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kclo4
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| Quote: | Originally posted by Picric-A
Has anyone made this before?
All the synthesis look difficult so i was wondering if anyone has found a way that is suitable to perform in a home lab.
This method looks feasable:
Raschig synthesis: Aqueous ammonium nitrite is reduced by HSO4−/SO2 at 0°C to yield a hydroxylamido-N,N-disulfate anion, which can be
hydrolyzed to give (NH3OH)2SO4.
NH4NO2 + 2SO2 + NH3 + H2O → [NH4]2[N(OH)(OSO2)2]
[NH4]+2[N(OH)(OSO2)2]2− + H2O → [NH4][NH(OH)(OSO2)] + [NH4][HSO4]
2[NH4]+[NH(OH)(OSO2)]− + 2H2O → [NH3(OH)]2[SO4] + [NH4]2[SO4]
Solid NH2OH can be collected by treatment with liquid ammonia. Ammonium sulfate is insoluble in liquid ammonia and is removed by filtration; the
liquid ammonia is evaporated to give the desired product
But the liquid ammonia would be a problem along with having to use Ammonium Nitrite which is dangerously explosive. |
Not to sure how it works, but it sounds like a good method.
" 40g potassium nitrite (KNO2) and 50g potassium acetate (CH3COOK) are dissolved in 100ml ice water. 750g finely crushed ice is added. Into this
solution a stream of sulfur dioxide (SO2) is bubbled until the solution smells of SO2. The temperature must be kept below 0°C through the whole
reaction. The salt of K2[HON(SO3)2] separates and is filtered off and washed with ice water. The salt is dissolved in 500ml 0.5 M HCl and boiled for
two hours. Still boiling a solution of Barium chloride (BaCl2) is added as long as barium sulfate (BaSO4) precipitates (maybe CaCl2 will do instead).
The BaSO4 is filtered off and the clear filtrate is evaporated to dryness. The residue consists of Potassium Chloride (KCl) and NH2OH*HCl. Anhydrous
ethanol(EtOH) is used for extraction of the Hydroxylammonium chloride, the KCl remains undissolved. The EtOH is evaporated on a water bath and the
product can be recrystallised from water (mp 151°C).
A similar method can be found in Organic Synthesis.(http://www.orgsyn.org/orgsyn/prep.asp?prep=cv1p0318)
Ref: Jander-Blasius, Lehrbuch der anal. u. prep. anorg. Chemie "
That is from the rhodium archive, here is a link to one of the many mirrors of it. http://www.m-pab.ru/docs/rhodium/hydroxylaminehcl.html
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Maja
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I have searched methods for preparing allyl alcohol and found one which uses anhydrous oxalic and glycerol.. So my question is : Can I use hydrated
oxalic acid ?
Oh, by the way ... Maybe someone can post allyl alcohol synthesis excluding Oxalic/Glyrecol route ? 
Thank you.
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solo
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this may help.....solo
Allyl alcohol, 2-propen-1-ol is an organic compound with the formula CH2=CHCH2OH. It is a water soluble, colourless liquid with an ethanol like odour
at low concentrations and a mustard-like pungent odour at higher concentration. Allyl alcohol is used as a pesticide and as a raw material for the
production of many chemical compounds.
Allyl alcohol can be obtained by many methods: hydrolysis of allyl chloride, by oxidation of propylene oxide with potassium alum at high temperature,
dehydrogenation of propanol, and by the reaction of glycerol and formic acid. Allyl alcohol is the smallest representative of the allylic alcohols.
Allyl alcohols in general can be prepared by allylic oxidation of allyl compounds by for instance selenium dioxide.
.......source,
http://en.wikipedia.org/wiki/Allyl_alcohol
http://www.organic-chemistry.org/synthesis/C1O/alcohols/ally...
http://www.freepatentsonline.com/3692849.html
Synthesis of oximes, aziridines, and allyl alcohols derived from substituted 1-phenyl-1-nonen-3-ones as potential cytotoxic and antitumor agents.
1: J Pharm Sci. 1978 Nov;67(11):1536-9.
[Edited on 3-11-2008 by solo]
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solo
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I don't understand this term....in reference to heating a solution......solo
"heated in a metal-bath"
or better the whole phrase,
"The light yellow solution was heated in a metal-bath at 120' to remove water, first at atmospheric pressure and finally at 130-140' (15
mm.)"
[Edited on 3-11-2008 by solo]
It's better to die on your feet, than live on your knees....Emiliano Zapata.
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Klute
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Maybe some kind of low melting alloy? I think such mixtures used to used a long time ago.. is this aold procedure?
You could just aswell use high boiling mineral oil I guess, or even a mantle...
[Edited on 3-11-2008 by Klute]
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S.C. Wack
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For instance
http://en.wikipedia.org/wiki/Wood%27s_metal
[Edited on 3-11-2008 by S.C. Wack]
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Sauron
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Would someone plase remind me of the url for the site that provides worldwide patents fulltext for free?
