Nitroethane ala Antoncho

[Bandil]

Hi!

Swim has attempted to make sodium ethyl sulfate, the way antoncho describes it in "kitchen nitroalkane success":

100 mL 96% H2SO4 was stirred, while dripping in 129,6 mL(90 mL for methanol...) denaturated ethanol(93%). Quite exothermic reaction. 60 g of bone dry Na2SO4 was poured in and the reaction was put in a boiling water bath for 15 minutes. It was not warm enough to induce reflux, so swim just put the erlenmeyer on the heating plate to warm it up. In a few minutes, the reaction was refluxing madly. Swim suspected that there might be forming ether and/or ethen, so he sniffed the top of the reflux condesor and after a few inhalations, swim was QUITE intoxicated(lotsa ether formed), so swim decided to turn down the heat and let it reflux for 10 minutes. After that the mixture was reddish as described by Antoncho and gel like... This was pulled through a filter using vacuum and the filter cake washed with ethanol. There were about 200 mL of reddish liquid, which was chilled and put in a dripping funnel. 230 mL ethanol was put in a 500 mL erlenmeyer and filled with 110 g Na2CO3, which was stirred. The ethylsulfuric acid was dripped in and the mixture went kinda goo'ey white with LOTS of precipiate.

I suppose that all went well, but i still have some questions:

1)
Is there a way to test that what i have actually is sodiumethylsulfate and not just sodium sulfate, without wasting a whole bunch of sodiumnitrite

2)
Antoncho writes: "A 5g samlpe gave 1.7 g precipiate, which, taking in account the 1/5 NaCO3 present in the mixture, means 73% to 27% MeSO4/SO4". Does he dissolve 5 grams in water? Sodium sulfate is quite soluble in water as far as i know, so that cant be it. How the h... does he test his sodium methylsulf?

3) Wish swim luck in the last synth, as swim is REALLY excitet to get his hands on some nitroethane for further dreaming!!!

Thanks!

Regards
Peter

[Antoncho]

Ummm.... Y'know, it was never intended to boil the mixtr, especially if you use eqiumolar amts of acid and alcohol. That is a certain way to get some ether - in fact, that's how it's industrially made .

The whole point of heating it is pretty unclear to SWIM , but he did it anyway, because that's what the proc on Rh's said - guess it speeds up the initial rxn, till it reaches equilibrium. Another point is that Na2SO4 won't bind water at higher than 32 C, so if you add it while hot and shake it as it is cooling to this temp, you will prevent caking, which is pretty necessary, i believe - the less Na2SO4 you use, the better.

I also want to note that SWIM's xperience suggests that it is often necessary to let the rxn proceed for some time - like, leave it overnight - to allow complete conversion. I really wish that someone w/TLC could look at the dynamics of this rxn, it's really confusing all the way.

I also wish very much that Foxy2 supply us all the additional details of that article on HEtSO4 preparation, esp. the time and proportion of alcohol 2 acid.

Another notion - i believe that when performing neutralization in alcohol, the degree of convertion of H2SO4 can't bee judged by the final SO4-- percentage, since alcohol undoubtedly reacts w/H2SO4 formed in hydrolysis.
What i'm trying to say, i'm not really sure as to what time, Na2SO4 quantity etc. are needed for optimal results, and this procedure needs very much to bee optimized - unfortunately, SWIM has neither money, nor equipment for doing this.

As for the test - it is based on the simple fact that CaSO4 is only very slightly soluble in water (200 mg per 100 ml), while CaAlkSO4 is well soluble. So what you do is make a conc. soln. of CaCl2, a conc. soln. of a weighed amt (somewhat less than CaCl2) of your salt, mix it, filter the precipitate, wash it w/aq., dry it well - roughly speaking, the weight of it will equal the weight of Na2SO4 in your salt (that is, if you dried the NaEtSO4 at above 32 C!).

This test is probably very imperfect, cause CaSO4 is still pretty soluble in water, more than that, presence of inorganic cations fucken increases its solubility - have no idea how much, does anyone?

Well, that's about all i can say thus far, but - an important notion - bee sure to fuse your nitrite bee4 the rxn, it seems to bee important, and it's usually quite wet (very hydroscopic).

Good luck,

Antoncho

[Bandil]

Sound like a bit confusing reaction. Swims not sure what to do with the supposed NaEtSO4 now... Swim'll probably try your Ca++ test, and see what that does. How pure does the sodiumethyl sulfate have to be when reacting it with the nitrite?

What do you think Antoncho? Should swim proceed with my white salt, or start over?

Thanks!

Regards
Peter

[Antoncho]

Well SWIM's friend Vitsh reported 32% yield from 50% Naethylsulfate, based on the ethylsulfate, of course. So it seems like you can do fine with at least 50%.

The key to success is having all the reagents dry and as finely mixed as possible - i recommend 1st grinding them separately, then combining them in small proportionate amt's and grinding the fuck out of'em.

Also keep in mind that SWIM doesn't know details of the rxn w/ethylsulfate. Particularly the temp. It was ~190 C for MeNO2, but the proc. on Rh's says ~130 C for EtNO2, so take care.

Antoncho