful anyway I googled again and turned up these two sites, as well as rose chemicals, http://www.thrivechem.com/01-kilogrammes-potassium-sulphide-poly-grg-15844-p.asp and http://www.suttontools.co.uk/consumables/chemicals/potassium-sulphide-100g.html. I will give thrivechem a try at £8.01 for 100g, enough for 13 liters, that will get me started.

DanielStone · Oct 2, 2012

you might want to try your local custom silversmith/jeweler. I use liver of sulphur on occasion when doing silverwork.

Dan

Robert Hall · Oct 2, 2012

Mine came in chunks that I had to break up with a hammer. For me, very hard to work with. It was almost impossible to break up.

kevs · Oct 2, 2012

Mr Man said:
<snip>

kevs, thanks for your reply. I did not realize liver of sulphur was potassium sulphide I thought it was a more messy mixture of chemicals. I'm sure I have googled potassium sulphide before and not turned up anything useful anyway I googled again and turned up these two sites, as well as rose chemicals, http://www.thrivechem.com/01-kilogrammes-potassium-sulphide-poly-grg-15844-p.asp and http://www.suttontools.co.uk/consumables/chemicals/potassium-sulphide-100g.html. I will give thrivechem a try at £8.01 for 100g, enough for 13 liters, that will get me started.

Hi Mr Man,

Just to clarify, my info came from a 1961 Dictionary of Photography (Iliffe Books, London; A.L.M. Sowerby, (ed.)); I just looked up 'Liver of Sulphur' - which says ' see Potassium Sulphide'. The entry says it's a substance of variable composition, but mainly potassium trisulphide, and potassium thiosulphate. Wikipedia says liver of sulphur is a variable mixture of "a poorly defined mixture of potassium sulfide, potassium polysulfide, potassium thiosulfate, and probably potassium bisulfide."

Anyway, I hope your toner goes well.

Cheers,
kevs

Gerald C Koch · Oct 2, 2012

Liver of sulfur is not a pure compound but is a mixture of potassium sulfide, potassium polysulfides, and potassium thiosulfate. It is flammable and there may be hazmat restrictions on its shipping. It is also unstable and spoils in about six months. Is the Moersch toner the only one available in the UK? There are toning formulas based on sodium polysulfide.

Mr Man · Oct 3, 2012

Gerald C Koch said:
Liver of sulfur is not a pure compound but is a mixture of potassium sulfide, potassium polysulfides, and potassium thiosulfate.

This is what I thought and the only place I can find that sells it is Photographers' Formulary however they will not ship it outside of the US. The Moersch toner is the only toner that I can be sure is a polysulfide toner. There are a couple of other toners available. Silverprint stock a Fomatoner Sepia which is described as a sulphide based toner however when you look at the safty data sheet on the website the active ingredient appears to be thiourea. Tetenal have a sulphide toner however I cannot find any further information on the Tetenal website and suspect that this is a sodium sulphide rather than polysulphide based toner.

Gerald C Koch said:
There are toning formulas based on sodium polysulfide.

Gerald do you have any of these formula? Or can I just substitute sodium polysulfide in the formula I already have? (Tim Rudman Master Photographer's Toning Book P40) Are the results the same? Although sodium polysulfide is as difficult to obtain as liver of sulfur I understand it is relatively easy to produce by dissolving sulfur in hot sodium hydroxide to produce a sodium polysulfide solution.

paul_c5x4 · Oct 3, 2012

Mr Man said:
Tetenal have a sulphide toner however I cannot find any further information on the Tetenal website and suspect that this is a sodium sulphide rather than polysulphide based toner.

Tetenal MSDS lists the main ingredient of the toner as disodium sulfide - I have some here, and it has the classic "rotten egg" smell...

Gerald C Koch · Oct 3, 2012

Thiourea easily decomposes to form sulfide ion and is therefore considered a sulfide toner. It has the advantage that it doesn't smell as bad.

Polysulfide Toner

This formula produces results similar to Kodak Brown Toner.

Distilled water 750 ml
Sodium polysulfide, 30% soln 25.0 ml
Sodium carbonate, monohydrate 2.4 g
Water to male 1.0 l

Use full strength and tone for 15 to 20 min at 20 C. After toning place the print in a 10% soln of sodium sulfite to stop toning and then wash to remove any yellow stain.

