Sciencemadness Discussion Board - Ammonium Sulfate to Ammonium Sulfide

Ammonium Sulfate to Ammonium Sulfide

tom haggen - 31-8-2004 at 20:32

Just wondering if there was a quick fix I could use to convert from ammonium sulfate to ammonium sulfide?
Thanks a million.

-Tom

Reverend Necroticus Rex - 1-9-2004 at 06:37

Why not just gas NH3 solution with H2S, that makes a fair amount of ammonium sulfide, nasty stuff though, toxic, and as I'm sure you know, smells bloody awful

chemoleo - 1-9-2004 at 06:54

I'd doubt very much there is a quick fix.
Only via some metathesis, or via H2S + NH3 as suggested.

tom haggen - 1-9-2004 at 08:23

Thanks guys

JohnWW - 1-9-2004 at 13:59

There is a thread on this going in the Roguescience forum presently. They say: pass a mixed stream of NH3 and H2S (caution - extremely poisonous) into a cooled vessel. (NH4)2S and NH4HS are formed.

John W.

BromicAcid - 1-9-2004 at 14:10

Couldn't a strong reducing agent in basic medium produce it? I've seen sulfate reduced to sulfide by some reducing agents, but they pass my mind right now. Don't see a reducing agent affecting ammonium cation either. Maybe basified hydrazine hydrate

The Ed - 1-9-2004 at 17:11

I can't really imagine any reducing agent being able to reduce sulfate all the way to sulfide. If anything it would probably just take the entire SO4 group and give off ammonia gas.

So yeah, just go with the NH3 H2S method. What's the best way to produce H2S anyway?

neutrino - 1-9-2004 at 17:41

H2S is ususally made in the lab by adding an acid to a sufide, usually iron sulfide (not pyrite).

Reverend Necroticus Rex - 1-9-2004 at 19:42

Another way, although not so good, is to heat candle wax with sulfur powder, this is messy and ill smelling at best, but it certainly does output a lot of H2S.

BromicAcid - 1-9-2004 at 19:48

Although ammonium salts and calcium salts are nowhere near similar enough to show a definitive trend in properties I recalled these two reactions:

3CaSO4 + 8Al -----> 4Al2O3 + 3CaS

CaSO4 + 4H2 ----> CaS + 4H2O

chemoleo - 2-9-2004 at 05:51

Isn't that the plaster of paris thermite (the first one)? wouldnt the CaS combust in air to give SO2 and CaO (at those high temps?)? At least, last time I tried it, the smell was very strong of SO2....

BromicAcid - 2-9-2004 at 15:00

It would, unless you protected it from atmospheric oxidation....

Theoretic - 13-9-2004 at 10:16

When you heat (NH4)2SO4, you get NH4HSO4. That could be reduced to NH4HS by C or, better, by H2 at a lower temperature with a catalyst - a Fe compound. When NH3 and NH4HS combine, you get (NH4)2S.

JohnWW - 13-9-2004 at 10:30

There are anaerobic sulfate-reducing bacteria, which obtain oxygen and energy by reducing sulfate to sulfide or elemental sulfur. Some sulfur deposits are due to them. They have been discovered living on deep-ocean hydrothermal vents.

John W.

Ammonium sulfide not obtained....

kazaa81 - 7-10-2004 at 12:47

Hallo to all,
I've tried to obtain ammonium sulfide by reacting acqueous 30% NH3 with H2S, which was pumped in the NH4OH solution.
Anyway, nothing has been precipitated or changed......why???

If anyone can explain the wrong things, I would appreciate very much.

Thanks for help!

BromicAcid - 7-10-2004 at 13:49

Ammonium sulfide and bisulfide, of which you have a mixture, is highly soluble in water, greater then 128.1 g / 100 ml at low temperatures. So there will be no precipitate.

Also, ammonium sulfide, bisulfide, hydrogen sulfide, and ammonium hydroxide are all clear in solution so there will be no visual indicator to the completion of the reaction.

Testing the pH to determine the reaction endpoint would be difficult considering all the species floating around affecting the pH.

