Sciencemadness Discussion Board - Irrational fear of diethyl ether?

Irrational fear of diethyl ether?

Droso - 16-8-2015 at 10:39

Hi all,
First post here
I now this has been discussed before numerous times, but still all that information hasn't calmed me down.
Anyway, heres just a summary of my situation. Being a chemistry student, about 3 days ago I have decided to purchase a 1 liter bottle of Diethyl ether if I ever plan to do some solvent extractions in the future (It was more of an impulse purchase, I admit). Shortly after arriving home, I opened the bottle and a high pressure pop was released, almost sending the inner cap into the air. I've looked on the net for the boiling point of diethyl ether and it is 35C°. I was aware of its low boiling point, but I didn't know it was that low! We can get summer temps close to 35C° during the day and this is really taking my sleep away.
I also was aware of the peroxide problem before the purchase but only thought it forms under special conditions. After reading all the information on the net I could find I have become even more paranoid about it. The store owner told me that it is stabilized, but the label doesn't say anything. Do all manufacturers stabilize their ether (mandatory)?

I somewhat regret buying the ether and even think about getting rid of (by evaporation in a large surface area outdoors)

I have some other questions if anyone is willing to anwser them:

During a hot day (30C°+) is there a chance that the 1L amber bottle could rupture, realising the ether?

Is there other compounds that could be used to neutralize ether peroxide, other than ferrous sulfate? FeSO4 is more difficult to find where I live and no, I cant get any from where i study.

If I test the ether and it comes positive, would it be okay to just leave the neutralizing solution (ferrous sulfate or other) inside the bottle for longer storage?

Will adding more BHT than the manufacturer (in case it's really stabilized) to the ether solve the peroxide problem?

Could I use homemade sodium iodide for the peroxide test or does it need to be reagent grade?

I apologize for the noncohesive text, I don't live in an English speaking country.

Thanks

[Edited on 16-8-2015 by Droso]

[Edited on 16-8-2015 by Droso]

aga - 16-8-2015 at 10:48

Keep it in a fridge (= cold, no sunlight).

It is a dangerous thing to keep hanging around if you have no immediate use for it.

I've toyed with the idea of making ether a few times, however the risks are too great, and currently there would be no reward.

Magpie - 16-8-2015 at 11:13

Beware of fridge/freezer switches. Ether explosions have been set off by them.

Don't store it with food. Ether is very lipid soluble. It will ruin your fat containing food, eg, meats. I know this from personal experience.

I recover ether from starting fluid when I need it. I add BHT and test it periodically for peroxide with iodine. I've never had a positive result.

It would be a shame to evaporate off that ether but your safety comes first.

Aqua-regia - 16-8-2015 at 11:35

As solvent i using instead diethyl ether MTBE (methyl-tert-butyl-ether. This stuff cheaper, no waching the authority, and has no peroxide, but the same solvent properties like the other.

fluorescence - 16-8-2015 at 13:07

I ordered some stuff recently and accidentally wrote Diethylether on the list,too. It was not much,
a small bottle but I never intended to buy it at least not in summer. So I was quite nervous when
the parcel was delivered when it had between 30 and 40°C lately. I had luck since the delivery car must have
had a very good air con. The parcel came quite cold and so nothing happened to that bottle of Ether.

byko3y - 16-8-2015 at 13:24

You can't make grignard with MTBE. And why would I need it otherwise? I've got dichloromethane (43°C), hexane (68°C) and ethyl acetate (77°C).
Diethyl ether is so precious, so I use it for huffing only. It's really hard to make a pure one from starting fluid via distillation, you need to distill it few times. At least it has no peroxides (AFAIK there's stabilizer).
Yes, you should store it in fridge, otherwise you need a pressure resistant vessel with a good seal.

Little_Ghost_again - 16-8-2015 at 14:22

I dont have a fridge but outside at the back of an outbuilding where there is shade, I stuck my bottle in a bucket with a lid and dug a hole 3 feet deep. The ground stays cool (not measured it but must be below 5c?). Not dug it up for ages but the few times I have it was fine.
Probably a bit hobo a method but in a pinch?

Magpie - 16-8-2015 at 14:47

I love the idea of having a styrofoam cooler placed in a shallow hole for year-round storage of volatile chemicals. It's the "root cellar" approach.

I store about 100 ml of ether in an amber bottle with ptfe seal in my garage with no problems. So it pressurizes a bit - so does a bottle of beer.

aga - 16-8-2015 at 15:08

Beer must be stored in an appropriate container that will preserve it's salient features at all times.

