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Upsilon
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I believe I have a reaction! To prevent decomposition of the oxalic acid, I created a stable temperature environment. I dissolved about 32g of
potassium hydroxide in 30 mL of water to create a solution that boils at ~120C. I then added 0.5g of sulfur and 1.97g of oxalic acid dihydrate to a
test tube and mixed thoroughly. The test tube is then submerged into the potassium hydroxide solution, which is carefully monitored for temperature so
that it does not boil (it wouldn't matter if it did, I just don't want to be splashing it everywhere).
With this setup I have successfully melted the mixture, and I am observing bubbling. It could possibly be water vapor, but I highly doubt it. It has
been bubbling for a decent amount of time now; I would think all water would have been driven off by now. To be sure, I will let it run to completion;
theoretically nothing should be left after all is done according to the equation:
H2C2O4 + S -> H2S + 2CO2
AJKOER2, looks interesting. I'll look more into it once I have finished my experiment.
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Metacelsus
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To be more sure, you could also try passing the gas through a copper sulfate solution, and watch for a CuS precipitate.
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blogfast25
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Quote: Originally posted by Upsilon  |
With this setup I have successfully melted the mixture, and I am observing bubbling. It could possibly be water vapor, but I highly doubt it. It has
been bubbling for a decent amount of time now; I would think all water would have been driven off by now. To be sure, I will let it run to completion;
theoretically nothing should be left after all is done according to the equation:
H2C2O4 + S -> H2S + 2CO2
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I think you should have smelled H<sub>2</sub>S by now. Its smell threshold is only 0.47 ppb.
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Upsilon
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I'll have to do that next time then. I don't have any test tube stoppers with holes. Even if I did I wouldn't really want to try and rig something up
while the reaction is taking place.
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Upsilon
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| Quote: Originally posted by blogfast25 | | Quote: Originally posted by Upsilon |
With this setup I have successfully melted the mixture, and I am observing bubbling. It could possibly be water vapor, but I highly doubt it. It has
been bubbling for a decent amount of time now; I would think all water would have been driven off by now. To be sure, I will let it run to completion;
theoretically nothing should be left after all is done according to the equation:
H2C2O4 + S -> H2S + 2CO2
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I think you should have smelled H<sub>2</sub>S by now. Its smell threshold is only 0.47 ppb. |
If I were sitting here over it in stagnant air, yes. But I know it is a dangerous gas, so I have taken some precautions. Those precautions being
outdoors with an enormous box fan blowing over the setup. Low tech but surprisingly effective.
Either that or it's because I have a headcold right now and dont have much of a sense of smell currently. Probably not the ideal time to do
experiments with hydrogen sulfide, but I've been out here with it for over an hour already, and I'm still very much alive. Like I said I am upwind
from the big box fan so I doubt very many H2S molecules are making their way over to me.
[Edited on 29-9-2015 by Upsilon]
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aga
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=470 parts per Trillion ?
Jeez.
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blogfast25
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Yes. Probably an evolutionary early warning system: it's also very toxic.
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Upsilon
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Just finished with the experiment. Not everything was reacted; curiously, the contents of the tube formed a solid column. About half of this column
stayed at the bottom of the tube, and the upper half migrated up the tube somehow and did not melt. There is also a little bit of foamy unreacted
sulfur left at the bottom of the tube. I weighed the contents and it came out to 1.93g, which is actually greater than the mass of the reactants
(excluding the weight of the water in the hydrated oxalic acid). It has been raining here all day and is quite humid, so maybe a lot of water was
absorbed. I can't say that these are conclusive results, but the molten portion of the mixture did bubble quite steadily for multiple hours until all
of the molten mixture was gone.
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blogfast25
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@Upsilon:
As I wrote above: had the reaction proceeded even at a small conversion rate you would have smelled rotten eggs. S<sub>8</sub> is a rather
sluggish reactant in many situations.
[Edited on 30-9-2015 by blogfast25]
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Upsilon
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| Quote: Originally posted by blogfast25 | @Upsilon:
As I wrote above: had the reaction proceeded even at a small conversion rate you would have smelled rotten eggs. S<sub>8</sub> is a rather
sluggish reactant in many situations.
