hodges
National Hazard
![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif)
Posts: 525
Registered: 17-12-2003
Location: Midwest
Member Is Offline
|
|
Do NH4OH and S React?
I've seen a couple of videos on YouTube where a stink bomb is made by cutting off the heads of matches and placing them in household ammonia in a
sealed container for several days. Supposedly, sulfur in the match heads reacts with ammonium hydroxide to produce ammonium polysulfides. That
reaction sounded questionable to me.
I tried adding some powdered sulfur to 10% NH4OH solution and letting sit for several days. After that time, there is no hint of sulfide smell, just
the ammonia smell, and the HN4OH is clear (no hint of yellow).
Not sure if the "match heads and ammonia stink bomb" is a fact or not - don't have any matches to test. But if it does work, it must be something
other than just the sulfur in the match heads that reacts.
|
|
vibbzlab
Hazard to Others
![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif)
Posts: 241
Registered: 6-11-2019
Member Is Offline
Mood: Always curious
|
|
Probably it's not sulfur that is reacting with it. Matchsticks may contain antimony sulfide ( sulfide salt) sulfide will react with ammonia to form
ammonium sulfide. And sulfur do not react with it
Amateur chemist. Doctor by profession
Have a small cute home chemistry lab.
Please do check out my lab in YouTube link below
This is my YouTube channel
|
|
S.C. Wack
bibliomaster
![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif)
Posts: 2419
Registered: 7-5-2004
Location: Cornworld, Central USA
Member Is Offline
Mood: Enhanced
|
|
The real question is, does KClO3 dissolve in ammonia...I'm not sure I want to test this. Obviously there is little S in matches. You can't obtain
matches? I wonder if this was in the Anarchists Cookbook. Strike anywhere matches might be interesting in several ways, but they and their P4S3 are
pretty much gone. The useless answer is...heat.
|
|
AJKOER
Radically Dubious
![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif)
Posts: 3026
Registered: 7-5-2011
Member Is Offline
Mood: No Mood
|
|
Try generating so-called nascent hydrogen (via many paths including Zn + HCl, NaOH + Al, photolysis of H2,.....) in the present sulfur!
To quote a reference (https://www.citycollegiate.com/atomichydrogen.htm ):
"Hydrogen gas liberated during a chemical reaction is always in atomic state, which is known as nascent hydrogen.
Zn+HCl --> ZnCl2 +2[H]
If a substance capable to react is present then it will react with it, otherwise it recombines into molecular hydrogen."
This is a path to some H2S formation ion the presence of sulfur. If one wants a reaction with aqueous ammonia, I would add NH3 (aq) to a mix of Al +
S + NaOH.
---------------------------------------------------------------------
No NaOH available, try adding S to aqueous NH3 with Vitamin B12 (or use a B-Complex pill) to serve as a photocatalyst in sunlight generating solvated
electrons, e-(aq), and electron holes, h+, with an improved reaction adding some alcohol to the system.
My thoughts leading to at least some H2S formation:
NH3 + H2O = NH4+ + OH-
OH- + h+ --> .OH
NH4+ = NH3 + H+
e- + H+ = .H
.H + S = .HS (albeit a slow reaction)
e- + .HS = HS-
H+ + HS- --> H2S
.HS + .HS = H2S2 = H2S + S (see https://link.springer.com/article/10.1007/s11434-010-3268-3 )
.OH + NH3 = H2O + .NH2
.NH2 + e- = NH2-
.HS + .NH2 = S + NH3
NH2- + H+ = NH3
...........
So, I would expect a continuing scent of NH3, also some H2S in time and possible visible evidence of colloidal sulfur.
[Edited on 20-11-2019 by AJKOER]
[Edited on 20-11-2019 by AJKOER]
|
|
UC235
National Hazard
![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif)
Posts: 565
Registered: 28-12-2014
Member Is Offline
Mood: No Mood
|
|
More brain dribble as usual AJKOER.
Hot NaOH or KOH solutions do dissolve sulfur forming yellow-orangey solutions of "liver of sulfur" which is a complex mixture of polysulfides and has
a unique, gross smell. Presumably, some sulfite or similar compound forms as an intermediate which allows attack on the bulk solid.
I'm unsure if ammonia solution is capable of doing the same. Ammonium sulfide could certainly react with sulfur though.
|
|
AJKOER
Radically Dubious
![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif)
Posts: 3026
Registered: 7-5-2011
Member Is Offline
Mood: No Mood
|
|
UC235:
I now referenced a source based on a nascent hydrogen presence.
