Sciencemadness Discussion Board

Sodium Ethyl Sulfate

Amy Winehouse - 1-11-2011 at 15:07

Hi SM how are you?

Great! me too!
:D

I want to discuss this section of a widely known synthesis for nitroethane:
[There is already a thread on nitroethane synthesis, but the question I have is NOT regarding nitroethane]

"113 parts by weight of sodium bisulfate and 20 parts by weight of pure grain
alcohol are combined in a flask and brought to boiling upon which time the sodium
bisulfate crystals disappear and sodium sulfate forms.

When the reaction has been completed, the flask is immersed in an ice bath and vigorously stirred until the tempurature rapidly goes below 32.3C. The formed sodium sulfate is thus filtered out leaving an anhydrous ethyl hydrogen sulfate/ethanol mix. The excess ethanol is distilled off, and the ethyl hydrogen sulfate is neutralized with an appropriate quantity of sodium carbonate leaving sodium ethyl sulfate. Simple... thats all there is to it!

The secret to how it works is the excess
sodium bisulfate when rapidly cooled below 32.3C forms the decahydrate, or Glaubers salt, and this sucks the water out of the reaction"

Sodium ethyl sulfate is needed for that Nitroethane reaction, but I just want to discuss the Sodium Ethyl Sulfate, specifically the part where i i suck at life.

Note:I used 75.5% grain alcohol because my local liquor stores ALSO suck at life but i figured the decahydrate would suck all teh h20s up.

Anyway, I nuked the ethanol/sodium bisulfate concoction in a RBF til it boiled and then vigorously stirred in an ice bath, but when the time came for step "thus the sodium sulfate is filtered out leaving an ethyl hydrogen sulfate/ethanol mix" I ran into a problem. What was left in the flask was a bunch of chunky gunk(i assume sodium sulfate) and a VERY small amount of liquid. I tried dumping it through filter paper and all the liquid stayed inside the chunky stuff.

What am i doing wrong besides being a Huge Noob? Should I use a buchner funnel to suck the liquid off of dat shit at the pump?

Thanks SM!

Foss_Jeane - 1-11-2011 at 20:23

Looks like a quote from an old source (archaic terms). I read "pure grain alcohol" to mean anhydrous ethanol. 151 proof vodka is far from pure, and should have been distilled to get 95% ethanol, and then dried to remove the remaining water. That's way too much water to remove with just the NaHSO4.

If you can't set up to distill and dry ethanol, you can't do this, and shouldn't even be trying.

Amy Winehouse - 1-11-2011 at 21:15

No man pure grain alcohol is just 95%. Im distilling it to get 95% right now, i dun figgered it was too much to remove with NaHS04 it doesnt need to be anhydrous the sodium sulfate does work when it turns into the salt.

But obviously absolute etoh would be ideal...is there a way to do it without a vacuum dessicator? I dont have one.

Bot0nist - 2-11-2011 at 04:24

I have had some luck using anhydrous copper sulfate to dry ethanol. I don't think it fully breaks the azeotrope, but it does remove some water from 95% ethyl alcohol (Golden Grain) when distilling.

Amy Winehouse - 2-11-2011 at 06:30

sweet thanks man, ill give that a try.
:o Distilling it to 95% is taking daaaaaays

#impatience

Bot0nist - 2-11-2011 at 07:27

Are you distilling from vodka? When I distill from white wine I find that salting the wine a bit with NaCl really helps by raising the BP of the water in the solution, allowing for a better fraction of alcohol to come over. It doesn't take much salt to notice this effect.

Amy Winehouse - 2-11-2011 at 16:00

Okay man, I like your signature a lot.

Im trying the NaCl im distilling from Grain Alcohol (Everclear).

Anyway, once i do boil the NaHSO4 with the EtOH whats the best filtration method for the sodium sulfate?

xwinorb - 2-11-2011 at 18:41

Hi Amy Winehouse :

I was considering using this method to make nitroethane, and looks like it does not work as stated.

Please see this thread, I started it :

http://www.sciencemadness.org/talk/viewthread.php?tid=13343&...


If you want nitroethane ( looks like not exactly what you want ) , better make ethyl bromide, then react in DMF with sodium nitrite.