This the Whole of the Law.

diddi - 16-8-2015 at 17:59

@aga - beer must be consumed before any chance of over pressurizing or wasting comes into play.

AvBaeyer - 16-8-2015 at 18:53

I buy ether in aluminum bottles with a two piece pressure cap. I have never detected any leaking vapors with these bottles. No light exposure and no danger of broken bottles or poorly sealing bottle caps. I would NEVER buy ether delivered in glass or store it in glass. As for storage, a separate "solvent box" with a fairly tight closure kept in a cool place has been more than sufficient.

AvB

gdflp - 16-8-2015 at 21:01

An OTC source of aluminum bottles that I used to use are some Coke bottles. They hold 250ml, are quite cheap, and work great for holding a small quantity of ether once they have been used for their original purpose

. I sand the labels off to make them look nicer, but that's really just a matter of aesthetics. They don't seem to have a plastic liner and are made out of solid aluminum. Here's an example:

FriedBrain - 16-8-2015 at 21:31

I would label them off, not just for asthetics, but because storing chemicals in food bottles is kind of dangerous. The chance should not be there, that any want is aware of drinking it, there always some idiots out there, maybe you have sometimes thirsty guests visiting you?

Magpie - 17-8-2015 at 02:55

Quote: Originally posted by AvBaeyer

I buy ether in aluminum bottles with a two piece pressure cap. I have never detected any leaking vapors with these bottles. No light exposure and no danger of broken bottles or poorly sealing bottle caps. I would NEVER buy ether delivered in glass or store it in glass. As for storage, a separate "solvent box" with a fairly tight closure kept in a cool place has been more than sufficient.

AvB

I have ether and pet ether in glass. I'm going to get some aluminum bottles.

What is a "two-piece pressure cap"?

Shouldn't solvents ideally be stored in a vented metal cabinet?

Little_Ghost_again - 17-8-2015 at 03:16

Never seen those bottles in Scotland, but then again not many shops around where I live. Dunno why but I prefer Glass, mine is in the bottle i got it in. I am going to dig it up later and take a look. i distilled some petrol and the lowest boiling point stuff I stuck in glass bottle. its in the garage :O! Now I am thinking maybe that should be in the hole.

Out of interest when distilling petrol would vermiculite do instead of sand? I thought it might be to good an insulator to pass heat through. but sand takes ages to get hot on my plate. I have a hot air paint stripping gun i use for shrink wrap wire tubing, may i should use that to heat the flask with the petrol? (carefully of course).

Little_Ghost_again - 17-8-2015 at 03:19

Quote: Originally posted by Magpie

Quote: Originally posted by AvBaeyer

I have ether and pet ether in glass.

Ok you love chemistry and are good at it, but giving a solvent a name and calling it a pet is getting a bit strange

, I know people used to have pet rocks as dad still has his LOL but pet ether?? OBSESSIONAL!

kecskesajt - 17-8-2015 at 03:23

I take my pet ether on a walk in the morning.
Pet. ether = petroleum ether.Use a dot.

woelen - 17-8-2015 at 03:26

Pet ether is not a pet

It stands for petroleum ether, which is a mix of alkanes with a certain boiling range (e.g. petroleum ether 40...60, or 60...90). These are nice quite inert non-polar solvents, useful for degreasing, but also a good replacement for the much more expensive hexane or heptane in many cases.

I store my ether in a glass bottle with a soft plastic cap and I put an Al-foil liner (cut from household aluminium foil) inside the cap to make it non-porous for the ether. The smell of ether around my bottle is only very faint.

Sulaiman - 17-8-2015 at 03:42

Looking at the wikipedia data page for diethyl ether https://en.wikipedia.org/wiki/Diethyl_ether_(data_page)

ether in an open container (1 atm or 760mm Hg) boils at 34.6 C

at 56 C in a sealed bottle there would be an internal pressure of 2 atm
so the container would have to support an effective (gauge) pressure of 1 atm
not a problem.
(until you open the container !)

not a really hot summer here in central UK, but I have 100ml glass bottles of
ether, chloroform, methanol, ethanol, carbon disulfide and toluene on a shelf in my shed/lab,
so far no problems.

So I would say that diethyl ether deserves 'respect'
but a fear of (small quantities of) diethyl ether is irrational.

P.S. my shed has natural ventilation (not too good in the winter) so I'm not too concerned about gradual build up of vapours

[Edited on 17-8-2015 by Sulaiman]

Magpie - 17-8-2015 at 05:12

I keep my 1L bottles of solvent, including my lawn mower gasoline, in an outside shed away from the house. It has 2 small vents and I leave the door open on occasion.