(This method only really yields ammonium bisulfide, the true ammonium sulfide is only stable in the absence of moisture below 0C, however ammonium bisulfide is often referred to as just ammonium sulfide therefore there is no reason we can't do the same.)

Ammonium sulfide may well decompose as you try to evaporate the water, hence the procedure to react gaseous ammonia with gaseous hydrogen sulfide to yield the desired sulfide directly without the water.

quest - 11-11-2004 at 07:05

You guys said that Ammonium Sulfide is in the stink bombs we can buy, is it pure Ammonium Sulfide or in solution?
If I use NH4OH solution 24% and convert it into Ammonium Sulfide will it be stinky enogh to use as a stink bomb?

AngelEyes - 11-11-2004 at 07:34

I belive that the commercial stuff is a weak solution of <10 percent iirc.

I have a (dubious) preapration here, and it is presented as is. I do not claim to have tried it nor do I claim to fully understand the reaction that is supposed to be happening here.

To make some, you mix four ounces of sulfur with eight ounces of hydrated lime
in a stew pot (at least half-gallon capacity). A quart of water is added and
the mess is heated and stirred until the sulfur has completely blended. The
hydrated lime will sink to the bottom of the pan and yellow liquid is then
poured off into a bucket.

Take the bucket outside, if you have any sense, and add one pound of sulfate
of ammonia. Stir it a minute and hold your nose. Then cover the bucket with
plastic wrap and let it set for about a half hour. Then pour off the liquid
slowly through a cloth filter into a bottle. If you don't have an outside you
can use your bathroom. Just hope no one has to go for an hour or so. The
liquid is vile but it is not poison.

Sulfur may be obtained from rose dust (an insecticide) which is very high
grade and makes excellent gunpowder. Rose dust has 10% inert ingredients so
10% more should be added to any formula requiring sulfur. Rose dust and
sulfate of ammonia (a fertilizer) may be purchased in the garden department of
a home improvement/hardware store. 

I think it reacts the lime with sulpur and get Calcium Suphide which reacts with the Ammonium salt to give an insoluble ppt of CaSO4 and Ammonium Sulphide in solution...but am fully prepared to be corected on that.

Mr. Wizard - 11-11-2004 at 08:31

Try mixing calcium poly-sulfide, available at garden centers as a "dormant sulfur spray" with ammonium sulfate. Maybe it will precipitate calcium sulfate and leave a combination of ammonium sulfides. The calcium poly sulfide in the spray is a saturated solution and is a dark orange liquid, sometimes with crystals in the bottle, which turn yellow on dilution with water. It will form a sulfide layer on copper immediately so there is plenty of the sulfide ion in solution. BTW it also stinks to high heaven. This will save you the step of boiling sulfur with lime, but costs a little more. A word of warning: H2S is more poisonous than Hydrogen Cyanide and your nose will soon become numb to the smell. It may even be absorbed through the skin from solutions. It's not just a bad smell.

NH4HS synthesis from a site...

kazaa81 - 14-11-2004 at 10:15

Hallo to all,
I've finded a synthesis of NH4HS (ammonium hydrogensulfide) in a site.
I post it:
-
Making Ammonium Sulfide

WARNING: Among other hazards, this procedure involves generation of hydrogen sulfide-- a very poisonous gas. If you choose to attempt this or any of the experiments or procedures described on this site, you do so entirely at your own risk.

Ammonium sulfide is a very useful reagent in mineral analysis. It's easy to prepare in any modestly-equipped laboratory, though there's the hazard of hydrogen sulfide during its production. Once made, however, a bottle of the reagent will last quite a long time.

Supplies: ammonia solution (ammonium hydroxide); test tube; support stand and clamp; one-hole stopper; gas delivery tube; conical flask or reagent bottle; powdered sulfur; paraffin wax shavings; alcohol lamp or candle.