My photolysis experiment remains an alternative, in my opinion, based on also the presence of .H (the hydrogen atom radical).
So now, my suggestion is at least a sourced academic level dribble and is ostensibly a path to ammonium sulfide.
[Edited on 20-11-2019 by AJKOER]
|
|
woelen
Super Administrator
![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif)
Posts: 7997
Registered: 20-8-2005
Location: Netherlands
Member Is Offline
Mood: interested
|
|
AJKOER, again, your reaction mechanism may occur, but in this way you only obtain tiny amounts of sulfide.
I also see some major issues in your reactions. I see NH2(-), amide ion. This cannot exist in aqeous solution. It immediately is destroyed by water,
forming NH3 and OH(-).
Without NaOH, even in sunlight and the suitable catalysts, I expect at best some trace amounts of sulfide after some time. Maybe you might smell some
H2S, faintly, very faintly. This definitely is not a practical route to ammonium sulfide (or ammonium polysulfides).
If you want more understanding over here, try to think more from a practical point of view and do not make things overly complicated, just to show
some tiny trace amount reaction, which _might_ occur, but in practice hardly can be observed.
|
|
woelen
Super Administrator
![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif)
Posts: 7997
Registered: 20-8-2005
Location: Netherlands
Member Is Offline
Mood: interested
|
|
Personally, I think that the concentration of hydroxide ions in aqueous ammonia is not high enough to get decent amounts of sulfide. If you boil
sulfur with a fairly concentrated solution of NaOH, then indeed you get a yellow solution. The sulfur disproportionates to thiosulfate and sulfide and
the sulfide in turns reacts with more sulfur to make polysulfides (these are responsible for the yellow color). The polysulfides can react with water
and thiosulfate to give even more complicated species, so-called polythionates. This entire mix is a whole mess of sulfides and oxo-sulfur anion
species.
I can imagine that in ammonia such reactions also can occur, but ammonia is a very weak base. So, you only have a very low concentration of OH(-) in
ammonia. If the reaction occurs, then it will be very slow, due to the low concentration. So, from a practical point of view: no, mixing sulfur with
ammonia is not a useful route to ammonium polysulfides.
----------------------------------------------------------------------------------------------------
Sb2S3, which is said to be present in some types of matches, can be dissolved in alkaline solutions, leading to antimonates and sulfide. I do not
know, however, if this also works in the weakly alkaline ammonia. I also think that the dark grey crystalline form of Sb2S3 does not react like that,
but the red/orange form may do so. The latter is more reactive and I think that this also is the form, present in matches (I'm not 100% sure though,
personally I have never seen matches with Sb2S3 in them). I have pure crystalline Sb2S3 (it can be obtained without any fuzz from eBay), but this
material is not that reactive, at least not at room temperature.
|
|
DraconicAcid
International Hazard
![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif)
Posts: 4301
Registered: 1-2-2013
Location: The tiniest college campus ever....
Member Is Offline
Mood: Semi-victorious.
|
|
Do aqueous ammonia and sulphur react? Yes, but not with each other.
Please remember: "Filtrate" is not a verb.
Write up your lab reports the way your instructor wants them, not the way your ex-instructor wants them.
|
|
draculic acid69
International Hazard
![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif)
Posts: 1371
Registered: 2-8-2018
Member Is Offline
|
|
30%ammonia +sulfur + ethanol + styrene= ammonium polysulfide and styrene willgerodt reaction mixture which is on this site somewhere. so yes but I
think you might need some ethanol to help dissolve the sulfur a bit first. so I reckon yeah to some extent you should get ammonium polysulfide.try it
and report back
|
|
draculic acid69
International Hazard
![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif)
Posts: 1371
Registered: 2-8-2018
Member Is Offline
|
|
Heat is probably also an ingredient
|
|
DavidJR
National Hazard
![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif)
Posts: 908
Registered: 1-1-2018
Location: Scotland
Member Is Offline
Mood: Tired
|
|
Implying there's a brain in there somewhere...
|
|
S.C. Wack
bibliomaster
![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif)
Posts: 2419
Registered: 7-5-2004
Location: Cornworld, Central USA
Member Is Offline
Mood: Enhanced
|
|
If one is not doing the Willgerodt (i.e. no organics are present) no solvent is needed.