However, I have some smaller glass bottles of 100ml or less of solvent for day use in my lab in the garage. I also have a gas hot water heater in my garage.

Almost every day in my community of ~ 200,000 population someone's house burns down accidentally.

aga - 17-8-2015 at 07:02

Quote: Originally posted by Magpie

Almost every day in my community of ~ 200,000 population someone's house burns down accidentally.

That's a clear sign that either you need stop building houses out of wood, or increase the average intelligence of the inhabitants.

unionised - 17-8-2015 at 10:45

Quote: Originally posted by aga

Keep it in a fridge (= cold, no sunlight).

It is a dangerous thing to keep hanging around if you have no immediate use for it.

I've toyed with the idea of making ether a few times, however the risks are too great, and currently there would be no reward.

No.
Don't store it in the fridge unless you have a specified "spark proof" fridge. (unless you paid a lot of money for this feature, your fridge hasn't got it).

Someone kept some urine samples which had been extracted with (and thus were saturated with) ether in an ordinary fridge where I work.

The vapour leaked out mixed with air and the thermostat ignited it. the resulting explosion tore the door off its hinges and threw it across the room where it smashed a hole in the wall.

The flash point of ether is a lot lower than the temperature of a fridge.

Aga, sometimes you should wait till you sober up a bit before you post.

gdflp - 17-8-2015 at 10:51

Quote: Originally posted by FriedBrain

I would label them off, not just for asthetics, but because storing chemicals in food bottles is kind of dangerous. The chance should not be there, that any want is aware of drinking it, there always some idiots out there, maybe you have sometimes thirsty guests visiting you?

I assumed this would be obvious, but it is still a good point. The bottle should be clearly labeled otherwise if the label is not sanded off. Although natural selection should apply if anyone decided to drink something in MY lab

. As long as they were off my property before they keeled over

AvBaeyer - 17-8-2015 at 18:43

Magpie:

In answer to your question: "What is a "two-piece pressure cap"?

Perhaps a wrong choice or terms. My aluminum ether bottles come with a plastic stopper which is pushed into the bottle mouth. A rubber gasket is between the lip of the stopper and the bottle top. Then a heavy plastic screw cap is used to hold the stopper in the bottle mouth. I guess it could be visualized as: bottle mouth-gasket-plug-screw cap. I hope this is clear.

AvB

Magpie - 17-8-2015 at 19:22

Yes, I see. Sounds like a fairly sophisticated closure system. It might be difficult to buy a bottle like that, specifically designed for ether & such.

Little_Ghost_again - 18-8-2015 at 03:27

ONLY on here could I crack a joke and get more information on Pet. Ether than I could ever read!! Just so we are clear and I look less retarded, I did know what was meant and the PET crack was just a joke

.

Never thought about the thermostat in a fridge sparking, easy to solve with something like a DS18s20 temp sensor and a few bits. No idea how you would seal a fridge enough to make the rest of it safe. Bit harsh on Aga seeing as clearly no one where you worked thought of it or you would still have a fridge with a door on! Not starting but just saying it was a bit harsh on him.

Amos - 18-8-2015 at 05:41

The formation of peroxides can be avoided by storing your ether over prills of sodium hydroxide, which in my experience is very convenient as they tend to stick to the bottom surface and sequester any water as well.

As for ferrous sulfate, it can easily be prepared quickly and in large amounts by a single replacement reaction between copper(II) sulfate(root killer in many places) and an excess of steel wool. Filter the solution, boil it down in a long-necked container to keep air out, and crystallize. Done.

Little_Ghost_again - 18-8-2015 at 06:05

Quote: Originally posted by Amos

The formation of peroxides can be avoided by storing your ether over prills of sodium hydroxide, which in my experience is very convenient as they tend to stick to the bottom surface and sequester any water as well.

As for ferrous sulfate, it can easily be prepared quickly and in large amounts by a single replacement reaction between copper(II) sulfate(root killer in many places) and an excess of steel wool. Filter the solution, boil it down in a long-necked container to keep air out, and crystallize. Done.

Just to clarify and sorry for the question.............. You mean putting the prills into the ether solution?

or did you mean in the container where the ether is being stored?
Sound great either way and tip noted

gdflp - 18-8-2015 at 10:45

Quote: Originally posted by Little_Ghost_again

Yes, directly in contact with the ether. The peroxides are not volatile so the hydroxide would have no effect on them if not in direct contact.