Procedure: Place an equal volume of paraffin shavings and sulfur powder into the test tube. Fit the test tube with a one-hole stopper through which a gas delivery tube has been pushed with thickly-gloved hands*. Hold this test tube / stopper / gas delivery tube assembly with a support stand and clamp.
Into the conical flask or reagent bottle, pour ammonia solution until the vessel is 1/2 to 2/3 full. Place the free end of the gas delivery tube into this solution.
The rest of the procedure must be done outside or in a fume hood! Hydrogen sulfide is poisonous and also tends to "saturate" the sense of smell; a lethal dose will smell no more unpleasant than a merely annoying concentration**.
Gently heat the test tube containing the paraffin and sulfur. These will melt and eventually turn brown; H2S gas will begin to bubble out of this mixture and into the ammonia solution at the other end. Keep bubbling the hydrogen sulfide gas through the ammonia solution for about 15 minutes. More time (that is, more H2S) is of course required to saturate a larger volume of ammonia solution. Do not heat the contents of the test tube too strongly, however. The molten paraffin-sulfur mixture could boil over, not to mention that it's flammable.
Withdraw the gas delivery tube from the ammonia solution before you stop heating the test tube. This will prevent liquid from drawing up into the hot test tube and shattering it.
When finished generating H2S, let everything cool and fill the remainder of the conical flask or reagent bottle with ammonia solution. Swirl gently. Stopper the container tightly and store in a cool, dark place. You should regard this reagent as a poison and treat it with appropriate caution. Do not get it on your skin; while it's often labeled "(NH4)2S", the reagent inevitably contains some NH4HS, which is actually more dangerous than hydrogen sulfide via skin absorption and can also be lethal (see Merck Index entry for "ammonium bisulfide"

. Wear vinyl or polyethylene gloves when handling ammonium sulfide reagent, and work in a well-ventilated area. Do not inhale the fumes- they are a mixture of hydrogen sulfide and ammonia.
The ammonium sulfide solution, prepared as outlined above, can be used to precipitate certain metal cations as sulfides (some, such as iron, precipitate as hydroxides if the pH is adjusted toward alkalinity). For detailed information on sulfide precipitations, see Orsino Smith's procedures P-8 and P-14 (1946). Smith's text also mentions several other uses for the ammonium sulfide reagent in spot tests and blowpipe analysis (1946).
-
I've finded this at www.crscientific.com/nh4sulfide.html

Thanks at all and have fun

quest - 3-12-2004 at 09:53

AngelEyes, after bubbling H2S inso NH3 solution and it didn't worked i tried your method.

I heated the sulfur and hydrated lime solution till the sulfur has completely blended, i filtered it and got some orange liquid.
mixed it with (NH4)2SO4 and in a close vessel.
after 35 minutes I filtered this again and got some orange liquid (again) and green solid (dunno what it is..)

the orange solution i got smell liek NH3+H2S
and not like ordinary stink bombs....

so i think i got the synthesis right and its just not the material used in comercial stink bombs

Reverend Necroticus Rex - 3-12-2004 at 19:37

I tried bubbling H2S into the standard ammonia water available in the UK (I can't recall the exact %)

I gassed it for a fair while, and an orangy-yellow liquid formed, I didn't try to seperate it out as crystals, but stored it in the form as is.

After a while something looking like sulfur seperated out as a spongy disk on the top of the solution in the bottle, it always does this.

I actually have used it as a stink bomb once, when I was a lot younger, shamefully enough, in a corner shop with owners that made rude comments to me one time.

I used a thin glass vial obtained from a mercury thermometer, it had a seperate actual thermometer inside a thin glass capsule, presumably to protect to some degree against Hg spills, salvaged the mercury, and filled the vial up about halfway with the ammonium sulfide solution and then carefully sealed with a blowtorch (creating a hefty stench in my lab at the time

)

I dropped this improvised stinkbomb in the shop, at the back, and paid for the goods I bought as an excuse, it was surprisingly effective actually, within about five seconds, I could smell it, and in ten, as I was leaving, the place absolutely stank

I don't mean to say it was clever, or a good thing to do, but I did it, and it worked, very effectively. I suppose I at least had a reason, as they had insulted me on the style of my clothing (gothic

)

So yes, it works as a stink bomb.

Quest, I am intrigued to what method you used to generate the H2S, I used the combination of heated sulfur powder/parrafin wax, and I imagine at least some SO2 was produced due to air present in the combustion chamber, perhaps the SO2 acted as a catalyst possibly.

quest - 4-12-2004 at 03:50

dont know what was wrong in my NH4OH + H2S method , but from what you wrote i think we got the same product - orange\yellow solution.