I am after a DDR (E.German) Patent 26660 (1960) to Heintz (I think the name is really Heinz, Dieter Heinz) and Thilo concerning preparation of
diphosphorus trioxide.
[Edited on 5-11-2008 by Sauron]
Sic gorgeamus a los subjectatus nunc.
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Klute
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espacenet.com?
Thilo has only one patent in 1960 on dichlorophosphoric esters... I didn't see anything on phosphorus oxide (III)...
http://v3.espacenet.com/publicationDetails/originalDocument?...
Research results:
http://v3.espacenet.com/searchResults?locale=fr_FR&IN=Th...
No results for Neintz in 1960...
[Edited on 4-11-2008 by Klute]
\"You can battle with a demon, you can embrace a demon; what the hell can you do with a fucking spiritual computer?\"
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Formatik
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There are no German patents that can be found for these two authors at DEPATISnet or espacenet. But Heinz and Thilo do have 1966 British patent: GB1027679. Which is likely the English variant of the same patent.
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Sauron
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Thanks. Heinz also authored the review I posted (in German) comparing his process with those of Thorpe (1890) and the 1945 German process using PCl3
and tetramethylammonium sulfite in liquid SO2.
As I can't easily get elemental P of any sort but can get (in fact have) PBr3 it is obvious that the latter method would be my only option if I wanted
to make P2O3.
My only motivation for doing so would be to test my hypothesis that the work of Roger Adams on making inorganic acid chlorides from certain oxides (in
JACS) can be extended to P2O3 -> PCl3. The reagent is oxalyl chloride.
So the combination of an onerous to make, toxic precursor and an expensive reagent and liquid SO2 solvent really render this a rather academic
exercise, although possibly a publishable one.
[Edited on 5-11-2008 by Sauron]
Sic gorgeamus a los subjectatus nunc.
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starman
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| Quote: | Originally posted by Maja
I have searched methods for preparing allyl alcohol and found one which uses anhydrous oxalic and glycerol.. So my question is : Can I use hydrated
oxalic acid ?
Oh, by the way ... Maybe someone can post allyl alcohol synthesis excluding Oxalic/Glyrecol route ?
Thank you. |
Hey Maja - Have done this one for formic acid with allyl alcohol as considerable side product.Water of crystallation is actually required or you need
to add H2O.The monohydrate is said to be optimal for HCOOH concentration,dont know if the anhydrous would be ideal to maximise the alcohol.
[Edited on 5-11-2008 by starman]
[Edited on 5-11-2008 by starman]
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Maja
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Thank you solo and starman!
One more question : Can phenylanthranilic acid be hydrolysed to anthranilic acid ? If yes, what conditions ?
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Nicodem
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| Quote: | Originally posted by Maja
One more question : Can phenylanthranilic acid be hydrolysed to anthranilic acid ? If yes, what conditions ? |
None of the many possible isomers - for which an incomplete name such as "phenylanthranilic acid" would fit - can be hydrolysed simply because there
is no hydrolysable bond (the possible isomers are N-, 3-, 4-, 5-, and 6-phenylantranilic acids). Only phenyl antranilate would be
hydrolysable, but that is a different compound from any of the phenylanthranilic acids.
…there is a human touch of the cultist “believer” in every theorist that he must struggle against as being
unworthy of the scientist. Some of the greatest men of science have publicly repudiated a theory which earlier they hotly defended. In this lies their
scientific temper, not in the scientific defense of the theory. - Weston La Barre (Ghost Dance, 1972)
Read the The ScienceMadness Guidelines!
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kazaa81
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Is it possible to reduce trichloroethylene in order to produce acetylene ?
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solo
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| Quote: | Originally posted by kazaa81
Is it possible to reduce trichloroethylene in order to produce acetylene ? |
--------------------------------------------------------------------------------
Reductive Dechlorination of DNAPL Trichloroethylene by Zero-Valent Iron
Robert Orth, Taiwo Dauda, David E. McKenzie,
Practice Periodical of Hazardous, Toxic, and Radioactive Waste Management, Vol. 2, No. 3, July 1998, pp.
123-128,
Abstract:
The reduction of trichloroethylene (TCE) by metallic iron was studied under conditions in which the trichloroethylene would exist as a separate phase
in a water/iron system. The products of the reaction were determined over time using gas chromatography (GC) and mass spectrometry (MS). The kinetics
of the loss of TCE and the formation of chloride were determined to follow zero-order kinetics under these conditions with zero-order rate constants
of 4.8 × 10–³ mg TCE hr–¹ g–¹ iron and 3.8 × 10–³ mg Cl hr–¹ g–¹ iron. The zero-order rate constant was observed to depend on the
mass or iron present. The reaction was carried out in deuterium oxide to compare the reaction pathways suggested in the literature for solution
reduction of TCE. It was observed that the major product was acetylene with minor components of ethane and ethene. The deuterium oxide showed that the
ethene and ethane were composed of a 68% total deuterated ethene and 32% ethene containing only one hydrogen. No deuterium was evident when acetylene
formed in the deuterium oxide system, indicating that all of the hydrogen in the dense nonaqueous phase liquid (DNAPL) arises from TCE. The result of
this study indicates that metallic iron can dechlorinate DNAPL TCE.