Droso - 19-8-2015 at 19:43

I'm less worried now about pressure built up in the bottle since temps, have been mild these days. I also have an old water cooler that I can use to submerge the bottle in chilled water during hot days.
The peroxide formation is what worries me the most at the moment. I got a response from the manufacturer via email and they said their ether is always stabilized with BHT, but I just don't seem to trust them. Would it be wise to add a few mg of BHT to my ether just to be safe?

Quote: Originally posted by Amos

Yes, I have been reading about sodium hydroxide in ether to stop peroxides, but will it work permanently?
That seems like a good way to make ferrous sulfate, but how would I avoid the contamination by small quantities of ferric sulfate during the reaction? No contact with atmospheric oxygen seems impossible. Would that make the ferrous sulfate useless to neutralize ether peroxide?

If there is really no way to stop the formation of explosive peroxide in the long run even if the ether is stabilized or by adding sodium hydroxide then most likely i'll get rid off, because right now it feels like I have a time bomb waiting to explode.

[Edited on 20-8-2015 by Droso]

gdflp - 19-8-2015 at 20:07

Quote: Originally posted by Droso

Would it be wise to add a few mg of BHT to my ether just to be safe?

There isn't any real downside except for a slightly larger BHT contamination in your final product if you perform any extractions. This isn't a big deal and is definitely worth it if you want peace of mind.

Quote: Originally posted by Droso

That seems like a good way to make ferrous sulfate, but how would I avoid the contamination by small quantities of ferric sulfate during the reaction? No contact with atmospheric oxygen seems impossible. Would that make the ferrous sulfate useless to neutralize ether peroxide?

Ferrous sulfate is actually quite resistant to atmospheric oxidation if kept in a slightly acidic solution, e.g. add a few ml of sulfuric acid. The reaction of ferrous sulfate to destroy peroxides is as follows, ROOR' + 2H+ + 2Fe2+ --> ROR' + H₂O + 2Fe3+. Thus, a small amount of ferric ion contamination in your ferrous sulfate has no impact as long as enough ferrous ions are still present to be oxidized. To be sure all peroxides have been removed if you suspect that your ferrous sulfate has been oxidized to ferric sulfate, test the ether afterwards for peroxides with acidified iodide. If still present, repeat as necessary.

My exciting discovery, to myself, of + pressure and seperation.

Amateurpharmacologist - 22-9-2015 at 10:32

Hey guys so this is something I just recently posted on reddit but, I would like to share it here because I think this a better environment to share things I've learned. So the following will be my copy-and pasted post.--- This is something I have just discovered, to myself. Whilst isolating, through fractional distillation, diethyl ether from starter fluid containing both light and heavy napthenic lubricants, I was able to visually separate the un-wanted lubricants from the aq. solution left in the reaction vessel by putting the heptane and lubricants under pressure. They first looked a cloud white distillate which now rests at the bottom. I find that really quite interesting. I will soon put my fresh anhydrous diethyl ether under the same vacuum and pressure experiments. The complete list of ingregients in this start fluid can were: heptane, ether, CO2, and light napthenic lubricant 64742-53-6, heavy napthenic lubricant 64742-52-5. I believe the precipitate is indeed the lubricant(s) because of the smell and high boiling point. awesome.

Thanks for reading and any input, advice, criticism, or similar experiences would be read joyfully.
-AmateurPharmacologist

Dan Vizine - 22-9-2015 at 12:58

I've never seen ether stored in a sealed glass container. I'm surprised that anyone would do that. This invites peroxide formation. That's why all chemical houses that sell ether (that I've ever seen in the US) use metal cans exclusively, either tin-coated steel with soldered seams or extruded and spun aluminum. The closures are really nothing special, mainly plastic with aluminum faced liners and they contain the vapor pretty well. You could be sitting 2 feet from 10 gallons of J.T. Baker ether in gallon cans and not even smell it.

Metal cans cost more to make than glass bottles, and the fact that all manufacturers of ether use metal should tell you something. Why actively court disaster? There's plenty waiting in hiding.

[Edited on 23-9-2015 by Dan Vizine]

aga - 22-9-2015 at 13:27

Quote: Originally posted by unionised

Aga, sometimes you should wait till you sober up a bit before you post.

Low probability of that.

Sometimes i post when sober.

Having the full range of human experience is also of some value, although not necessarily savoury or acceptable.

zed - 22-9-2015 at 16:19

Hot-Air gun, to heat highly volatile flammables? Fuck no.

Explosion proof items only.

When working with Ether, I used to sometimes use hotplates on waterbaths. Those hot plates were connected to long extension cords, that were plugged in, in a distant part of the house. The controls were preset, then to turn the hot plate on or off, I'd walk to that remote switch or plugin to activate. Likewise, if you have a light switch in the room, it must either be of an explosion-proof type, or you must tape it over to prevent accidental use. Lightbulbs should be the heavy duty plastic coated type, that do not fail catastrophically.