BTW, i left the solution in open vessel over night and whan i came back after 5 hours it was clear and had white solid in it (and didn't had the stench any more)

so i gess next time i will try to make it (maybe today) i will save it in close vessel

AngelEyes - 6-12-2004 at 04:25

A small point...but I never suggested bubbling ammonia through hydrogen sulphide - that was the good Reverend...

It should work though, probably just a crappy yield is all.

Reverend Necroticus Rex - 13-12-2004 at 05:41

Quest, you said whatever component of the yellow oil that causes that odious stench volatilised after some time, I would be intrigued as to the results that would be obtained by careful distillation of the oil, and condensing the distillate :cool:

I can't try it myself, as I have no lab access at the moment and quite possibly won't for some time

Rudical - 7-2-2005 at 21:52

Quote:

Originally posted by AngelEyes
I belive that the commercial stuff is a weak solution of <10 percent iirc.

I have a (dubious) preapration here, and it is presented as is. I do not claim to have tried it nor do I claim to fully understand the reaction that is supposed to be happening here.

To make some, you mix four ounces of sulfur with eight ounces of hydrated lime
in a stew pot (at least half-gallon capacity). A quart of water is added and
the mess is heated and stirred until the sulfur has completely blended. The
hydrated lime will sink to the bottom of the pan and yellow liquid is then
poured off into a bucket.

Take the bucket outside, if you have any sense, and add one pound of sulfate
of ammonia. Stir it a minute and hold your nose. Then cover the bucket with
plastic wrap and let it set for about a half hour. Then pour off the liquid
slowly through a cloth filter into a bottle. If you don't have an outside you
can use your bathroom. Just hope no one has to go for an hour or so. The
liquid is vile but it is not poison.

Sulfur may be obtained from rose dust (an insecticide) which is very high
grade and makes excellent gunpowder. Rose dust has 10% inert ingredients so
10% more should be added to any formula requiring sulfur. Rose dust and
sulfate of ammonia (a fertilizer) may be purchased in the garden department of
a home improvement/hardware store. 

I think it reacts the lime with sulpur and get Calcium Suphide which reacts with the Ammonium salt to give an insoluble ppt of CaSO4 and Ammonium Sulphide in solution...but am fully prepared to be corected on that.

Hi there. I don't know much about chemistry at all so excuse my lack of knowledge. I really love stink bombs and have been buying a lot lately (pulling gags on my friends and stuff). I recently came accross a a site that told me how to make my own. It told me to basically put match heads in a jar, fill it with ammonia and let it sit for a week with the cap on. I have a huge jar of sulfur precipitate. If I mix that and ammonia together, would it work? Would I still have to wait a week? If I wanted to use the instructions above, could I use the sulfur precipitate and hydrated lime? Thnaks guys.

Mumbles - 8-2-2005 at 14:37

I don't think that wout work. With the hydrated lime it definatly wouldn't work. Calcium Sulfide doesn't decompose like ammonium sulfide so you wouldn't get the lovely H2S, at least without being able to mix it with an acid on breakage.

I don't believe that match heads contain elemental sulfur so I don't think the other method you described would work. I think they have antimony sesquisulfide.

Ammonium sulfide

TetraOzone - 17-5-2005 at 20:09

Quote:

Originally posted by Reverend Necroticus Rex
I tried bubbling H2S into the standard ammonia water available in the UK (I can't recall the exact %)

I gassed it for a fair while, and an orangy-yellow liquid formed, I didn't try to seperate it out as crystals, but stored it in the form as is.

After a while something looking like sulfur seperated out as a spongy disk on the top of the solution in the bottle, it always does this.

Sounds like you guys are getting some formation of ammonium polysulfide, which has a non-stoichiometric composition that can be... a messy, yellow-orange mass, containing even some free sulfur.

I'm also wondering if prolonged bubbling of the H2S will in itself produce the polysulfide. It is quite possible-- I have to try it until I get the same result.

Is any of the molten wax-sulfur mixture boiling over into your receiving tube?