Amy Winehouse - 3-11-2011 at 07:00

Oh okay, i DO want nitroethane. DMF is pretty tough to get, does substituting it for dimethyl sulfoxide work?

And someone in your thread [I apologize for not finding it the search i did was for sodium ethyl sulfate specifically] suggested using sulfuric acid and ethanol, but that just produces ethyl sulfide?

[Edited on 3-11-2011 by Amy Winehouse]

Bot0nist - 3-11-2011 at 07:45

Did you see Antancho's (sp) thread?

[Edited on 3-11-2011 by Bot0nist]

More info

xwinorb - 3-11-2011 at 12:39

Some more information for you then :

I am aware of the Antoncho way to make nitroethane, I think it is more dangerous and prone to error and low yielding. Uses high temperature also.

The DMF is relatively easy, take care with the work up, not dangerous if not distilling the nitroethane. You might get low yields for not doing a good workup. DCM works well as a solvent here ( I mean DCM, not DMF, for the work up, not for the reaction )

No, you CAN'T use DMSO, instead of DMF, it does not work.


Like most other methods I am aware of, including Antoncho's, it uses a LOT of solvent and nitrite to get a relatively small amount of nitroethane.

I made 80 g of ethyl bromide, at circa 75 % yield. From this one I was able to make circa 30 g ( a bit less ) of nitroethane. Yield here at circa 50 %.

I did not distilled the nitroethane, instead I distilled out the DCM as much as I could. First with aspirator vacuum, then w/o.

Slight yellow color, good smell, transparent, and worked very well. It smells a bit like airplane model glue.

Amy Winehouse - 3-11-2011 at 13:15

I have DCM, just not DMF. Where do you get your DMF? I live in America.

xwinorb - 3-11-2011 at 15:42

Have emailed you, please check it.

aaparatuss - 4-11-2011 at 00:06

What of the sulfamic acid technique, i hope to try this soon.

i bet the dry distillation of ammonium ethyl sulfate ala

"1.5 mole sodium nitrite (103.5g) is intimately mixed with 1 mole of sodium ethyl sulfate (158g) and 0.0625 moles of K2CO3 (8.6g). The mixture is then heated to 125-130°C, at which temperature the nitroethane distills over as soon as it is formed. "
by Aurelius (format & minor edits by metanoid)

works it must be tried at least.

second ... getting 3A or 4A molecular sieve beads is not a hassle, drying alcohol is the least of our worries.

third.... evil lurker should be trust worthy ...cool the mixture faster i have not tried this method ither....


[Edited on 4-11-2011 by aaparatuss]

Alteration to the method of US Patent 3024263

madcedar - 4-11-2011 at 06:17

Preamble:
Sodium Bisulphate (anhydrous) mw=120 mp=315
Sodium Bisulphate (mono hydrate) mw=138 mp=58.5

ethanol mw=46 density (of 95%)=0.789
one mole of 95% ethanol weighs 46/0.95=48.4g (48.4/0.789 = 61.4ml)
water mw=18

one mole of 95% ethanol has (0.05*1/0.95) * (46/18) = 0.134 mole water

2NaHSO4.H2O + C2H5OH <=> C2H5HSO4 + Na2SO4 + 3H2O (87% yeild)
113 parts + 20 parts -> 45.3 parts

Na2SO4 can adsorb 10 moles of water => 7 mole to play with.

Altered Method:
The original patent method uses 20 parts of 95% ethanol to 113 parts of sodium bisulphate. Anyone who has tried this knows that that amount of ethanol hardly wets the sodium bisulphate. Looking at the reaction equation it is clear that ten times the amount of ethanol can be used while only 50% of the Na2SO4 water absorbtion capacity is used.

Next thing to note that the monohydtate of sodium bisulphate melts at about 58 degrees (it also turns stainless steel black - so use glass).

This is what I did: My sodium bisulphate came from a swimming pool supply store so I heated some sodium bisulphate up to find out if it was anhydrous. Since it didn't melt at about 70 degrees I assumed it was anhydrous. So, for one mole of room temperature anhydrous sodium bisulphate I added 18 ml of water. This was then heated until it melted. Then I dumped in about 200 ml of hot ethanol (about 70 degrees) and instantaneously the two liquids formed a solid mass of what I assumed to be sodium sulphate. I didn't reflux at all, I just let the whole lot cool and then filtered off the solid (sort of squeezed it through an old T-Shirt). When I added sodium bicarbonate to the filtrate there was a lot of hissing going on and for a long time as I needed to add a lot to get the pH to above 7.

