hankdavis
Harmless
Posts: 12
Registered: 28-6-2008
Member Is Offline
Mood: No Mood
|
|
Hydrogen Sulfide: Generation and Storage
I've used H2S in a handful of reactions (namely a mischievous one with household ammonia) and anyone who has used it know generating it often involves
collecting the gas from a strong acid attacking another sulfide such as FeS. The only problem with this method is that the evolving gas carries acid
droplets/vapor with it, requiring a further purification step. I thought I'd share a fairly simple process that gives only H2S gas and water vapor and
is easy to have on hand. This is far from complicated, but I'm covering every detail because H2S is still a poison.
Al2S3 Production
You'll need:
Powdered sulfur
Powdered aluminum
High temp ignition source (magnesium, flash powder etc)
Wooden reaction vessel (a crucible is fine, but not preferable)
Mix 1.18 grams of sulfur for every gram of aluminum you use. This mixture is perfectly stable, I usually whip up an excess for later use. I usually
use a 2x4 with a dip cut out of it to hold the powder, or a better reaction vessel can be built by drilling out a section of 2x4 with a door drill bit
and closing off the bottom with another piece of wood. This is because Al2S3 has a tendency to adhere to ceramic and glass, and the only way to
completley remove the Al2S3 is to quench it with water (dangerous + terrible smelling).
2Al + 3S >> Al2S3 + lots of heat
Once you have a pile of powder in your container of choice, get the reaction started with a fairly high temp in the same way you'd get thermite
started. A easy way to do this is by cutting a firecracker in half and leaving the flashpowder end of the fuse in the mixture. Aluminum and sulfur
reacts fairly violently so stand back, and mind the SO2 fumes from the excess sulfur burning off. Once the red hot Al2S3 goo has cooled, you should
have a gray "rock" of your product plus flaming wood. DO NOT put this fire out with water, again with the terrible smell. After the fire goes out the
burned wood should allow you to simply peel off the sulfide and break it up into pebble sized chunks (powdering not recommended).
Storage
There are a few things to be weary of when storing your sulfide. Al2S3 is extremely moisture sensitive and must be stored in an airtight container
that is acid-proof. Also, it is a good idea to keep it with a drying agent. It is stable when dry and I've been able to keep it indoors without risk
of poisoning. Also, H2S molecules are relatively small, somewhat larger than water, so a stoppered bottle will leak small amounts of gas over time.
From here, generating H2S gas simply involves reacting your pebbles with water to give a fairly slow evolution of H2S to be bubbled through your
solution of choice. Acid speeds this reaction up.
Al2S3 + 6H20 >> 2Al(OH)3 + 6H2S + some heat
Spent aluminum hydroxide can be reacted with HCl to give a much less violent synthesis of AlCl3, a bonus reagent!
I'm currently working on an all-in-one vessel made from pvc parts and silicone. Al2S3 goes in a large valve at the top, and when H2S is needed, one
simply uses a syringe to inject water into a second valve and the gas is collected from the first. With the valves closed, the vessel doubles as
storage. However, I don't yet know if H2S attacks silicone, so use caution.
I've been scolded on boards about this reagent. So I'm finishing up with handling procedure...
SAFETY
First off, H2S is very poisonous at concentrations as low as 150 ppm in the air. It will deaden your sense of smell at these levels,
so don't toy around it. Luckily, H2S is detectable at a thousandth of these levels, tends to sink to the ground, and will cause intense nausea before
harm truly sets in.
From my experience, using H2S on the small scale is mostly harmless, especially with an Al2S3/water generator because H2S is produced more
slowly. Always use ventilation during these reactions and preferably outdoors on a dry day. If you absolutely need to use H2S indoors, bubble
your excess gas through an diffuser and a scrubbing solution that traps the sulfide ion. Sodium salts are undesirable as the sulfide will slowly
decompose back into H2S. Personally, I dissolve KMnO4 into dilute HCl and H2O2 until MnO2 forms. The manganese ion will trap the sulfide and the MnO2
catalyzes the formation of the less toxic sulfate ion. Finally, H2S will readily form lingering smelly sulfides on surfaces indoors such as wallpaper
so indoor use can be destructive to your property.
Again, sorry for the wordiness, but I felt it necessary. Good luck!