Good ventilation is helpful. Provided that any fans used, are explosion proof!
Ideally, use of a fume hood(explosion proof), or working in a open/outside area, is desirable.

No pilot lights. No spark sources. Etc., etc.

Me and the boys down at the general store, used to figure that any accident involving unplanned combustion of Ether, Gasoline type hydrocarbons, or Natural Gas..... would probably result in death. Or worse, becoming a crispy critter.

[Edited on 23-9-2015 by zed]

byko3y - 23-9-2015 at 11:23

What reaction happens between diethyl ether peroxide and stabilizers? One thing I know for sure - iron or copper salt produce hydroxyl radicals leading to acetaldehyde production, while acetaldehyde is an OXIDATION CATALYST, thus when you've mixed the diethyl ether and ferrous or copper salt, you need to distill it, otherwise your ether will slowly be converted into acetaldehyde.
But I have no idea what happens with NaOH or some other stabilizer.

karlos³ - 23-9-2015 at 20:02

Put some copper wire in it. Prevents peroxide formation even more... and don´t be so scared of Et2O, its not that dangerous, purchased one not the least bit!

clearly_not_atara - 25-9-2015 at 10:31

Unfortunately, on the Internet, the only way to determine if someone's advice is valid is to wait a few years and see if they disappear all of a sudden.

Can dioxane or dioxolane be used for Grignards? They have much higher flash points... easier to store for those without proper chemical refrigerators.

byko3y - 25-9-2015 at 13:00

Dioxane can't be used for grignard, because it forms a strong adduct or some other kind of shit with grignard.
Dioxolane can't solvate the grignard complex.
Something like dibutyl diglycol could be used. It can be made by reacting bromobutane with diglycol and alkali. It seems to be less toxic than glymes (dimethyl ethers), but I think they might be less effective than THF or diethyl ether. EP0632043B1
As you can see, grignard reagent preparation requires heating, but the positive side is that you can actually perform some grignard coupling, that requires strong heating, without changing the solvent, because glymes boil reeeealy high.

[Edited on 26-9-2015 by byko3y]

Justin Blaise - 25-9-2015 at 18:40

When you add dioxane to solutions of MeMgBr or EtMgBr, you precipitate MgBr2 and form the dialkyl magnesium compounds. These are very pyrophoric as a recent experiment has taught me.

[Edited on 26-9-2015 by Justin Blaise]

xfusion44 - 30-9-2015 at 19:57

@op

I stored it in amber bottle, with a piece of electrical tape (it would be better to use PTFE tape) and I had no problems with it, even in summer time (temperature in room didn't get over 30°C). The pressure does build up, but it's far too low to cause bottle to explode, so don't worry. Unless you'll leave it closed outside on sun or you live in the desert, there's no problem.
Please don't throw away your ether, that would be such a loss. It's very hard to get ether in my country, unless you distill it from starter fluid. Once I ordered it on ebay (200ml for about 25eur with shipping - may look very expensive for you, but that's all I could get) and now the mentioned offer on ebay is gone... I'd be very happy to have 1000ml of ether if I'd be you

Amos - 30-9-2015 at 20:09

Quote:

Diethyl ether is so precious, so I use it for huffing only.

u wot m8?

[Edited on 10-1-2015 by Amos]

byko3y - 1-10-2015 at 09:05

xfusion44, simple distillation device, sulfuric acid and ethanol are sufficient to make you own diethyl ether. That's how chemists in the old times used to obtain it, while chloroform was much more costly to prepare.

aga - 1-10-2015 at 09:14

Quote: Originally posted by byko3y

xfusion44, simple distillation device, sulfuric acid and ethanol are sufficient to make you own diethyl ether. That's how chemists in the old times used to obtain it, while chloroform was much more costly to prepare.

Please explain/provide a reference for that.

So much better if people can follow up on these things.

Detonationology - 1-10-2015 at 10:09

I think this is what byko is talking about.
Preparation of Diethyl Ether

aga - 1-10-2015 at 11:32

Excellent Detonationology.

Thanks.

xfusion44 - 1-10-2015 at 21:09

Quote: Originally posted by byko3y

Yeah, I wanted to make it that way, but I'm still missing one of reagents... Sulfuric acid. Unfortunately there isn't any H2SO4 in drain cleaning products in our country. The only way I could get it is probably lead acid battery electrolyte...

Thanks anyway

byko3y - 1-10-2015 at 23:47

85-90% H2SO4 is enough to make ether.