Sciencemadness Discussion Board - Antimony Sulfide

Antimony Sulfide

otonel - 24-1-2011 at 14:54

I can make antimony sulfide from sulfur and antimony casting pieces by melting together?
I don`t find on the internet how to make that chemicals and i need to use in priming mixture

Xenoid - 24-1-2011 at 17:21

The "black" form of Sb2S3 can be produced by heating antimony and sulphur together.
The "orange" form can be produced by bubbling H2S through an acidified solution of antimony trichloride;

2SbCl3 + 3H2S --> Sb2S3 + 6HCl

The orange form converts to the black form on heating.

otonel - 13-2-2011 at 04:34

My try to make Sb2S3 by adding S to melting Sb is failed,the result was a black mixture from grey Sb and black residue of melting sulfur
Best result i have with tin sulfate making with melting process
About the method to produced by bubbling H2S is not easy for me

not_important - 13-2-2011 at 11:18

Add a hot solution of sodium thiosulfate -photographer's hypo -to a hot solution of SbCl3 containing enough HCl to avoid hydrolysis. Do so with good ventilation, as H2S is formed. A dark precipitate of Sb<sub>2</sub>S<sub>3</sub> will be formed; doing the reaction at temperatures below 40to 50 C gives the red form of the sulfide, while adding too much thiosulfate dissolves some of the sulfide being formed.

Lion850 - 19-11-2020 at 22:20

I had a go at making antimony sulphide more or less based on patent Patent CN102259912B

https://patents.google.com/patent/CN102259912B/en

although I must stress 'loosely' as I did not have all the exact compounds specified.

- 5.1g Sb2O3 and 18g concentrated HCl placed in a beaker, stirred and heated (patent called for Sb2O5 but I did not have any).
- Once hot (not boiling) the oxide dissolved reasonably fast, into a clear solution.
- Add 3g tartaric acid and stir till dissolved.
- Let solution cool to below 50 and then add equal volume of water. At this point the solution became cloudy, with a white ppt. I dont think this was supposed to happen, I probably added too much water or the temperature should have been lower before adding the water?
- Filter the solution, obtaining a clear filtrate and a little bit of white remainder.
- Dissolve 7g Na2S in 30ml water (patent calls for ammonium sulphide but I did not have).
- Drip the Na2S solution into the SbCl3 solution with fast stirring.
- An orange suspension quickly formed. Initially there was no H2S smell, but when about 75% of the Na2S solution was added it suddenly started to make bubbles of H2S as more was added. I assumed this was the point where all the SbCl3 was displaced and the Na2S was started to react with the excess acid, so stopped adding Na2S.
- Transfer to large beaker and add 400ml water, stir, let settle, decant, add water, stir, settle, decant.
- Transfer remainder to vacuum filter and wash again in funnel.
- In solution the volume of the remainder looked huge, not so much once filtered and recovered to a crucible.

- Dry the product on a steam bath until the weight was stable. Pulverize in a mortar.
- 3.6g of soft orange-brown powder recovered. This is a yield of roughly 50% based on the initial amount of Sb2O3.

Cleaning: This stuff is fine and sticks to everything. Best way I found was to wash with water, then clean with paper towel, then rinse with concentrated HCl. And get a whiff of H2S a few times as the acid reacts with the antimony sulphide.

It is mentioned online that a golden color is also achievable. I think this reaction will yield many different color shades depending on ratios, temperatures, starting materials, stirring rates etc.

woelen - 20-11-2020 at 00:28

I actually think that you have a nice result. Yield probably could be a little better, but your product looks nice. I myself made Sb2S3 many times, but never took the effort to isolate it and dry it. I also purchased Sb2S3, but that is the crystalline black material. The black material is much less reactive than the orange material, that's why I made the orange compound several times as a basis for other experiments. The black crystalline solid appears to be only marginally interesting. It seems to have applications in pyrotechnics, but I don't do that and then not much remains to be done with the black material.

I do not understand why the patent calls for Sb2O5. Isn't that a mistake? Sb2O5 is oxidizing and if you dissolve that in acid, you get antimony(V) in solution, which will oxidize sulfide to free sulfur. Your product then will be strongly contaminated with sulfur. So, you did the right thing to start with Sb2O3. Btw., I have some Sb2O5, and this stuff is MUCH more inert than Sb2O3. Dissolving even a tiny bit of this compound in conc. HCl takes ages, even when boiling and fuming you workspace with HCl.