\"When you use a quote, put a famous name on the end, that\'s where all the jazz is!\" -- Jesus
|
|
|
NeutralIon
Harmless
Posts: 28
Registered: 19-6-2005
Member Is Offline
Mood: No Mood
|
|
Another option: According to Merck thioacetamide, C2H5NS, can be made by heating Al2S3 with ammonium acetate, i.e.:
3[C2H7NO2] + Al2S3 --> 3[C2H5NS] + 2Al(OH)3
Again, from Merck, thioacetamide is a "Pleasant substitute for H2S in the lab."
Knowledge is Good
|
|
|
UnintentionalChaos
International Hazard
Posts: 1454
Registered: 9-12-2006
Location: Mars
Member Is Offline
Mood: Nucleophilic
|
|
I've made tiny quantities of aluminum sulfide and it really does reek even just as the reaction stops. The small samples were prepared by ignition
with magnesium filings and proceeded quite energetically. The sulfur melted together with dark aluminum powder with no obvious reaction..like the
original post mentions, it needs to be lit like a thermite. I did not have an immediate use for it, so I quenched it with 6% H2O2 to destroy it which
initially released a small amount of H2S (quick escape of bubbles from the surface of the samples perhaps) but it quickly stopped smelling altogether
(and I'm sure it was not from deadening of my sense of smell...the sample was extremely small.....maybe a single gram)
[Edited on 6-29-08 by UnintentionalChaos]
Department of Redundancy Department - Now with paperwork!
'In organic synthesis, we call decomposition products "crap", however this is not a IUPAC approved nomenclature.' -Nicodem
|
|
|
dann2
International Hazard
Posts: 1523
Registered: 31-1-2007
Member Is Offline
Mood: No Mood
|
|
Have a read at this (very scary) story in relation to using the stuff.
http://www.sciencemadness.org/talk/viewthread.php?tid=10491&...
Dann2
|
|
|
garage chemist
chemical wizard
Posts: 1803
Registered: 16-8-2004
Location: Germany
Member Is Offline
Mood: No Mood
|
|
I want to add that the Al/S reaction should be protected from atmospheric oxygen if possible, since such sulfides are very easily oxidised to sulfates
otherwise, losing yield.
Very good synthesis though. Much better than the sulfidogen method (heating paraffin with sulfur, giving H2S and carbon) which renders the test tube
it is done in useless since the coke deposit cannot be removed.
|
|
|
hankdavis
Harmless
Posts: 12
Registered: 28-6-2008
Member Is Offline
Mood: No Mood
|
|
Hah sorry guys.. seeing as how I decided to write this post after a weekend bender at 4 am, disregard what I said about the "scrubber". First off, I
was referring to a failed H2S removal that I ended up trashing. Secondly, contrary to my drunken ramblings, the filtration had nothing at all to do
with the Mn+2 ion. What I did at the time was tried to make a thick suspension of MnO2 by adding permanganate to slightly acidic peroxide until the
reaction ate all the acid and turned to a brown jelly. Running waste H2S through a column of this made the setup look AND smell like real live
feces!--so I scrapped the venture entirely. I figure that unless you're a factory, it's much easier and economic to just vent the stuff as far the
hell away as possible.
Garage chemist has a point, fluffier mixes give the worst yields and kick Al2S3 dust everywhere, so always tamp it down like a thermite. As far as the
surrounding atmosphere goes though, try adding a dash of excess sulfur to the mix (1.25 instead of 1.18). It will burn along the surface as the
aluminum sulfide cools for a minute or so, shielding it from O2 while its most vulnerable.
\"When you use a quote, put a famous name on the end, that\'s where all the jazz is!\" -- Jesus
|
|
|
Klute
International Hazard
Posts: 1378
Registered: 18-10-2006
Location: France
Member Is Offline
Mood: No Mood
|
|
Hydroxide and hypochlorites are very effective at removing H2S in scrubbers, i would rather stick to them that MnO2, the way you describ it  .
With hydroxides you end up with a sodium (poly)sulfide solution which cna be usefull (although bad smelling). Be carefull not too use a too conc.
solution or over-run it, as the sulfides will start precipitating and can clog the wash bottle's tube (happened to me); on the other hand,
hypochlorite leaves a fine sulfur deposit, but fine enough to to pose a clogging hazard. Both type of scrubbers can heat up significantly if large
amounts of gas are to be neutralized.