That's as far as I went with the reaction.

Other things to know:
A solution of sodium ethyl sulphate can be heated and reduced without destroying the sodium ethyl sulphate as long as the pH is kept above 7. I read somewhere (maybe on this forum, and very sorry because I don't have a reference) that sodium hydroxide can not be used to raise the pH, it must be a carbonate. Now I don't know if that's true or not.

I hope someone out there double checks what I did and comes up with a way to isolate sodium ethyl sulphate.

To get a better yeild of nitroethane the sodium ethyl sulphate must be wet distilled as dry distallation with sodium nitrite gives close to 6% yeilds. See https://www.sciencemadness.org/whisper/viewthread.php?tid=4711&page=2#pid192565

Cheers

Nicodem - 4-11-2011 at 11:04

So now we have another thread for the too lazy to UTFSE to get engaged in idle talk. Can you now all please stop and read Antoncho's thread already?

madcedar - 4-11-2011 at 17:11

You as a moderator should have stopped this bullshit thread at post #1 if you care so much about it. As for finding stuff, that's what search engines are for and information can be anywhere and everywhere - a computer will find it and display a nice list of results for us poor humans.

The problem with this site is that the search engine is useless. For example, search (limit to subject only) for "nitroethane" and then search for "nitroethane again" and see the difference in results! To search this site properly us users have to use Google as follows: "nitroethane site:sciencemadness.org".

There is also another huge problem with creating a single thread on one subject and that is that the thread becomes too long to be of any use at all, just look at the sticky potassium thread, it's next to useless... mainly because of this sites next-to-useless search engine. People ask the same questions many times over in the same thread because no one has the time to read it from start to finish. So next time you want to waste your time and tell someone to UTFSE YDC (you dumb c*nt) think first okay. Do your job and delete the thread at post #1 if you care so much.

[Edited on 5-11-2011 by madcedar]

Bot0nist - 5-11-2011 at 04:41

Madcedar, I agree that the search engine isn't the best. It would work better if more people would make a meaningful subject for their posts that contain useful information. For instance, instead of naming your post "Alteration to the method of US Patent 3024263" which is detailed and accurate, you could have named it something that people who are looking for the info you posted might search for.

Nicodem is doing his job. He is trying to encourage us to read and add to existing threads, rather than start a new one on the same topic. This also would make the FSE a little more usable. As far as calling the SuperMod a dumb cunt, well , I'm not touching that one.

Good luck.

madcedar - 5-11-2011 at 17:37

Thank you for your mature and erudite reply. Sorry for my silly abuse but it wasn't directed at Nicodem, I have read many of his posts and he is (I assume he is a he) very intelligent. It's just that when I see UTFSE in a post I assume the real connotation is UTFSE YDC and in this particular case I felt it was directed at me. No harm done.

Cheers

dann2 - 6-11-2011 at 14:08


UTFSE should be changed, for the ScienceMadness Board, to DBUTFSEAIIAFU (dont bother using the f&*^%$* search engine as it is absolutely F&^%*$% USELESS)

When the 'search' facility button in pressed it should take you to a page that tells you how to google the sci board board using google
IE. in google box you type 'string to be searched' :site www.sciencemadness.org

or put a google search box at the top of the board for all and sundry to use.

Perhaps there is a reason why this is not as straight forward as it would seem (cannot search refs??) etc
My 2 cents worth

chucknorris - 23-4-2012 at 07:45

Is there even a theoretical risk that when producing sodium ethyl sulfate using sodium bisulfate and ethanol that diethyl sulfate could be formed during the process?

slinky - 17-8-2012 at 14:16

The search engine works fine for me. It's the reason I have so few posts. Nearly every question I've ever had has already been asked an answered.

