Author Topic: Ether  (Read 2076 times)

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ADDkid

  • Guest
Ether
« on: May 06, 2004, 10:23:00 PM »
I know this question is a very amateur question, but I will risk the flaming for the answer.

When dealing with very volatile solvents like ether, can one safely keep it in a glass bottle with a screw-top lid, does the vapor reach equilibrium or can the pressure build up and break the glass, or the top.  If ether was kept in a glass flask with a calcium guard tube would this be better. Also, would it be better to keep ether in the freezer? ADDkid

ApprenticeCook

  • Guest
im thinking you mean ether as diethylether,...
« Reply #1 on: May 06, 2004, 11:02:00 PM »
im thinking you mean ether as diethylether, the most common one used, ether is a term for a functional group, not one individual chemical.

as for diethylether storage (from the msds document for it):

Storage Precautions:
Store in cool place and out of direct sunlight. Store in well ventilated area. Store away from sources of heat or ignition. Store away from oxidizing agents. Store away from acids. Keep containers closed at all times.

Other Storage Info:
Periodically test for peroxide formation on long-term storage. If peroxide formation is suspected, do not move or open container/s. Do not distill or allow to evaporate to near dryness. Opened containers should be purged with nitrogen and resealed.

Boiling Point: 34.5 °C

Vapour Pressure: 442 mm Hg @ 20 °C



The pressure wont build up unless you heat the container.
No to your idea, the container must be sealed.
Freezer? not a bad idea...

-AC


ADDkid

  • Guest
Thanks for your input, The Term "ether
« Reply #2 on: May 06, 2004, 11:29:00 PM »
Thanks for your input,
The Term "ether", is a term used because the prefix "di" is neglected when naming symmetrical ethers.  It is however not as good as the common name "diethyl ether", but if you really want to be correct the name is ethoxyethane. ADDkid

P.S.  When something is heated pressure does build up, and when something is highly volatile pressure can also accumulate.  So I guess my question should be clearer.

Does ether have a strong enough vapor pressure to cause a glass bottle to explode, or break the top? Example, care must be practice when doing a ether extraction.

ApprenticeCook

  • Guest
True... was only making the correction so i...
« Reply #3 on: May 06, 2004, 11:35:00 PM »
True... was only making the correction so i could look up the VP and BP.

_mu_

  • Guest
>Freezer? not a bad idea...
« Reply #4 on: May 07, 2004, 02:12:00 AM »

>Freezer? not a bad idea...


Freezer is a *very* bad idea. You will have ether fumes in your freezer, and a sparkling motor nearby. It's not a question if your freezer will explode, only when.

starlight

  • Guest
Ether
« Reply #5 on: May 07, 2004, 04:09:00 AM »
Ether is normally stored in dark glass bottles with a screw cap lid. The bottles must be kept away from direct sunlight and heat sources.

If you buy ether it will come in a glass bottle.

If you distill ether from starter fluid, this process will remove any stabilizer that is present, therefore making the ether liable to peroxidization. Peroxides of Diethyl ether are explosive shock/friction sensitive. If distilling starting fluid, it is best not to keep the result for a long time no matter what sort of bottle you are putting it in. Using a guard tube rather than a screw cap is just asking for trouble as it will leave the ether exposed to atmospheric oxygen (which oxidizes the ether and forms the peroxides).

Ether should be used away from all sources of ignition and that includes sparks which are present in all fridges and freezers apart from those specifically designed to cope with volatile, inflammble, explosive solvents.

embezzler

  • Guest
freezer = bad
« Reply #6 on: May 07, 2004, 04:57:00 AM »

Osmium

  • Guest
Ether will not solidify in the freezer.
« Reply #7 on: May 07, 2004, 05:04:00 AM »
Ether will not solidify in the freezer.
The expansion of water while it freezes is a rare exception. Nearly all other substances contract during solidification.


hypo

  • Guest
??
« Reply #8 on: May 07, 2004, 05:09:00 AM »
a foaf always stores his ethereal solutions in a freezer.
it never happened that the glass broke or that the thing
exploded. (glass only breaks when filled with water, since
it is one of the few substances that expand on cooling and
ofcourse _all_ solutions should be tightly closed, so no risk
of fumes either)

as for storage: as long as it's tightly closed, no problem
in a cool (<=25°C) place. of course there is some pressure
build up, but with increased pressure boiling point does
increase too. don't use a normal glass stopper without
clamp though, or you know what happened when it makes
"popp..........................clank"  ;D


embezzler

  • Guest
swim stands corrected
« Reply #9 on: May 07, 2004, 05:12:00 AM »
swim stands corrected


randolph_carter

  • Guest
storing ether exposed to O2 is dangerous...
« Reply #10 on: May 07, 2004, 10:53:00 AM »
i know some will have different opinions as did i before this incident....