Like most all chemistry, whether this is practical or not depends on the equipment on hand.
|
|
AJKOER
Radically Dubious
![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif)
Posts: 3026
Registered: 7-5-2011
Member Is Offline
Mood: No Mood
|
|
In fairness, I did NOT ever propose my examination of many possible interactions (my so-called 'thoughts') between S and atomic hydrogen as a path to
any significant H2S creation. My final words:
"So, I would expect a continuing scent of NH3, also some H2S in time and possible visible evidence of colloidal sulfur."
My further speculation was that a possible path might be promoted in a medium favoring solvated electrons, which implies employing say ethanol. To my
surprise:
Quote: Originally posted by draculic acid69 ![](images/xpblue/lastpost.gif) | 30%ammonia +sulfur + ethanol + styrene= ammonium polysulfide and styrene willgerodt reaction mixture which is on this site somewhere. so yes but I
think you might need some ethanol to help dissolve the sulfur a bit first. so I reckon yeah to some extent you should get ammonium polysulfide.try it
and report back |
which also remarkably agrees with my take on possible H2S2 formation (via .HS + .HS), and therefrom ammonium polysulfide.
Relatedly, with respect to possible active surface chemistry, here is a prior comment of mine relating to the use of surface promoted hydrogen atoms
and there use in a possible commercial leaching application:
Quote: Originally posted by AJKOER ![](images/xpblue/lastpost.gif) |
..................
For reducing, I recommend in situ creation of the hydrogen atom radical (cited as the major reducing specie by Buxton in solution, see Eq 3 on page 2
at https://pdfs.semanticscholar.org/d696/b35956e38351dd2eae6706...). Chemisorption of the radical on the surface of metals like Zn, Al and Mg with a
limited lifespan is also possible. My prior related comment:
Quote: Originally posted by AJKOER ![](images/xpblue/lastpost.gif) |
.......
Next, imbue the surface of Mg or Al with the hydrogen atom radical (from the traditional nascent hydrogen generation methods based on say Al/NaOH).
One may assume that the •H radical functional behaves (per its seemingly reversible formation reaction: e- + H+ = •H ) as apparently a (e-,H+)
pair acting on ions. For an example from 'Hydrometallurgy 2008: Proceedings of the Sixth International Symposium', p. 818, a commercial reductive
leaching equation, to quote:
" PbS + 2 •H = Pb + H2S (5) " (see https://books.google.com/books?id=1etfSdk55SYC&pg=PA818&... )
which I view functionally as follows:
Pb(+2)S(2-) + 2 (e-, H+) = Pb + H2S (g)
......
[Edited on 4-10-2018 by AJKOER] |
Although some on this forum, even given the above proposed commercial application of surface active hydrogen radicals, remain skeptics....
[Edited on 24-12-2018 by AJKOER] |
[Edited on 20-11-2019 by AJKOER]
|
|
Tsjerk
International Hazard
![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif)
Posts: 3026
Registered: 20-4-2005
Location: Netherlands
Member Is Offline
Mood: Mood
|
|
The ammonia sulfur styrene reaction is done in a pressure chamber to be able to heat it enough to get the reactants to react.
|
|
AJKOER
Radically Dubious
![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif)
Posts: 3026
Registered: 7-5-2011
Member Is Offline
Mood: No Mood
|
|
Quote: Originally posted by Tsjerk ![](images/xpblue/lastpost.gif) | The ammonia sulfur styrene reaction is done in a pressure chamber to be able to heat it enough to get the reactants to react. |
Yes, extreme conditions, but it may lend itself to radicalization.
Just found an old reference (THE LANCET, Volume 9, Issue 228, 12 January 1828, Pages 552-554) that, in part, appears to verbally confirm the action of
nascent hydrogen acting on sulfur creating hydrogen sulfide (other than the source noted previously at https://www.citycollegiate.com/atomichydrogen.htm):
To quote from LECTURES ON CHEMISTRY by PROFESSOR BRANDE, delivered at the Royal Institution of Great, LECTURE XXII. On the Combinations of Sulphur
with Hydrogen, Chlorine, and Iodine ; and on Phosphorus, link: https://www.sciencedirect.com/sdfe/pdf/download/eid/1-s2.0-S... :
"THE combination of sulphur with hydrogen comes next to be considered, a compound which was first discovered by Scheele about fifty years ago; it may
be obtained by presenting sulphur to hydrogen in its nascent state, as by acting upon sulphuret of iron with dilute sulphuric acid."
The last part of the above comment makes me believe it is necessary to confirm by having someone add S to HCl+Zn (or, S to Al+NaOH), to actually
confirm that the action of nascent hydrogen on sulfur either significantly (or NOT) results in H2S.