Formalomaniac - 16-5-2016 at 05:46

Hi bees , as i read i see you dont know how to andle the so needed sodium salt.
Jus try this denaturated alcool(ethanol,32 gr) 40ml ,15ml of sulfuric acid where placed in a 250 ml rbf under reflux (below 140deg.) for at least 45 min, a solution of sodium carbonate (40g/100 ml h2o,prepared and shaken with a magic bullet lot of time is saved here ) wait to the sodium carbonate solution becoming clear,and neutralise first youll see sodium bicarbonate precipitate out as it is almost insoluble in ethanol ,filtrate out,let the solution concentrate on low heat,again youll probably have to filter to remove another crop of bicarbonate crystals,between each filtration add some mdthanol or ethanol to force precipitate out the carbonate leaving alone the sidoum ethyl sulfate as eh is very soluble in heated methanol at the end you should be left with a alcoolic solution of sodium ethyl sulfate(when no more bicarbonate precipitate from the alcoolic solution).Reduce this mother liquor but beqare when it will start to boil hard projecting drips of the solution its time to recrystalize,cool down a bit add 10-20 ml acetone and pour on a pyrex glass,it was for me some of the nicest crystals on earth they look like humans hairs during crystalizing(or more needles like to others) voila the remaining product for this batch after purification is 14.33g of sodium ethyl sulfate. PS: if you heat more longer youre mother liquor the bicarbonate will convert into carbonate much more easy to purify the product as it is completely insoluble in acetone and anhydrous alcool.

Fantasma4500 - 9-3-2022 at 11:14

Hi bees- As i read, i see you dont know how to handle the needed sodium salt. (NaHSO4)

Try this: denaturated alcohol (ethanol,32 gr) 40ml and 15ml of sulfuric acid were placed in a 250mL RBF under reflux (below 140deg) for at least 45 min.
A solution of sodium carbonate (40g/100mL water, prepared and shaken with a magic bullet (lots of time is saved here)
Wait for the sodium carbonate solution to become clear, then neutralise.(?)
First you'll see NaHCO3 precipitate out as it is almost insoluble in ethanol, filter out, let the solution concentrate down on low heat, again you'll probably have to filter it to remove another crop of NaHCO3 crystals. -Between each filtration add some mdthanol or ethanol to force precipitate out the carbonate leaving alone the Sodium Ethyl Sulfate as it is very soluble in hot methanol.
At the end you should be left with a alcoholic solution of Sodium Ethyl Sulfate (when no more bicarbonate precipitates from the alcoholic solution).
Reduce the solution but beware when it starts to boil hard, projecting drips of the solution(?help) its time to recrystalize.
Cool down a bit and add 10-20 mL of acetone and pour into a glass pan.

It was for me some of the nicest crystals on earth, they look like human hairs during crystallization (or needles). Voila! The remaining product for this batch after purification is 14.33g of Sodium Ethyl Sulfate.
PS: if you heat the solution longer the bicarbonate will convert into carbonate much more easily, to purify the product as it is completely insoluble in acetone and anhydrous alcohol.

Texium - 9-3-2022 at 12:32

Did... did you just bump a 6-years-dead thread just to partially correct the (admittedly, atrocious) spelling and grammar of the previous poster? ...well, I guess I've seen worse ways to revive old threads. Here, I'll take it one step further!
Quote:

Hi, fellow chemists. As I read, I see you don't know how to handle the needed sodium salt. Try this: denatured ethanol, 32 g (40 ml) and 15 ml of sulfuric acid were placed in a 250mL RBF under reflux (below 140ºC) for at least 45 min. A solution of sodium carbonate (40 g/100 mL water), was prepared and shaken with a Magic Bullet (lots of time is saved here). Wait for the sodium carbonate solution to become clear before using it to neutralize the ethanolic sulfuric acid.

First, you'll see NaHCO3 precipitate out, as it is almost insoluble in ethanol. Filter this out, then let the solution concentrate down on low heat. You'll probably have to filter it again to remove another crop of NaHCO3 crystals. Between each filtration, add some methanol or ethanol to force precipitate out the carbonate, leaving the sodium ethyl sulfate in solution, as it is very soluble in hot methanol. At the end, you should be left with an alcoholic solution of sodium ethyl sulfate (when no more bicarbonate precipitates from the alcoholic solution).

Concentrate the solution. Once it starts to boil hard, projecting drips of the solution, it is time to recrystallize.