Attachment: Reductive Dechlorination of DNAPL Trichloroethylene by Zero-Valent Iron.pdf (657kB)
This file has been downloaded 763 times
It's better to die on your feet, than live on your knees....Emiliano Zapata.
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497
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Here's a question or two:
What exactly happens when SO2Cl2 reacts with water? I have read that with excess SO2Cl2 it forms chlorosulfuric acid, could this be a useful route in
preparing ClSO2OH? Also what kind of equilibrium is there between water and ClSO2OH? Like ClSO2OH + H2O <-> H2SO4 + HCl. More importantly, could
this possibly be useful in preparing H2SO4 of decent concentration? It seems like it would work since AFAIK HCl is not very reactive at all toward
conc. H2SO4, only toward SO3. Or alternatively could one use a catalyst to make 2ClSO2OH --> SO2Cl2 + H2SO4 and prepare anhydrous H2SO4 while
distilling off the SO2Cl2? I have seen that reaction mentioned but never any details.
I think this could be useful since SO2Cl2 looks fairly easy/cheap to synthesize. And I would really like to have some chlorosulfonic acid because it
works so nice to make tosyl chloride. Also might be useful if conventional sources of H2SO4 disappear.
[Edited on 10-11-2008 by 497]
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Formatik
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The old Gmelin mentions that sulfuryl chloride decomposes in water under a strong liberation of heat, forming H2SO4 and HCl acid. A little bit of
water does form chlorosulfuric acid and hydrochloric acid. The newer Gmelin might give a lot more information about its hydrolysis. It dedicated like
two-thirds of a page to POCl3 hydrolysis. There are some references stating that SO2.OH.Cl reacts explosively with water (Chemie: Grundwissen für
Ingenieure by G. Blumenthal, et al. (2006), p. 296). That would be a tricky way to pursue H2SO4.
In the case of regular H2SO4, why not instead bubble Cl2 into an SO2 solution oxidizing it, then just boil the water and HCl off (it could work to
bubble both gases simultaneously into H2O, and one could probably even bubble these gases up until the H2SO4 gets concentrated, which in the end might
need some boiling to get rid of the rest HCl), that way there is also no need to go through effort of preparing SO2Cl2 and work around the violent
reaction of it with water.
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smuv
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Ann.
What journal does Ann. stand for? Annales De Chimie?
"Titanium tetrachloride…You sly temptress." --Walter Bishop
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solo
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.........see journal abbrev.'s.......solo
http://www.geocities.com/baskargreen/journalabbr.htm
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smuv
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I had previously checked that page and it doesn't just have ann. it has ann. XYZ.
thank you though.
"Titanium tetrachloride…You sly temptress." --Walter Bishop
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Formatik
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Ann.
It's Annalen der Chemie, a.k.a. Justus Liebig's Annalen der Chemie, or just Annalen.
http://en.wikipedia.org/wiki/Annalen_der_Chemie
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smuv
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Thank you!
"Titanium tetrachloride…You sly temptress." --Walter Bishop
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497
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| Quote: |
In the case of regular H2SO4, why not instead bubble Cl2 into an SO2 solution oxidizing it, then just boil the water and HCl off (it could work to
bubble both gases simultaneously into H2O, and one could probably even bubble these gases up until the H2SO4 gets concentrated, which in the end might
need some boiling to get rid of the rest HCl), that way there is also no need to go through effort of preparing SO2Cl2 and work around the violent
reaction of it with water. |
I agree, that would be easier. I too have seen it mentioned that SO2Cl2 reacted "explosively" with water, but I don't think that means it wouldn't be
possible to use that route. I have also seen it said that SO2Cl2 forms a hydrate in cold water, so that leads me to believe the reaction
wouldn't be too hard to handle. You could even recycle the HCl back to make more Cl2 
I'm also after ClSO3H, this seems to be a very useful compound.
Since
ClSO3H <--> SO2Cl2 + H2SO4
is known to work, maybe one could synthesize it by simply absorbing SO2 and Cl2 into H2SO4, since SO2Cl2 could be formed in situ? Would that work?
Here is a good book on all the uses of chlorosulfonic acid, too bad google books only lets you see a third of it. If anyone has a complete copy I
would love have it...
[Edited on 11-11-2008 by 497]
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woelen
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SO2Cl2 does not react explosively with water. Actually, it reacts very slowly. I have this chemical and when I add this to water, it forms a blob at
the bottom, which slowly dissolves (takes tens of minutes with plain water at room temperature).
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497
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Thank you for that information. I guess that's why they say it can react explosively. Maybe at high temperature and large amounts?
According to Kirk-Othmer the reaction of stoiciometric amounts of SO2Cl2 with H2SO4 produces ClSO3H and is reversible with a mercury catalyst. No
other details given..
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