Note: I have found a reference that nascent hydrogen will react with a sulfide (including organic compounds containing S) to generate H2S. See, for
example, https://link.springer.com/article/10.1007%2FBF01216655 .
[Edited on 20-11-2019 by AJKOER]
|
|
hodges
National Hazard
![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif)
Posts: 525
Registered: 17-12-2003
Location: Midwest
Member Is Offline
|
|
NaOH + S + Al definitely makes some sulfides. That was the first reaction for making sulfides I stumbled on when I was growing up. I had read that
sulfur dissolves in NaOH. So I dissolved some. I sat there staring at the solution for a while, wondering what to do with it. Then I recalled that
NaOH solution reacts with aluminum, and I assumed that would still be the case even with the sulfur present. So I added aluminum foil. It produced
hydrogen as expected, and left an orange solution that turned green upon cooling. For fun, I decided to "neutralize" the remaining NaOH with muriatic
acid. I was working outside. As soon as I added the muriatic acid, there was much bubbling and a slight vapor cloud coming from the container.
Within a couple minutes, one of my parents came running out of the house to ask me what I was doing to make such a bad smell!
Not sure I ever figured out exactly what was produced by the NaOH + S + Al, but one of the products being aluminum sulfide seems pretty likely based
on that experience. If nothing else, the NaOH would remove the oxides from the aluminum and allow it to react with the sulfur.
|
|
AJKOER
Radically Dubious
![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif)
Posts: 3026
Registered: 7-5-2011
Member Is Offline
Mood: No Mood
|
|
Thank Hodges for sharing!
One would think that a reaction resulting in H2S via nascent hydrogen acting on S would at least be better known as my dated source is from the year
1828 (a little short of two centuries).
One reason is that an understanding of the underlying chemistry remains advanced, in my opinion. For example, the usual action of sulfur with OH-
normally occurs at higher temperatures (see, for example, https://chemiday.com/en/reaction/3-1-0-11095 ).
My take on the possible mechanics starts with a radical reaction occurring at normal temperatures:
S•− + OH• = S + OH- (see https://www.degruyter.com/view/j/hfsg.2005.59.issue-3/hf.200... for parallel reaction with O2 )
As higher temperatures could induce radicalization of the action of OH- on sulfur, I would expect the above equilibrium reaction could be moved to the
left. I take this to imply a possible path based on S•− may result in associated reactions occurring at a lower temperature. In fact, the action
of a solvated electron acting on sulfur at room temperature, for example:
S + e-(aq) = S•−
where the solvated electron can be sourced, for example, from the hydrogen atom radical as follows:
H• <---> e- + H+
And, hydrogen sulfide:
H• + S = HS•
HS• + HS• = H2S2 = H2S + S (see https://link.springer.com/article/10.1007/s11434-010-3268-3 )
[Sidebar: Interestingly, one can argue (for ALL reactions above) the same chemistry presented substituting for S with namely oxygen, O2]
----------------------
And further, in the presence of oxygen per a 2019 source (https://pdfs.semanticscholar.org/533e/9a0b2e5d938abc555e267f... ), associated reported product formation:
HS•/S•− + O2 --> SO2•- (+ H+) (Source Page 7, Eq (7))
SO2•- + SO2•- --> S2O4(2-) (Same source, per comment)
Then, per Wikipedia on dithionite (see https://en.wikipedia.org/wiki/Dithionite ), notes that dithionite undergoes a so-called acid hydrolytic disproportionation reaction to thiosulfate
and bisulfite (presence of CO2 may assist):
2 S2O4(2-) + H2O --> S2O3(2-) + 2 HSO3-
which are some reported products with air/oxygen upon boiling sulfur in aqueous NaOH.
[Edited on 21-11-2019 by AJKOER]
[Edited on 21-11-2019 by AJKOER]
|
|
draculic acid69
International Hazard
![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif)
Posts: 1371
Registered: 2-8-2018
Member Is Offline
|
|
Quote: Originally posted by Tsjerk ![](images/xpblue/lastpost.gif) | The ammonia sulfur styrene reaction is done in a pressure chamber to be able to heat it enough to get the reactants to react. |
Makes sense that a pressure vessel is required as boiling aqueous ammonia solution would need to be contained to not lose potency at the temp needed
to react with the sulfur.
|
|
Corrosive Joeseph
National Hazard
![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif)
Posts: 915
Registered: 17-5-2015
Location: The Other Place
Member Is Offline
Mood: Cyclic
|
|
Quote: Originally posted by AJKOER ![](images/xpblue/lastpost.gif) |
One would think that a reaction resulting in H2S via nascent hydrogen acting on S would at least be better known as my dated source is from the year
1828 (a little short of two centuries).
