Sodium Ethyl Sulfate from CaCO3, H2SO4, EtOH

MistaMiyagi · Dream Team

A condensation from the late Rhodium's Nitroalkane FAQ:

Materials
23g CaCO3, finely powdered
16mL conc. H2SO4(aq)
40mL EtOH
200mL H2O
suff. sat. Na2CO3(aq) to basify
suff. CaCl2 to dessicate

Procedure

Slowly add 16mL H2SO4(aq) to 40mL EtOH.
Heat to a gentle boil for 45 minutes, then let cool.
Pour solution into 200mL H2O.
While stirring vigorously, add 23g CaCO3 to solution.
Heat solution to 60°C and, while hot, collect product via suction filtration, discarding solids.
Basify filtrate with Na2CO3(aq) dropwise.
Evaporate filtrate on a water bath to saturation and let stand overnight.
Collect product via suction filtration, discarding solids.
Dry in a dessicator with CaCl2.

Yield: 12g sodium ethyl sulfate

thenewrunne · Chemically Balanced

Would it be OK to use:

45% EtOH and 35% H2SO4 directly in this reaction? Difference in mols of course being factored into it.

I assume that the end product, sodium ethyl sulfate is a nonpolar liquid?

Richy · Thu Jun 09, 2005 5:43 pm

Bushroot · Sat Jun 11, 2005 1:07 am

I strongly not recommend you to use the method above.

To achieve high yields of ethylsulphate you need to decrease the hydrolysis of ethylsulfuric acid. To do this you must perform all reactions in corresponding alcohol (Ethanol in case of ethylsulphate). You will get all your ethanol back after completion.

Procedure.
In 500 ml RB Flask was added 100 ml EtOH. 96% Sulphuric acid 100 ml (180g) in small portions was added carefully with cooling. Na2SO4 60 grams were then added and the mixture heated to 120C and kept at that temp for 1 hour. Na2SO4 was filtered off and gave 130 ml of pink ethylsulphuric acid.
In a 500 ml RB flask in 300 ml EtOH (its essential to use not less alcohol, you'll se why if you wont) were added 66g unhydrous K2CO3. 75 ml of ethylsulphuric acid were added dropwise with mixing. The ethanol is then distilled off. The wet salt was heated on a plate standing on a water bath removing the remants of ethanol . Yield approx 85g.

Bushroot · Sat Jun 11, 2005 1:09 am

Sodium ethyl sulphate is a white cristalline powder. It's a SALT dude, SALTS are never liquids (except TiCL4)
You can't do this reaction with diluted H2SO4 or alcohol

thenewrunne · Chemically Balanced

^^^

Bushroot · Sat Jun 11, 2005 3:55 pm

Water in this reaction is used as a solvent but it fits here very badly
By adding h2so4 to ethanol you get sulphuric acid monoethyl ether (C2H5OSO3H). This ether is then being neutralized by Na2CO3 to etylsuphate. During neutralization the reaction mix thickens and you won't be able to add any more ethylsulphuric. You can do this reaction in water with low yields (less then 12g - such small amounts wont thicken the rm noticable) or in alcohol with higher yield (almost 85g).

If you are going to make nitroethane from it you must know that from 50g of sodium ethyl sulphate and 50g NaNO2 you will get maximum of 6 ml of nitroethane... So to scale the reaction with water to suitable amounts you will need crazy amounts of H2SO4 and ethanol. Filtering Calcium ethylsulphate is a real pain in the ass as many ppl say

thenewrunne · Chemically Balanced

Ahh.. well I'm glad I asked then! I'll use 99% or best I can manage for the ethanol.