[Edited on 30-9-2015 by blogfast25] |
Not sure if you saw my post earlier or not, where I said that I had a giant box fan blowing over the setup which I was sitting upwind from, as well as
having very poor sense of smell currently due to a head cold.
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blogfast25
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| Quote: Originally posted by Upsilon |
Not sure if you saw my post earlier or not, where I said that I had a giant box fan blowing over the setup which I was sitting upwind from, as well as
having very poor sense of smell currently due to a head cold. |
Hmmm... even in those conditions 0.47 ppb is easily reached. Next time have some filter paper soaked in CuSO<sub>4</sub> placed 'down
wind'? It seems a little odd to set up a nice experiment that has no means of detecting a reaction product that's so easily... detected! 
[Edited on 30-9-2015 by blogfast25]
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Upsilon
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| Quote: Originally posted by blogfast25 | | Quote: Originally posted by Upsilon |
Not sure if you saw my post earlier or not, where I said that I had a giant box fan blowing over the setup which I was sitting upwind from, as well as
having very poor sense of smell currently due to a head cold. |
Hmmm... even in those conditions 0.47 ppb is easily reached. Next time have some filter paper soaked in CuSO<sub>4</sub> placed 'down
wind'? It seems a little odd to set up a nice experiment that has no means of detecting a reaction product that's so easily... detected!
[Edited on 30-9-2015 by blogfast25] |
I know; next time I'm going to try actually bubbling the gas into a copper sulfate solution to see if I get a precipitate. I was hoping that I would
be able to run the whole reaction to completion. Having nothing left in the tube would be pretty clear evidence of the hypothesized reaction, I think.
Another oddity to note is that my potassium hydroxide temperature buffer solution got way hotter than the boiling point elevation calculation
predicted. I only wanted to elevate the boiling point by 20C; the calculation called for about 32g of KOH in 30mL of water. But it got darn close to
150C on a few occasions and showed no signs of boiling. A lot of water did evaporate off, though. Maybe the evaporating water caused the solution to
supersaturate, thus allowing a very high BP elevation? When I let it cool, I got these really cool KOH crystals forming.
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deltaH
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Using KOH is a big mistake IMHO. If you did form H2S, it would have most surely formed K2S which is completely odourless at very high pH. You see H2S
is a weak acid. Similarly, if you formed CO2, then you would, in fact, have formed K2CO3.
Also, strong electrolyte solutions will MAKE SURE no sulfur can dissolve because the sulfur in non-polar and the solution highly ionic. This then
means that your reaction becomes purely a surface heterogeneous one, which with sluggish kinetics won't do much.
Finally, oxalic acid can form and be sold as the dihydrate. This wouldn't be a good version to use for this reaction because the melt would then be
strongly ionic since oxalic acid is moderately a strong acid. Anhydrous oxalic acid, on the other hand, is a non-polar molecule because it is
symmetrical and so might even dissolve a little sulfur at elevated temperature. Do you know for sure whether you have anhydrous oxalic acid or the
dihydrate?
I strongly suggest you just take a TINY amount of sulfur and oxalic acid (preferably anhydrous) neat and gently melt them in a test tube immersed in
some hot oil if desired, to test this. You might even use excess oxalic acid. The sulfur should be reduced faster than the oxalic acid decomposes with
any luck.
Glad you're taking the appropriate precautions.
Thanks for posting your results and good luck!
[Edited on 30-9-2015 by deltaH]
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madcedar
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Lime sulphur controls a range of fungal diseases and pests on fruit trees, tomatoes, grapes, roses etc. It's available from your nearest
horticultural store and it's basically a solution of calcium polysulphides. Just add HCl and Bob's your uncle.
How to kill yourself using the "detergent method" of suicide
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blogfast25
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| Quote: Originally posted by deltaH | Using KOH is a big mistake IMHO. If you did form H2S, it would have most surely formed K2S which is completely odourless at very high pH. You see H2S
is a weak acid. Similarly, if you formed CO2, then you would, in fact, have formed K2CO3.
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The KOH solution was only there as an isothermal heating medium, surrounding the reactor. Small amounts of any H<sub>2</sub>S
formed would have been absorbed but unlikely all of it. The use of KOH solution as a heating medium is a strange choice but it doesn't invalidate the
experiment, IMHO.