Lion850 - 20-11-2020 at 01:16

Woelen thanks for your comments. The patent also says the product is antimony pentasulphide (Sb2S5) which may be why they are starting with the pentaoxide?

What is the purpose of adding tartaric acid, is that to keep the pH low and prevent hydrolysis of the SbCl3?

woelen - 20-11-2020 at 02:02

The patent still looks strange to me. Whether Sb2S5 is a real compound or a very intimate mix of Sb2S3 and S seems to be still a subject of debate. Sb2S5 is orange, just like Sb2S3. I actually do have some orange Sb2S5, just as a lab curiousity, and I keep it around as a display sample.

Tartrate ion forms a very specific complex ion with antimony. Sb(3+) entities are coordinated to tartrate ions in this complex, with the H-atoms stripped off from the hydroxyl groups. This complex increases the solubility of antimony in water and makes hydrolysis less of a problem. The potassium salt of this complex is available commercially. It is a very strong emetic and still is used for this purpose in some cases.

Look at this beautiful official IUPAC name for this commercially available salt:

dipotassium 3,6,10,13-tetraoxo-2,7,9,14,15,16,17,18-octaoxa-1,8-distibapentacyclo[10.2.1.1¹,⁴.1⁵,⁸.1⁸,¹¹]octadecane-1,8-diuide

A little more info can be found here: https://en.wikipedia.org/wiki/Antimony_potassium_tartrate

joseph6355 - 28-5-2022 at 09:55

Any recommendations for synthesizing Antimony Sulfide from elementar Antimony?
I'm thinking of welding steel bar stock in a cube shape, filling it with Sulfur and Antimony and heating it to 750°C-ish. Regarding this method, I've got two questions:
1. Antimony Sulfide reacts with oxidizers under heat. Wouldn't such mixture rupture the container when it reacted upon heating?
2. If so -- and to prevent that -- I could top up the containing with an additional excess of Sulfur and compress it prior to welding in order to leave little to no air inside. But upon heating wouldn't the mixture expand or something and cause the same problem?

Last thing I want is to breathe in a toxic cloud of Antimony. I'm too young to have cancer

.

[Edited on 28/5/22 by joseph6355]

unionised - 29-5-2022 at 02:45

I'm fairly sure that Sb2S3 will react with steel.

joseph6355 - 1-6-2022 at 16:27

Quote: Originally posted by unionised

I'm fairly sure that Sb2S3 will react with steel.

How could one make Sb2S3 from Sb and Sulfur then? It has to be heated inside of something that can withstand those temperatures, right?

clearly_not_atara - 1-6-2022 at 16:56

Sulfur reacts at high temperatures with every metal except gold. So you would need something that forms a passivating layer, because inertness to sulfur ain't happening. You also need a flow process, because sulfur at 750 C has a vapor pressure of dozens of atmospheres. Oh, and the reaction is reversible, so you'll want finely divided antimony. Oh, and be sure to contain the exhaust with good cooling, because sulfur's autoignition temperature is just 260 C. I think you could use alumina ceramic components with gold "solder".

This sounds very hard. Are you sure you wouldn't rather react the antimony with chlorine and use the easy method? I honestly cannot think of a single reaction conventionally performed using sulfur gas.

SplendidAcylation - 2-6-2022 at 03:07

Quote: Originally posted by clearly_not_atara

I honestly cannot think of a single reaction conventionally performed using sulfur gas.

There's always the old preparation of carbon disulfide!

P.S. where did you get your time machine?

ManyInterests - 26-3-2023 at 20:18

I decided to bump this thread up because I am going to try to go for an antimony trisulfide synthesis. I do need some assistance in getting the chemical formulas for making it by reacting potassium antimony tartrate and ammonium thiocyanate. I started another thread that has more details. If you can provide assistance I would be very grateful.

https://www.sciencemadness.org/whisper/viewthread.php?tid=15...

teodor - 27-3-2023 at 12:43

Quote: Originally posted by ManyInterests

for making it by reacting potassium antimony tartrate and ammonium thiocyanate

I think this is rather exotic way. Could you post the reaction equations here?