on many occasions i let diethyl set about in the freezer, with nary a problem......

but i know from real meatspace experience that an aldrich anhydrous diethyl tin opened one time only and stored in a freezer for about 4 weeks blew the fukn freezer totally up!!!!

lost a fair amount of product being rextalled to boot!!!

from my experience it will destabilize......
it is purely a matter of time/luck?....

produce/open only what you can actually consume in a short period of time is the best course of action...

or use another less volatile solvent possibly......

beeaware!!!!


Aurelius

  • Guest
Frig
« Reply #11 on: May 07, 2004, 01:12:00 PM »
some are made for storing chemicals.  (explosion proof)

still, it's a good idea to close the bottle/container tightly and wrap the opening with parafilm.  (stretchy wax film that can be bought several places on the internet- and no, nobody cares if you purchase this stuff.  it's used for the same type of purpose in biological studies all the time)

I've never seen diethyl ether sold in a glass bottle.  It's always been in an aluminum can with a plastic screw cap.  the bottom has a depression that will pop out if too much pressure is building up.  As long as you're storing ether at RT or below, pressure in the container shouldn't be a problem.


ADDkid

  • Guest
Yes, you are right, I have only seen it store...
« Reply #12 on: May 07, 2004, 09:23:00 PM »
Yes, you are right, I have only seen it store in a Al container, I would think that a toluene or acetone container should be fine, Peroxide can be check wit jones reagent, and they can be removed easily with Ag/NaOH solution. ADDkid

starlight

  • Guest
depends where you buy it
« Reply #13 on: May 08, 2004, 08:01:00 AM »
Whether ether comes in a glass bottle or an aluminium can will depend upon where you are buying it from. In some countries glass bottles are the norm.

Organikum

  • Guest
Adding some copper wire will prevent any ...
« Reply #14 on: May 08, 2004, 08:23:00 AM »
Adding some copper wire will prevent any peroxide formation - it will not destroy already formed peroxides.
So storing ether exposed to air isnt so good an idea anyways, but some copperwire will stabilize it well.


Vaaguh

  • Guest
BHT
« Reply #15 on: May 09, 2004, 07:09:00 AM »
A tiny ammount of the food preservative BHT (butylated hydroxytoluene) can also be used to stabilize ether.


ning

  • Guest
Yes
« Reply #16 on: May 09, 2004, 10:48:00 PM »
It's a damn strong reducing agent.
Actually, I bet they use it to dry the ether too, as it will destroy any water it touches as well.

But if you have CaH2, you should make some alkoxides with it.

Organikum: How about aluminum strips, given that it is a better reducing agent? Or is this one of the reasons they keep ether in an aluminum bottle in the first place?


abolt

  • Guest
Steel drum
« Reply #17 on: May 09, 2004, 10:50:00 PM »
I have seen Ether in plain old 20 litre S/S drums.

politoxicomania

  • Guest
Ethers
« Reply #18 on: May 11, 2004, 11:05:00 AM »
Store them over hydroxides. Dry them with Na/K.

biffman

  • Guest
My freezer remains intact
« Reply #19 on: May 13, 2004, 04:23:00 PM »
Swim here has always obtained ether (diethyl of course) in a glass 4 liter bottle and has always kept it in the freezer.  If anyone has had any explosion happen this way it was because their container was not sealed properly.
  I've actually never seen diethyl ether come in a metal container as apparently other people here have.  I've had lots of solvents supplied in metal containers with their notoriously hard to seal screw caps but ether?  That's just nuts.
  Transfer it to a good glass jug and just be aware of the dangers of distilling to dryness due to the possibility of accumulation of the unstable oxides that can form.
  Although I've never had to do it myself, but accordinng to Merck they should be fairly easily removed by shaking with Ferrous Sulfate (if I remember correctly).

moo

  • Guest
Literature on peroxides in ethers with refs
« Reply #20 on: July 25, 2004, 12:10:00 AM »
The Chemistry of Functional Groups: The Chemistry of Ether Linkage, Interscience, London, 1967, p.694:


3. Inhibition of peroxides

No single method seems to be suitables for inhibiting peroxide formation in all types of ethers, although storage and handling under an inert atmosphere would be a generally useful precaution.