[Edited on 30-9-2015 by blogfast25]
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deltaH
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| Quote: Originally posted by blogfast25 | | Quote: Originally posted by deltaH | Using KOH is a big mistake IMHO. If you did form H2S, it would have most surely formed K2S which is completely odourless at very high pH. You see H2S
is a weak acid. Similarly, if you formed CO2, then you would, in fact, have formed K2CO3.
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The KOH solution was only there as an isothermal heating medium, surrounding the reactor. Small amounts of any H<sub>2</sub>S
formed would have been absorbed but unlikely all of it. The use of KOH solution as a heating medium is a strange choice but it doesn't invalidate the
experiment, IMHO.
[Edited on 30-9-2015 by blogfast25] |
 Sorry, brain freeze, I completely missed that immersed in a bath of it
I should stop skimming threads early in the morning before rushing off lol
Okay, perfectly fine then and it's not looking good for the method.
Perhaps oxalic acid dihydrate is being employed and this is forming a strongly ionic melt and so sluggish to the kinetics? If Upsilon
can confirm he is using anhydrous oxalic acid, then I think this thing is officially dead down to bad kinetics, but again, I'd try heating it
purposefully to decomposition to see if there's any hope.
****************
Lime-sulfur can easily be prepared from lime and sulfur and I think that should react cleanly with oxalic acid to form H2S, CO2 and calcium oxalate.
Lime-sulfur consists of ionic polysulfides, mainly S5(2-) which ought to be reduced in solution by oxalic acid much more easily than the unactivated
non-polar S8 molecule. In some ways, the polysulfides can be viewed as an 'activated' form of sulfur.
Lime-sulfur recipe from wikipedia:
| Quote: | | A New York State Agricultural Experiment Station recipe for the concentrate is 80 lb. of sulfur, 36 lb. of quicklime, and 50 gal. of water (192 g
sulfur, 86 g quicklime of high purity per 1000 g (1 liter) of water). Ca. 2.2:1 is the ratio (by weight) for compounding sulfur and quicklime; this
makes the highest proportion of calcium pentasulfide. If calcium hydroxide is used, an increase by 1/3 or more (to 115 g/L or more) might be used with
the 192 g/L of sulfur. If the quicklime is 85%, 90%, or 95% pure, use 101 g/L, 96 g/L, or 91 g/L; if impure hydrated lime is used, similarly increase
its quantity. Avoid using lime that is less than 90% pure. Boil for an hour, stirring and adding small amounts of hot water to compensate for
evaporation. |
Lime-sulfur may react from solution with oxalic acid to form H2S, just another suggestion to get around the sluggish kinetics of sulfur.
[Edited on 30-9-2015 by deltaH]
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blogfast25
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| Quote: Originally posted by deltaH |
Sorry, brain freeze, I completely missed that immersed in a bath of it
I should stop skimming threads early in the morning before rushing off lol
Okay, perfectly fine then and it's not looking good for the method.
Perhaps oxalic acid dihydrate is being employed and this is forming a strongly ionic melt and so sluggish to the kinetics? If Upsilon
can confirm he is using anhydrous oxalic acid, then I think this thing is officially dead down to bad kinetics, but again, I'd try heating it
purposefully to decomposition to see if there's any hope.
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http://www.sciencemadness.org/talk/viewthread.php?tid=63790&...
He's using the dihydrate. It's easy to dehydrate: just heat to about 200 C, off the top of my head.
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deltaH
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| Quote: | | He's using the dihydrate. It's easy to dehydrate: just heat to about 200 C, off the top of my head. |
Isn't 200C too high, the TGA plot I attached above suggests that it decomposes fully by 200C?
If it dehydrates easily, then it should dry if molten and held say at 120C for some time, where it won't decompose. This may be the bubbling
upsilon observed, i.e. just steam.
Anyway, as I said, the observation posted thus far doesn't bode well for the idea, I suggest moving on to preparing lime-sulfur, which is VERY easily
done and then try reacting oxalic acid with that. Should solve the kinetic problem.
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deltaH
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Apologies for its morbidity, but I just read that a large number of people in Japan commit suicide by making H2S by reacting lime-sulfur containing
bath salts with acid. See this bulletin on the disturbing trend https://info.publicintelligence.net/MAchemicalsuicide.pdf
So that lends more weight to the lime-sulfur + oxalic acid route. Note, while any acid mixed with lime sulfur yields some H2S... enough to even kill
you, I think one would get much better yields of H2S on a sulfur basis if using oxalic acid since you still need a reducing agent to convert 4/5 of
the sulfur present theoretically.