\"You can battle with a demon, you can embrace a demon; what the hell can you do with a fucking spiritual computer?\"
-Alice Parr
|
|
|
hankdavis
Harmless
Posts: 12
Registered: 28-6-2008
Member Is Offline
Mood: No Mood
|
|
Yeah no joke, all it took was a humid, still day and I was trying to quench the stuff the yard. All the sudden the smell disappeared and I got a
sensation in my lungs along the lines of, "Hm, this isn't air--" I got the hell out of the area and promptly puked.
Back in the day I got so much flame on the boards for even thinking about H2S you'd think it was a PhIKAL reagent, but absolutely no help
with using/making it. This is actually the reason I took the time to refine the Al2S3 method and post it. Nothing against Dann2 at all, just other
people who think ignorance is a safety measure.
On a lighter note, will the hypochlorite solutions still form polysulfides? The biggest pain using this reagent even during ion analysis is warning
the neighbors about the smell.
\"When you use a quote, put a famous name on the end, that\'s where all the jazz is!\" -- Jesus
|
|
|
Klute
International Hazard
Posts: 1378
Registered: 18-10-2006
Location: France
Member Is Offline
Mood: No Mood
|
|
No, hypochlorite will oxidize the sulfides. INto what i am not sure, surely various oxygenated sulfur compounds (sulfites,s ulfates, etc). There was a
insoluble yellow solid forming, not sure what I could have been..
\"You can battle with a demon, you can embrace a demon; what the hell can you do with a fucking spiritual computer?\"
-Alice Parr
|
|
|
ScienceSquirrel
International Hazard
Posts: 1863
Registered: 18-6-2008
Location: Brittany
Member Is Offline
Mood: Dogs are pets but cats are little furry humans with four feet and self determination! 
|
|
The initial product from the reaction of hydrogen sulphide with most oxidising agents ( hypochlorite, hydrogen peroxide, sodium bisulphite, etc) is
colloidal sulphur.
The sulphur may then react further eg to form thiosulphite in basic sodium sulphite solutions.
|
|
|
Klute
International Hazard
Posts: 1378
Registered: 18-10-2006
Location: France
Member Is Offline
Mood: No Mood
|
|
Ok, so it was sulfur then. Thanks for poiting that out.
\"You can battle with a demon, you can embrace a demon; what the hell can you do with a fucking spiritual computer?\"
-Alice Parr
|
|
|
Ritter
Hazard to Others
Posts: 370
Registered: 20-6-2008
Location: Earth
Member Is Offline
Mood: Curious
|
|
| Quote: | | H2S is still a poison |
Yes it is. And I believe it is more toxic than HCN. I think the mode of toxicity is binding to the heme iron in red blood cells.
One of the bad things about working in sulfur chemistry is that most of these materials smell similar to the gas odorants added to natural gas, etc.
Their potency & that fact could bring the FD & police to your door very quickly.
Ritter
=============================
\"The production of too many useful things results in too many useless people.\"
Karl Marx
|
|
|
ThScience
Harmless
Posts: 1
Registered: 30-6-2008
Location: Norway
Member Is Offline
Mood: No Mood
|
|
Wikipedia has a list for the toxicity of H2S:
| Quote: | http://en.wikipedia.org/wiki/Hydrogen_sulfide
• 0.0047 ppm is the recognition threshold, the concentration at which 50% of humans can detect the characteristic odor of hydrogen sulfide [1],
normally described as resembling "a rotten egg".
• 10-20 ppm is the borderline concentration for eye irritation.
• 50-100 ppm leads to eye damage.
• At 150-250 ppm the olfactory nerve is paralyzed after a few inhalations, and the sense of smell disappears, often together with awareness of
danger,
• 320-530 ppm leads to pulmonary edema with the possibility of death.
• 530-1000 ppm causes strong stimulation of the central nervous system and rapid breathing, leading to loss of breathing;
o 800 ppm is the lethal concentration for 50% of humans for 5 minutes exposure(LC50).
• Concentrations over 1000 ppm cause immediate collapse with loss of breathing, even after inhalation of a single breath.
|
Another way to make hydrogen sulfide is to melt iron (Fe) powder and sulphur (S) in a test tube and get FeS.
And so mix the FeS whit HCl, = H2S + FeCl
It stinks very badly 
Yeah, I know my English suck, but give me a chance  |
|
|
dann2
International Hazard
Posts: 1523
Registered: 31-1-2007
Member Is Offline
Mood: No Mood
|
|
H2S from Vaseline and S.