ManyInterests - 27-3-2023 at 14:10

Quote: Originally posted by teodor

Quote: Originally posted by ManyInterests

for making it by reacting potassium antimony tartrate and ammonium thiocyanate

I think this is rather exotic way. Could you post the reaction equations here?

That's actually what I am looking for. I assume you haven't looked at the thread I made in another subforum, so I will quote my post here:

Quote:

I've been meaning to make priming mixtures for firearm primers for a while, and I think the time has come that I start to make some basic reagents for the tasks.

I know that antimony trisulfide is an essential fuel in making priming mixtures and I looked at various ways that it can be made. PoorMansChemist has several videos on how he made some, and I would like some documentation if possible on its synthesis. Here is the video in question:

https://youtu.be/wE_ebGPvyYE

So in the 2nd half of the video after he tries the first method (union of the elements) he boils potassium antimony tartrate and ammonium thiocyanate together until it forms antimony trisulfide which is then filtered away. It seems simple enough, but PMC doesn't say how much ammonium thiocyanate he used (other than a comment that he had to add an additional 15-20 grams of sodium thiocyanate to the mixture). He does have another video where he bubbles hydrogen sulfide into an antimony chloride solution, but I am not interested in doing that method currently.

I've tried to search for documentation on how he made that, but it was to no avail. I also looked on this forum but found little about it, so I am making this thread. In my typical autistic manner, I will list my questions in list form.

1: Does anyone have any documentation on their production in a home lab?

2: Any idea on the proportions needed for the reaction to occur correctly? I am referring directly to the video that PMC made. I actually asked him directly on discord, but he isn't replying.

3: In terms of dangerous gasses produced. What kind of gasses would be released? I have a good gasmask that is rated for hydrogen cyanide if needed, but it is good to know what I would be dealing with (I will be reacting it on my balcony and watching through a glass window).

4: The leftover liquid after filteration. Any idea on what it might be and how to safely dispose of it? PMC just recommended putting it an old plastic bottle and throwing it in the trash. I would rather be a bit more responsible than that.

5: In terms of the antimony trisulfide itself. Is it hygroscopic? What are the appropriate measures for safely storing it for later use? Can I simply put it a plastic tupperware after it dries? Can it explode? I am thinking not as it is not explosive antimony, but any concern of friction or impact that I need to worry about?

Thanks for all the help

The video I have linked is for PoorMan'sChemist who does the antimony trisulfide synthesis via the union of the elements (which he also includes ammonium thiocyanate in for some reason. Which I haven't seen mentioned anywhere else) and reacting ammonium thiocyanate with potassium antimony tartrate in water and boiling it down to (near) dryness.

He also has another video of him making it via bubbling hydrogen sulfide into a solution of potassium antimony tartrate. This method is something I might be interested in doing in the future, but for now I want to use my thiocyanate in something.

The problem is he doesn't even have the proportions of the reagents used nor does he write the chemical formula. I would like that so I can copy-paste it into a stoichiometry calculator and find the correct ratios that I need of all reagents involved.

[Edited on 27-3-2023 by ManyInterests]

teodor - 27-3-2023 at 14:41

I didn't see the video. But anyway, you said he didn't explain the reaction with thiocyanate.
SCN- ion could deliver S- anion only when it is split, and the rest is CN- which is quite toxic, so you should know what are you doing (and why).
Also, in that part of the world where I live thiocyanate salts are expensive. If you have no advantage to use it (over just sulfide salt) I see no benefits.
I've made Sb2S3 once from Sb2O3 which I bought in a pottery shop and I believe it is the most cheap source of Sb.
I've described the process here: http://www.sciencemadness.org/talk/viewthread.php?tid=153785

If you can get Sb2S3 (according to your sources) from the mixture which contains K+ and NH4+ ions probably there is no point to use H2S, you can use sulfide salts instead.

There is known method of getting Sb2S3 by reacting Sb containing salts with (sodium) thiosulfate. But it could be some other byproducts as well depending on the reaction conditions. If you have no sulfides probably you can experiment a bit with this path.