Again, WARNING anyone reading this about the extreme toxicity of H2S gas!
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Upsilon
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It just seems strange to me that it would continue bubbling steadily for hours if it was just steam. The sulfur and oxalic acid formed a clear
honey-colored melt which slowly vanished over time. Studying the test tube closely, the bubbles would appear at random places in the melt and rapidly
grow until taking off upwards.
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deltaH
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| Quote: | | The sulfur and oxalic acid formed a clear honey-colored melt which slowly vanished over time. |
hmm, this is indeed an interesting observation and more encouraging that something happened than what I initially understood things to be,
particularly the observation that it vanished. It could be that the sulfur did form H2S or it formed something else. Not sure what 'else' could have
formed... I can speculate carbon oxysulfide (COS), water and CO2 perhaps? Although COS is also described to have a bad smell.
The honey colour seems indicative of dissolved sulfur, so I'd say you probably successfully dehydrated the oxalic acid.
Speculative alternate hypothesis equation:
HOOCCOOH(l) + S(l) + heat => H2O(g) + COS(g) +CO2(g)
blogfast, is there a simple filter-paper-type test for COS?
If things indeed went this route, then at least there's an interesting and simple way to make COS 
There's always the lime-sulfur route to H2S...
[Edited on 30-9-2015 by deltaH]
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Upsilon
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I'm going to attempt the experiment again likely tomorrow; this time I'll cover the tube with filter paper soaked in CuSO4 solution. If it's really
H2S gas then it should slowly turn black. Of course some basic copper carbonate would form as well (because of the CO2 gas), but that shouldn't matter
since it's not even close to black.
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Upsilon
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Just finished with my second attempt. Much more conclusive results this time. I was able to melt all of the mixture this time, and almost all of it
reacted. I even took some videos and photos so you all can see what happened (videos are in GIF form because I'm too lazy to upload a real video  ). Details:
0.5g of sulfur powder and 1.97g of oxalic acid dihydrate were thoroughly mixed together in a test tube. A piece of filter paper was fixed over the
mouth of the test tube with a rubber band. The test tube was then submerged in hot canola oil, which never got hotter than 150C. The filter paper on
the test tube opening was doused with copper(II) sulfate solution via pipette, but not so much was added as to have some run down into the reaction
mixture. The reaction was allowed to run for approximately 6 hours. Within a couple of hours the copper(II) sulfate-soaked filter paper began to turn
noticeably black. By the time the heat was turned off, only a very small amount of melt was left, and reaction rate had drastically slowed. Strange
crystal structures were found above the leftover melt.
Weight of reactants (excluding the water in the oxalic acid dihydrate): 1.91g
Weight of tube contents at end: 0.98g
Reaction soon after the contents melted (color is not as obvious as before since the canola oil is colored as well)
Reaction about 4 hours in
Reaction about 5 and a half hours in
Reaction immediately after turning off heat, about 6 hours in (strange crystal formation is visible partially submerged in the melt; strange
crack-like formations on test tube visible, though they are not actually cracks in the glass)
Tube recovered from the oil after cooling (crystal is hard to see but present, crack-like formations again visible)
Top of tube, illustrating the effect on the CuSO4-doused filter paper
Inside of the recovered filter paper, clearly showing the probable CuS precipitate
And that's all! I would say this is pretty conclusive that the hypothesized reaction took place.
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blogfast25
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@Upsilon:
Nice experiment and write-up (we really need a lot more of the latter on SM, so keep up the effort!)
What all this means (probably) is that reaction rate is very small and what little reaction does happen is driven by removal of two of the reaction
products (CO2 and H2S) from the mix - Le Chatelier principle.
It doesn't appear to be a practical way to produce H2S though...
[Edited on 2-10-2015 by blogfast25]
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Upsilon
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Most certainly. It took 6 hours to get rid of a mere 2.5g of reactants; I can't imagine how long it would take to actually get a substantial amount of
gas. Not to mention that it's mixed with CO2 which would cause unwanted effects in many cases. Still, it was cool to do.
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