Taken from another thread here:
http://www.sciencemadness.org/talk/viewthread.php?tid=19639
Attachment: chemicals_sulfide_hydrogen_preparation_from_sulfur_prothiere1902_french.zip (608kB)
This file has been downloaded 578 times
|
|
|
Paddywhacker
Hazard to Others
Posts: 478
Registered: 28-2-2009
Member Is Offline
Mood: No Mood
|
|
Cooking oil works too, and the left over red oil is a wondrously stinkey commodity.
|
|
|
Paddywhacker
Hazard to Others
Posts: 478
Registered: 28-2-2009
Member Is Offline
Mood: No Mood
|
|
Does anyone have any elemental selenium or tellurium to test whether this process, heating with paraffin wax, will produce H2Se or H2Te?
Please don't try this inside at home, school or work, but I'd like to know if it works. A facile source of these hydrides would be useful.
|
|
|
dann2
International Hazard
Posts: 1523
Registered: 31-1-2007
Member Is Offline
Mood: No Mood
|
|
Hello,
Scan below taken from another thread (Making Carbon Disulphide).
Also onyone messing with H2S should read this:
http://www.sciencemadness.org/talk/viewthread.php?tid=10491
|
|
|
Paddywhacker
Hazard to Others
Posts: 478
Registered: 28-2-2009
Member Is Offline
Mood: No Mood
|
|
Quote: Originally posted by Paddywhacker  | Does anyone have any elemental selenium or tellurium to test whether this process, heating with paraffin wax, will produce H2Se or H2Te?
... |
At long last I can report that heating olive oil with either selenium or with tellurium produces no noticeable smell. Fusing selenium or tellurium
with sulphur and then heating the product with oil produces only the smell of hydrogen sulphide. My new career as a phantom stinkbomber has died at
birth.
|
|
|
HammerOfLight
Harmless
Posts: 18
Registered: 9-8-2007
Location: Clear Lake City, TX
Member Is Offline
Mood: ZeN
|
|
I once used aluminum sulfate (garden center) and Calcium, lime, rust generic toilet bowl cleaner to make H2S. We had a badger get into mom's garage
and had decided to hold up in a cabinet under the workbench, using some make shift body armor and a military gas mask with SWISS NATO filters I went
in with a bucket of the aluminum sulfate and poured in a 50/50 mix of toilet bowl cleaner and water. then exited the garage and locked the door, we
opened the windows in the house, and then left the house. 4 hours later we came back, I used the garage door opener to open the garage door, and vent
the place. we spotted the dead badger near the gargage door after it opened, along with a few mice we didn't know about.
-Bad people are punished by societies law, good people are punished by Murphy\'s law.
|
|
|
AndersHoveland
Hazard to Other Members, due to repeated speculation and posting of untested highly dangerous procedures!
Posts: 1986
Registered: 2-3-2011
Member Is Offline
Mood: No Mood
|
|
If sulfur is boiled with aqueous alkaline solution, polysulfides and thiosulfate form. Reaction of acid with polysulfides liberates H2S and sulfur,
but the acid also reacts with the thiosulfate to release SO2 (and more sulfur). H2S and SO2 immediately react with eachother, so I do not understand
how any H2S can be released, but apparently this reaction does release poisonous H2S...
Perhaps the thiosulfate react at a different rate than the polysulfides with acid? I would think it would be best to find a way to separate the two,
if possible, before adding the acid.
|
|
|
chloric1
International Hazard
Posts: 1146
Registered: 8-10-2003
Location: GroupVII of the periodic table
Member Is Offline
Mood: Stoichiometrically Balanced
|
|
| Quote: Originally posted by HammerOfLight | | I once used aluminum sulfate (garden center) and Calcium, lime, rust generic toilet bowl cleaner to make H2S. We had a badger get into mom's garage
and had decided to hold up in a cabinet under the workbench, using some make shift body armor and a military gas mask with SWISS NATO filters I went
in with a bucket of the aluminum sulfate and poured in a 50/50 mix of toilet bowl cleaner and water. then exited the garage and locked the door, we
opened the windows in the house, and then left the house. 4 hours later we came back, I used the garage door opener to open the garage door, and vent
the place. we spotted the dead badger near the gargage door after it opened, along with a few mice we didn't know about. |
Got a good chuckle at your DIY fumigation endeavors. But I wanted to mention that hydrogen sulfide is not only deadly poison ☠️ but reasonably
corrosive as well. Hope no serious damage was done to anything in the garage.
Fellow molecular manipulator
|
|
|
![[*]](images/xpblue/default_icon.gif){kind=icon}