Cool the solution and add 10-20 mL of acetone and pour into a glass pan. It was for me some of the nicest crystals on earth, they look like human hairs during crystallization (or needles). Voila! The remaining product for this batch after purification is 14.33g of sodium ethyl sulfate.

PS: if you heat the solution longer, the bicarbonate will convert into carbonate. This makes it much easier to purify the product as carbonate is completely insoluble in acetone and anhydrous alcohol.

S.C. Wack - 9-3-2022 at 15:04

Perhaps he wanted to point out that neutralizing sulfuric acid with sodium carbonate does not produce sodium bicarbonate, and denatured alcohol is not just fine, and neither is refluxing.

Maybe he was going to say that 1-posters are full of shit but decided not to be so negative and obvious.

Better an old garbage thread than a brand new garbage thread.

I wonder how many people have died from heating this with nitrite without ventilation.

Fantasma4500 - 10-3-2022 at 07:15

yes texium, the writing puzzled me for about half an hour, my brain just went on a standby and i knew my duty was to write it up in a proper way so that others, if they realized what i had down one post further down wouldnt have to go through that, and i even ended up learning something that was before incomphrehensive to me from my own corrections, it was very much a challenge that left my mind sore for a bit after. i see you also gave up on the "projecting drips of the solution" bit, unless its just me that doesnt understand it- yet.
it is a very neat input he produced however, and as its his only post it would seem that he was either disgruntled that it left the thread dead afterwards or simply died, it could be his dying breath and his last gift to this world.

i believe also the reaction of alcohol with NaHSO4 will become increasingly interesting as freedom is sodomized, one day at a time.

SC Wack, you mean to say that there must be some risidual acidic remains that generates some NOx? as for the credibility, the jumbled wordsalad would entail that he might have had success with- whatever he was attempting.

S.C. Wack - 10-3-2022 at 16:28

The reaction with nitrite generates more volatiles than the nitroalkane regardless, which is generally not mentioned.

It's hard to get past the whole dumbing down thing...there's a certain level that should not be crossed, and it's society in general. That something may have been obtained is immaterial...Claesson mixed equimolar amts. acid and alcohol and heated to an unspecified point on a water bath for 15 min., diluted with water, neutralized with KOH, evaporated, extracted with boiling alcohol, obtained 52% yield of the salt...in 1879. (BTW he also extracted a little ethyl sulfate with chloroform from such a diluted mixture, cooled with ice first)

Fantasma4500 - 28-5-2022 at 03:43

i wanna chime in on this normally thought difficult process, typically 80mL H2SO4 is used with 180mL EtOH
-- why?
80mL H2SO4- 78g reacts with 36g EtOH?
one annoying step that really messes up this process is using Na2CO3. also long reflux time- 3H is normally advocated for
i found one youtube video that explains only refluxing for 30 minutes, and with my vague reflux lets call that an hour at just barely EtOH's BP, done as simple as 500mL RBF with a 25mL erlenmeyer flask fitted upside down on the top and with a small container with water ontop of the flask

NaOH can be used just fine and prevents excessive foaming as with Na2CO3- and now comes the scientific part. when a liquid evaporates it cools down, evaporative cooling. so having a bit of extra ethanol in will explain you when the neutralization is done, so you wanna add in NaOH solution rapidly, the EtOH will do the cooling. once you add in NaOH solution and the EtOH doesnt shockboil out- then its neutralized, this easily cuts time spent on this step to maybe 1/5 maybe even further

then the solution is cooled down as far as possible and filtered, the solution now is NaEtSO4 + Na2SO4 - at 0*C Na2SO4 is 4.9g/100mL - it seems redundant to do EtOH extraction though thats easily done by heating up EtOH with the dried out solid and thereafter decanting and putting that in freezer, a slushy crystal mass will be attained which can then easily be vacuum filtered- and then subjected to drying out once again- but as practically all solids dissolved in the EtOH i wager this step as waste of time and resources

i found another user stating that alkaline pH causes NaEtSO4 to degrade, not even with NaOH this seems to be the case

care must also be taken to not excessively heat the NaEtSO4 as i found about 31% drop in weight after subjecting 0.81g of it in oven at 180*C for a few hours

in short: 1:1 H2SO4:EtOH
reflux 1H 50*C
neutralize NaOH solution until EtOH doesnt boil up anymore
cool down
filter
boil dry