Some of the materials which have been used to stabilize ethers and inhibit formation of peroxide include the addition of 0.001% hydroquinone or diphenylamine33,35, polyhydroxyphenols, aminophenols, and arylamines. 0.001 g of pyrogallol in 100 cc ether was reported to prevent peroxide formation over a period of two years32. Water will not prevent formation of peroxides in ethers, and iron, lead, and aluminium will not inhibit the peroxidation of diisopropyl ether38 although iron does act as an inhibitor in diethyl ether. Dowex-1 has been reported effective for inhibiting peroxide formation in diethyl ether39; 100 p.p.m. of 1-naphtol for diisopropyl ether 40, hydroquinone for tetrahydrofuran 41, and stannous chloride or ferrous sulfate for dioxane40 and substituted stilbenequinones have been proposed42 as stabilizers against oxidation of ethers and other compounds.

4. Removal of peroxides

Reagents which have been used for removing hydroperoxides from solvents are reported by Davies32 to include sodium sulfite, sodium hydrogen sulfite, stannous chloride, lithium aluminun hydride (caution: see notes in sections II.G and IV.B), zinc and acid, sodium and alcohol, copper-zinc couple, potassium permanganate, silver hydroxide, and lead dioxide. Decomposition of the peroxides with ferrous sulfate is a commonly used method--454 g (1 lb) of 30% ferrous sulfate solution in water is added to each 11.4 l (30 gal)43. Caution is needed since the reaction may be vigorous if the solvent contains a high concentration of peroxide.

Reduction of alkylidene or dialkyl peroxides is more difficult but reduction by zinc in acetic acid or hydrochloric acid, sodium in alcohol (see note on case of ignition of hydrogen liberated from water), or the copper-zinc couple might be used for purifying solvents containing these peroxides32.

Addition of one part 23% sodium hydroxide to 10 parts of diethyl ether or tetrahydrofuran removed peroxides completely after agitation for 30 minutes; sodium hydroxide pellets reduced but did not remove the peroxide contents of tetrahydrofuran after two days28. Addition of 30% N chloroform to tetrahydrofuran inhibited peroxide formation until the eighth day with only slight change during 15 succeeding days of tests28. The peroxides were removed from the mixture by agitating it with 1% aqueous sodium borohydride for 15 minutes (with no attempt made to measure temperature rise or evolution of hydrogen).

A simple method for removing peroxides from high quality ether samples without need for a distillation apparatus or appreciable loss of ether consists of percolating the solvent throught a column of Dowex-1 ion-exchange resin39. A column of alumina was used to remove peroxides and traces of water from diethyl ether, dibutyl ether, and dioxane44 and also for removing peroxides from tetrahydrofuran and diisopropyl ether32.

Calcium hydride can be used for obtaining anhydrous and peroxide-free p-dioxane45, by refluxing followed by distillation. The use of sodium and potassium borohydrides to reduce peroxide in tetrahydrofuran and diethylene glycol dimethyl ether (diglyme) and to inhibit them for some time against further peroxidation has been reported46.

For removing peroxides from ethers the need and value has been expressed for an insoluble solid which can be separated by filtration or decantation. Cerous hydroxide (Ce(OH)3) fulfills these requirements47. Cerous hydroxide, prepared from a cerous salt solution by sodium hydroxide, changes from white to reddish brown within a minute or two after addition to an ether if peroxides are present; removal of peroxides can be completed within 15 minutes. The peroxyceric compound and unchanged cerous hydroxide can be removed by centrifugation (caution:: flammable vapors ignite if the sentrifuge is electric and not explosion-proof) and decantation. After treatment with cerous hydroxide each of twelve ethers which had previously contained peroxides gave negative potassium iodide tests. After the removal of peroxides, the ethers were tested for the prescence of cerium by the benzidine test, with negative results except for allyl ethyl ether and benzyl n-butyl ether. It was noted that di-t-butyl peroxide did not liberate iodine from acidified potassium iodide solution nor did it react with cerous hydroxide47.