|
Quote: |
Nascent hydrogen is a concept that was once invoked to explain dissolving-metal reactions, such as the Clemmensen reduction and the Bouveault–Blanc
reduction. Since organic compounds do not react with H2, a special state of hydrogen was postulated. It is now understood that dissolving-metal
reactions occur at the metal surface, and the concept of nascent hydrogen is discounted, and even ridiculed.
|
https://en.wikipedia.org/wiki/Nascent_hydrogen
Also......
https://www.sciencemadness.org/whisper/viewthread.php?tid=25...
https://www.sciencemadness.org/whisper/viewthread.php?tid=14...
https://www.sciencemadness.org/whisper/viewthread.php?tid=19...
/CJ
Being well adjusted to a sick society is no measure of one's mental health
|
|
SWIM
National Hazard
![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif)
Posts: 970
Registered: 3-9-2017
Member Is Offline
|
|
How about just boiling sulfur with calcium hydroxide and then adding ammonium sulfate?
Haven't tried it, but it is my nascent hope (as they say in the city of transcendentalists) that it will work.
Maybe throw a little NaOH in there on the first reaction to speed things up a bit.
|
|
AJKOER
Radically Dubious
![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif)
Posts: 3026
Registered: 7-5-2011
Member Is Offline
Mood: No Mood
|
|
The precise species I am referring to is the hydrogen atom radicals (or hydrogen atoms), which apparently, are the cause of hydrogen embrittlement in
select metals (see, for example, my cited source, which also employs the term 'Hchemisorbed', at https://www.sciencemadness.org/whisper/viewthread.php?tid=10...). Interestingly, in the case of aluminum with Hchemisorbed, there is actually a
commercial leaching application (read bottom of page 818 at https://books.google.com/books?id=1etfSdk55SYC&pg=PA818&... ).
------------------------------------------
A good source for radical chemistry is Buxton, and the hydrogen atom is discussed on first page at https://pdfs.semanticscholar.org/d696/b35956e38351dd2eae6706... . To quote:
"The hydrogen atom is the conjugate acid of e-(aq), and it is the major reducing species in acidic solution, Eq. (3).
e-(aq) + H3O+ ---> H (aq) (3) "
Hence, its suggested use in commercial leaching applications.
----------------------------------------------------------------------
On further reflection, one could also argue that the reaction: S•− + OH• = S + OH- is moved to the left in presence of H• owing to the removal
of the hydroxyl radical by the reaction:
H• + OH• = H2O + photon
And the S•− also via:
H• + S•− = HS-
[Edited on 22-11-2019 by AJKOER]
|
|
AJKOER
Radically Dubious
![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif)
Posts: 3026
Registered: 7-5-2011
Member Is Offline
Mood: No Mood
|
|
Quote: Originally posted by AJKOER ![](images/xpblue/lastpost.gif) | Quote: Originally posted by Tsjerk ![](images/xpblue/lastpost.gif) | The ammonia sulfur styrene reaction is done in a pressure chamber to be able to heat it enough to get the reactants to react. |
Yes, extreme conditions, but it may lend itself to radicalization.
.......
|
It is interesting to compare the above comments with my suggested operating mechanics:
Quote: Originally posted by AJKOER ![](images/xpblue/lastpost.gif) |
... For example, the usual action of sulfur with OH- normally occurs at higher temperatures (see, for example, https://chemiday.com/en/reaction/3-1-0-11095 ).
My take on the possible mechanics starts with a radical reaction occurring at normal temperatures:
S•− + OH• = S + OH- (see https://www.degruyter.com/view/j/hfsg.2005.59.issue-3/hf.200... for parallel reaction with O2 )
As higher temperatures could induce radicalization of the action of OH- on sulfur, I would expect the above equilibrium reaction could be moved to the
left. I take this to imply a possible path based on S•− may result in associated reactions occurring at a lower temperature. In fact, the action
of a solvated electron acting on sulfur at room temperature, for example:
S + e-(aq) = S•−
......................
|
where the parallel reaction with oxygen in place of sulfur is:
O2•− + OH• = O2 + OH-
Supporting my argument for the reverse of the above reaction is this work, 'Characterization of active oxygen species under oxygen-alkali bleaching
conditions', at https://www.degruyter.com/view/j/hfsg.2005.59.issue-3/hf.200... , to quote, in particular:
"By comparing this value with the hydroxyl radical obtained by Ek et al. [Holzforschung 43 (1989) 391] we conclude that the active oxygen species in
the early stage of the reaction are hydroxyl radicals."
