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Preparation of Diethyl ether

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Preparation 1

This is somewhat dangerous to perform with the right equipment, and


without the right gear, very dangerous!

Diethyl ether, or CH3CH2-O-CH2CH3, is a great solvent for many things, but


is extremely flammable. Professional chemists will be well appraised of the
hazards presented in using ether, but the layperson is less likely to be aware
of these dangers. Diethyl Ether vapors 'hug' the ground, and in dry air
explosive peroxides can form. In other words, even in a spark/flame free
environment, explosions can still happen when ether vapour is encountered.
For this reason its probably a good idea to have some way of removing
vapours from the vicinity (a fume hood would be a fine example) and
(Zaphraud suggests) one should not use ether on days with extremely low
humidity. Because diethyl ether is so flammable, and prone to ingition, this
procedure should be carried out using a hotplater/stirrer designed for use in
flammable environments. Such a heater/stirrer does not produce a contact
spark when the hotplate is turned on, and generally employs a brushless AC
motor for the stirrer, because DC motors with brushes generally produce
small sparks which could ignite any stray vapours.

Diethyl ether is prepared from ethanol (a.k.a grain alcohol, ethyl alcohol,
drinking alcohol) by heating it with concentrated. The reaction proceeds thru
an intermediary, "Ethyl sulfuric acid", as do most reactions of this type.
Preparation 1

by Zaphraud

The reaction is conducted as follows:

Dry (anhydrous) or nearly dry ethyl alcohol is allowed to flow into a mixture of
alcohol and sulfuric acid heated to 130 c-140 c. The vapors are collected, and
ether and some alcohol and water condense out. The sulfuric acid is a
catalyst, but since it becomes more and more dilluted as a consequence of
the water produced by the reaction, the process becomes inefficient (which is
why anhydrous ethanol is the best!)

The temperature of the reaction should be controlled carefully. At


temperatures below 130 c, the reaction is too slow and mostly ethanol will
distill. Over 150 c, the ethyl sulfuric acid decomposes, forming ethylene
instead of combining with ethanol to form ether.

95% ethanol may be recovered from water + CH3CH2OH pulled from the
bottom of the fractioning column (marked 'out')... by connecting it to another
column and distilling it...

This may be converted to 100% ethanol by mixing the 95% with calcium
oxide and distilling - the water is used up to make Calcium hydroxide! This in
turn can be re-fed to the "FEED TANK" after cooling.
Preparation 2
by Eleusis

Though this is not the most pleasant process, Diethyl Ether may be produced
by the condensation of ethanol. To do this, assemble a typical fractional
distillation setup with a vigreux column and a three neck flask. Don't forget to
drop a stirrer magnet into the flask before clamping everthing up, and you
will be heating this on an oil bath (no flames allowed when Ether is around,
you know). The vigreux column goes in the central neck, an addition funnel in
one side beck, and a thermometer goes in the other side neck.

Add 2x moles (where the x is a multiplier, 1 = 2 moles, 1.5 = 3 moles, etc...)


of the azeotrope of Ethanol (ie. 95% ethanol, Everclear) to the flask. Add 2x
moles of concentrated (98%) Sulfuric Acid (ie - Instant Power Drain Opener)
to the Ethanol slowly (it will heat because of the water). Turn on the stirrer,
turn on the heat, and bring the flask up to 130C. Make sure your condenser is
well supplied with cold water, and continue heating till the contents of the

reaction flask reach 135 C or so.

Once distillation commences, slowly add up to another 2x moles of Ethanol


through the addition funnel at a rate equal to the drops coming from the
condenser. 2 moles of alcohol (114g) should take 1 hour with a decent
vigreux column. A shorter column (or, gasp, no column at all) will require
slower distillation (and if you don't use a column, you will have to do some
extensive washing of the product with saltwater).

Dump the receiver flask contents into a large beaker or bowl and swirl with
10% Sodium Hydroxide solution until the pH is neutral. Pour this mixture into
a separatory funnel to separate the Ether from the aqueous hydroxide and
wash twice more with equal volumes of half-saturated Sodium Chloride
solution (~18g/100mL of water @ room temp). Let the last wash solution +
Ether rest in the flask until everything has settled, then carefully drain off the
wash, and pour the Ether out of the top into a round bottom flask. Add 15g of
Calcium Chloride (Damp-Rid) for every mole of Ether, drop in stirrer magnet
and stir for 2 hours.

Distill the Ether from the Calcium Chloride by heating on a bath (oil or water)
at no higher than 45C! Collect distillate that comes over in the range of 31-36
C.
Preparation 3

Diethyl Ether

This is also called ethyl ether or ether and must not be confused with
petroleum ether. If, for example, you see a formula calling for ether, then it
refers to diethyl ether, if it does not specify petroleum ether, then do not use
petroleum ether. 100g of ethanol (dry ethanol is best) is placed in a 1/2 liter
distilling flask, and with good cooling, 180g of concentrated sulfuric acid
(98% H2SO4 is added slowly. This flask needs a thermometer fitted, so that
the bulb dips down below the liquid surface. The addition funnel should
extend below the surface, so that the ethanol can be added below the
surface of the acid. Heat and maintain the mixture's temp at 140-145 c by
heating on a sand bath. Ethanol is run in from the addition funnel at the same

rate as the liquid distills over (about 2 drops per second). Mark the flask
before distilling, so that you can be sure of the addition rate. After about
150g of alcohol (ethanol) has been added, stop heating. The distillate will
require the following purification steps: Shake twice with 50 cc of 10% sodium
hydroxide solution, to free from sulfuric acid. Shake twice with 50 cc of
saturated sodium chloride solution, to free from ethanol. The ether is then
dried over anhydrous calcium chloride for 24 hours and distilled on a water
bath, collecting the fraction boiling at 35 C. Yield: 100g.

Anhydrous Ethyl Ether. This is for those formulas calling for dry, pure, or
anhydrous ether. The ether product from above is dried over thin slices of
metallic sodium (metallic sodium wire works well also) for 24 hours. Then the
ether is distilled on a water bath, over fresh (fresh means a different batch
than what you used to dry with) metallic sodium. Note: Ether develops
explosive peroxides upon sitting for any length of time, even if just purchased
from a supply house. Therefore, before handling ether, which has been
stored, shake with ferrous sulphate or with lead peroxide. To keep peroxides
from forming in fresh ether; add several sections of copper or iron wire to the
dark container and store in a cool place.

10) Preparation of Absolute Ethanol from Grain Alcohol


Absolute, or 99.5% water-free, Ethanol is frequently necessary in many
organic operations. It is quite easy to prepare from the azeotrope with water
such as "Everclear" brand grain alcohol, "moonshine" or "Rectified Spirits" (an
old term for the same thing).

Dehydrate 75g of fresh anhydrous Calcium Oxide in a vacuum dessicator for


24 hours (a bit redundant, I know) or heat in an oven at 200C for 2 hours,
then immediately transfer to the vacuum dessicator until use. Setup
glassware for simple refluxing with a water-cooled condenser and a Calcium
Chloride guard tube. Place 350mL of Ethanol into the flask, quickly add the
Calcium Oxide and hold at gentle reflux on the water bath or heating mantle
for 6 hours. Allow the mixture to stand overnight, then distill off the alcohol,
discarding the first few mL (it may be more convenient to just vent the
condenser to the atmosphere for the first couple of minutes after distillation
has commenced). Yield should be better than 315mL. Store the absolute

Ethanol in a tightly closed glass container as it will pick up water from the air
rapidly.

- eleusis@netcom.com - The Methylamine FAQ v2.5 - 02/28/96 -