Some people claim that different formula sulfide toners produce slightly different brown colors. If a certain brown tone is critical then you might have to try several formulas.

There are also hypo-alum toners such as Ilford IT-2. They are easy to make and work better as they age. The toning is slow but can be hastened by heating the bath.

Olli J · Oct 3, 2012

I'm producing and selling polysulfide toner in small scale. It's made according to the IPI Silver Lock formula. You can contact me if you are interested.

Olli

jochen · Oct 8, 2012

Hello,
I don't know if this can help you: Here in Germany you can obtain "Schwefelleber" = liver of sulfur from a company named "Kremer Pigmente". They sell it for blackening of copper for artistic effects.

Mr Man · Oct 12, 2012

Thank you all for your replies.

Jochen: I looked up "Kremer Pigmente" they appear to have a very useful selection of chemicals. what they are selling as "Liver Of Sulfur" is listed as sodium polysulfide while this would be useful for Gerald's recipe it looks like it would be a pain to get it shipped as they ask for ID card details (thankfully we don't have ID cards in the UK) and won't provide an online quote for shipping to the UK. however I will keep them in my bookmarks for future reference.

Gerald: Thanks for the recipe. I am not a chemist, your recipe calls for 25ml of Sodium polysulfide, 30% soln. The instructions I have to make sodium polysulfide are:
Make a solution of 5 g of sodium hydroxide in 100 cm3 of water. Heat the sodium hydroxide solution until it is boiling. Add the 8 g of sulphur and a drop of washing up liquid to help the sulphur mix with the aqueous solution. Continue to boil the mixture and stir until the sulphur has dissolved to give a dark red-brown solution of sodium polysulphide. Decant the liquid off any small lumps of sulphur which remain undissolved.
Does this give me a 100% solution of sodium polysulfide? which I can then mix 7.5 ml sodium polysulfide solution to 17.5ml water to make 25ml of 30% solution.

I have ordered 100g of potassium sulphide from thrivechem as it is described as Potassium sulphide (poly) which Rose Chemicals describe as potassium polysulphide. It's all a bit confusing, I will let you all know what turns up an if it is of any use.

Gerald C Koch · Oct 12, 2012

Hard to say whether your recipe approaches a 30% solution since it does not produce only sodium sulfides but a mixture of sulfide, sulfite, and thiosulfate.

Sodium polysulfide is not a definite substance but rather a mixture of sulfides, Na2Sn where n = 1 to 5. It can be prepared by dissolving sulfur in a sodium sulfide solution. This must be done slowly and carefully since the reaction is exothermic.

Mr Man · Oct 12, 2012

Gerald C Koch said:
Sodium polysulfide is not a definite substance but rather a mixture of sulfides, Na2Sn where n = 1 to 5. It can be prepared by dissolving sulfur in a sodium sulfide solution. This must be done slowly and carefully since the reaction is exothermic.

Hi Gerald, thanks for that.
I thought sodium polysulfide was probably a bit of a messy concoction as is potasium polysulfide. I didn't know sodium polysulfide could be made by your method of dissolving sulfur in a sodium sulfide solution, which sounds less bother than the sodium hydroxide method, do you have any proportions or quantitys for that as I have some sodium sulfide and can easily get hold of some sulfur

Gerald C Koch · Oct 12, 2012

Sodium polysulfide is a mixture of sulfides. In the mixture the amount of each polysulfide decreases as n increases. I would make up a 30% solution of sodium sulfide and keep dissolving sulfur in it until no more will dissolve.

The structure consists of a chain of sulfur atoms with a sodium at each end. For Na2S4 this would be Na-S-S-S-S-Na. You can have a chain of perhaps a maximum of 6 sulfur atoms. The exact number varies depending on what text you read.

Mr Man · Oct 12, 2012

Gerald, thanks so much for the information you have provided.

Now I need to order some sulfur and experiment. The potassium sulphide (poly) order from thrivechem.com is not going well they sent me an e-mail at 16:55 today, three days after the order was placed, telling me I needed to fill out the attached form and supply a scan if a piece of ID to make a purchase. Not a problem but there was no form attached to the e-mail and now they are shut for the weekend, typical British service. I will post results at a later date.

Liver of Sulphur

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