Per another source (see https://www.tappi.org/content/PRESS/TOC/0101r331.pdf ) on the topic of oxygen-alkali bleaching, with respect to operating conditions to effect the
reverse reaction, the comment:
"The oxygen delignification process is operated at relatively high temperature and pressure at either medium or high consistency in a single or
two-stage system."
with apparent similarities between the oxygen and sulfur alkali systems.
[Edited on 21-11-2019 by AJKOER]
|
|
AJKOER
Radically Dubious
![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif)
Posts: 3026
Registered: 7-5-2011
Member Is Offline
Mood: No Mood
|
|
Per a recent comment on a related thread:
Quote: Originally posted by AJKOER ![](images/xpblue/lastpost.gif) |
... Also, commentary in Bretherick, Volume 1, page 23-24, to quote:
"A student mixed aluminium foil and drain cleaner in a soft drink bottle, which started emitting gas. Another student carried the bottle outside and
was claimed to have been overcome by the toxic fumes [1]. Most drain cleaners are alkalis, so that aluminium will dissolve to produce hydrogen. The
bleach that it is is suggested may have been present will produce no toxic fumes in alkali, and one would be surprised to find arsenic or antimony
compounds present. If the collapse was not purely hysterical, the remaining, though remote, possibility would be phosphine. The soft drink the bottle
had contained was one of the many perhaps best described as impure dilute phosphoric acid [2]. "
A related comment attributing the formation of gases like arsine and stibine from nascent hydrogen at https://pubs.acs.org/doi/pdf/10.1021/ed011p308.
Education on nascent hydrogen interaction is important so as to avoid toxic gases that may be inadvertently and unexpectedly created in significant
amounts.
|
For safety, I would recommend for anyone electing a nascent hydrogen path should be performed only a small scale employing only the highest purity
reagents to create a H2S generator (from dissolving S in NaOH (aq) and adding pure Al. Treat with NaHSO4 to release H2S).
Lead the H2S (or place the hydrogen sulfide generator) into a large vessel containing NH3 fumes from an aqueous ammonia source in excess residing in
say a beaker.
A gas-phase reaction is expected forming solid NH4HS (see http://articles.adsabs.harvard.edu/cgi-bin/nph-iarticle_quer... and a plugging of ducts at https://www.honeywellprocess.com/library/marketing/whitepape...) per the equation:
NH3 (g) + H2S (g) = NH4HS (s)
And possibly:
NH3 (g) + H2S2 (g) = NH4HS2 (s)
Collect the ammonium hydrogen sulfide (polysulfide) off the walls of the container.
Note: NH4HS is not stable in the presence of moist air containing any acid gas (like CO2) liberating H2S, which is actually a pretty toxic gas (see my
comment at https://www.sciencemadness.org/whisper/viewthread.php?tid=12... and https://www.sciencemadness.org/whisper/viewthread.php?tid=21... ).
[Edited on 23-11-2019 by AJKOER]
|
|
AJKOER
Radically Dubious
![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif) ![*](images/xpblue/star.gif)
Posts: 3026
Registered: 7-5-2011
Member Is Offline
Mood: No Mood
|
|
Did recall a recent former thread comment:
Quote: Originally posted by AJKOER ![](images/xpblue/lastpost.gif) | Per a source (see http://web.iiar.org/membersonly/PDF/CO/databook_ch2.pdf ), a simple low temperature path to a sulfide (and not a polysulfide), to quote:
"Sulfur vapor and ammonia react to give ammonium sulfide and nitrogen. Sulfur also reacts with liquid ammonia to produce nitrogen sulfide."
with the cited reaction in the case of liquid ammonia:
10 S + 4NH3 → 6H2S + N4S4
However, with sulfur vapors, a possible reaction with dry ammonia gas:
4 NH3 (g) + S (vapor) --> (NH4)2S (s) + N2 (g) + 2 H2S (g)
And, with excess NH3:
8 NH3 (g) + 3 S (vapor) --> 3 (NH4)2S (s) + N2 (g)
which is precisely as was claimed per the source above.
Now, dry ammonium sulfide is apparently unstable even at room temperature, liberating NH3 and H2S.
(NH4)2S (s) + Heat --> 2 NH3 (g) + H2S (g)
.....................
[Edited on 8-9-2019 by AJKOER] |
|
|