24. R. B. Moffett and B. D. Aspergren, "Tetrahydrofuran can cause fire when when used as a solvent for LiAlH4", Chem. Eng. News., 32, 4328 (1954).
28. E. Fleck, Merck, Sharp & Dohme Company Memo, May 11, 1960.
32. A. G. Davies, "Explosion hazards of autoxidized solvents", J. Roy. Inst. Chem., 386 (1956).
33. G. Lindgren, "Autoxidation of diehtyl ether and its inhibition by diphenylamine", Acta. Chim. Scand., 94, 110 (1946).
35. A. G. Davies, Organic Peroxides, Butterworths, London, 1961.
38. P. R. Dugan, Ind. Eng. Chem., 56, 37 (1964).
39. R. N. Feinstein, "Simple method for removal or peroxides from diethyl ether", J. Org. Chem., 24, 1172 (1959).
40. Encyclopedia of Chemical Technology, Vol. 5, (Ed. R. E. Kirk and D. F. Othmer), Interscience Publishers, New York, 1950, pp. 871, 142.
41. Encyclopedia of Chemical Technology, Vol. 6, (Ed. R. E. Kirk and D. F. Othmer), Interscience Publishers, New York, 1950, p. 1006.
42. D. G. Jones,

Patent GB699079

(1953); Chem. Abstr., 49, 3262f (1955).
43. Chemical Safety Data Sheet--SD 29, Ethyl Ether, Manufacturing Chemists' Association, Washington, D.C., 1956.
44. W. Dasler and C. D. Bauer, "Removal of peroxides from ethers", Ind. Eng. Chem. Anal. Ed., 18, 52 (1946).
45. E. R. Birnbaum, personal communication, August 11, 1964.
46. Manual of Techniques, Metal Hydrides, Inc., Beverly, Massachusetts, 1958.
47. J. B. Ramsey and F. T. Aldridge, "Removal of peroxides from ethers with cerous hydroxide", J. Am. Chem. Soc., 77, 2561 (1955).




Organic Peroxides, Butterworths, London, 1961, p. 344:



Removal of Peroxides

The gradual formation of peroxides in many organic compounds, particularly solvents and the purified hydrocarbons derived from petroleum industry, made it inevitable that means would be devised whereby such compounds could be removed or decomposed so as to avoid explosions during subsequent processing.

The use of lead dioxide for decomposition and prevention of peroxides in ether100 reflects the discovery by Criegee, Pilz and Flygare101 that hydroperoxides are converted to other compounds (generally ketones) on treatment with lead tetra-acetate or lead dioxide. Presumably the exploside cyclic peroxides present in autoxidised ether are unaffected by this reagent.

Solid potassium hydroxide102, calcium hydroxide precipitated from calcium chloride by sodium hydroxide103 and a copper-zinc couple104 have also been proposed as efficient means of removing peroxides from solvents. Some solvents can be freed from peroxides by passage through a column or alumina; this method has been found to be particularly applicable to dioxan and di-n-butyl ether, but is not so successful for diethyl ether105.

Two methods have recently been reported for treating autoxidised ether. The first utilised an acid solution of ferrous sulphate for washing the ether, and it is claimed that peroxides are reduced to at least 2.5 parts per million by this means106. In the second method the ether was treated with the hydroxyl form of the anion-exchange resing, Dowex 1; it was also noticed that if fresh ether was stored over this resin peroxide formation was largely prevented107.

Methods of removal of peroxides from olefins by treating with alkali or sulphides108, from various hydrocarbons by use of finely divided iron109, and from cracked gasolines by hydrogenation110, have all been proposed.

It has been claimed that tetrahydrofuran can be stabilised against peroxide formation by the addition of cuprous chloride111.


99. S. Dykstra and H. S. Mosher, J. Amer. Chem. Soc., 1957, 79, 3474.
100. F. R. Fisher and R. A. Baxter, Mines Mag., 1940, 447.
101. R. Criegee, H. Pilz and H. Flygare, Ber., 1939, 72, 1799.
102. W. Lepper, Chem. Ztg., 1942, 66, 314.
103. J. B. Ramsey and F. T. Aldridge, J. Amer. Chem. Soc., 1955, 77, 2561.
104. H. Fierz-David, Chimia, 1948, 1, 246
105. W. Dasler and C. D. Bauer, Ind. Eng. Chem. Anal. 1946, 18, 52
106. J. A. Dukes, Chem. Abs., 1959, 53, 11194.
107. R. N. Feinstein, J. Amer. Chem. Soc, 1959, 24, 1172.
108. Shell Dev. Co.,

Patent US2545199

.
109. Standard Oil Dev. Co.,

Patent US2563598

.
110. Standard Oil Dev. Co.,

Patent US2542471

.
111. Farbwerke Hoechst,

Patent GB948506

.





I guess the above can be interpreted so that storing diethyl ether over NaOH will stabilize it. ;)