[Hiernst]

Hello everyone,

I've been researching the hazards of working with ether and I thought it would be extremely helpful to get some advice from people that know way more about these things than I do.

I will hopefully be working on a wet-plate collodion photography project soon. I've taken a workshop for the process, but now that I'm going to try and do this from home, I want to make certain I'm doing things in a safe and intelligent manner - particularly with the ether, concerning the vapor buildup and storage.

For working with the photographic plates, I was thinking that I could pour the working solution (see recipe below) onto the plates outside (probably using no more than 5ml per plate) - to diffuse the vapors as much as possible - and then bring the plates indoors to work with. 

My question is - would this process be enough to eliminate vapor buildup concerns? Or would I still have to fret significantly about vapor buildup using the already poured plates in a less well-ventilated space (ie. my basement, where there could be sparks or small naked flames on occasion)?

Also, for storing the working solutions and the remaining ether (container no larger than 500ml and stored to be mixed later for future batches), I was thinking that I could store them in glass bottles with plastic caps (as full as possible), and then possibly in airtight plastic containers (with O-ring or equivalent), outside in a shed.

Does that seem reasonable and safe?  I guess my major worry is about the temperatures and possible peroxide formations.....would this be perfectly fine during NY winters? Conversely, would this be terrible in NY summers? I've read about the extremely low flashpoint, but I don't know if storing at 10 - 32 degrees Fahrenheit is good or bad.

Also would I really need to be greatly concerned about peroxide formations if I used a semi-full bottle within 6 months of first opening it? (one problem I could foresee is that the ether bottles from the distributor I'd be purchasing them from are brushed aluminum - any crystals would not be visible).

For the recipe specifics, it's all pretty low volumes. The batches of working solutions will contain: 50ml of Diethyl Ether Anhydrous, ACS, 99.99%, Certified, (for Photographic Applications), 120ml of Collodion, 100ml of Grain Alcohol (Everclear), 3ml of distilled water, 0.8g of cadmium bromide, 0.7g of ammonium bromide, and 2.5g of potassium iodide.

Maybe this is too many questions/too much information, but again - I'd love some advice on safe home usage (that doesn't involve me turning my basement into a full-fledged chemistry lab). Any comments about my ideas above or other suggestions/recommendations would be immensely appreciated.

Thanks in advance!

[billnotgatez]

I've taken a workshop for the process,

What safety precautions were done for the class?
Did the workshop discuss safety?
Did they use fume hoods or the like?

We discussed elsewhere on this forum about ether precautions
http://www.chemicalforums.com/index.php?topic=70585.0
There are other links that might be helpful as well

[Hiernst]

Thanks for replying, billnotgatez, and for the link to the other page. I had not found that one in my initial search. (glad to see that ethanol actually helps prevent peroxide formation, since grain alcohol/everclear is a big part of the recipe).

In answer to your questions, safety was discussed for the mixing and use of the collodion, but nothing really for transferring the process to home use and nothing for the longer term storage of items.  We were in a more controlled environment, as their darkroom had a ventilation system.  My home darkroom does not have a ventilation system, so that's why I was concerned about vapor buildup and why I thought pouring the plates outside would hopefully remedy most of that issue.

In trying to be conscientious about working with a volatile substance and researching the dangers, I may have gotten myself more worried than I need to be - but again, I thought it would be best to put my questions to people who have a better understanding of the nature of ether. 

Again, I'd love to hear any advice/recommendations - particularly for the outside storage (temperatures) and if using such small amounts initially outdoors would pose a risk for vapor buildup when bringing the plates indoors.

Thanks so much!

[Archer]

For the recipe specifics, it's all pretty low volumes. The batches of working solutions will contain: 50ml of Diethyl Ether Anhydrous, ACS, 99.99%, Certified, (for Photographic Applications), 120ml of Collodion, 100ml of Grain Alcohol (Everclear), 3ml of distilled water, 0.8g of cadmium bromide, 0.7g of ammonium bromide, and 2.5g of potassium iodide.

You also have Potassium Iodide in your formulation, this removes peroxides from ether converting 2I^- to I₂.

You also have distilled water in your formulation so don't waste money on expensive anhydrous ether and then add water to it.

You need to check to see if the ether you are using contains any inhibitors such as butylated hydroxytoluene (BHT) as this gives ether a much longer shelf life. I can't see any reason why 1-10ppm of BHT would affect your process.

Ether has a relatively low Lower Explosion Limit (LEL) of 1.9%. Even so that is a lot of vapour in the atmosphere. The biggest issue with ether is that the vapour is denser than air so it tends to creep along the bench if a bottle is left open and once it reaches a source of ignition the flame runs along the bench and into the bottle.

It is important that you have good ventillation and good movement of air to prevent any part of the room reaching 1.9% gaseous ether. What are the dimensions of your darkroom?

RE storage the numbers you have said are between 0 and -12°C, this is fine for storing ether. We keep ours at 20°C (68°F) without any major problems. If it gets too hot, for example 35°C (95°F) then you hit the boiling point of ether and this is when you discover if the container can take the increased pressure.

[Borek]

It is important that you have good ventillation and good movement of air to prevent any part of the room reaching 1.9% gaseous ether. What are the dimensions of your darkroom?

That was my line of thinking as well. With density of 0.71 g/mL 50 mL is about 35.5 g of liquid ether, which, once gaseous, occupies around 12 L:

<a href="http://www.youtube.com/v/oYXcbVUkGEE" target="_blank" rel="noopener noreferrer" class="bbc_link bbc_flash_disabled new_win">http://www.youtube.com/v/oYXcbVUkGEE</a>

At 1.9% it means if the ether is well mixed with a volume of a gas larger than about 630 L it is below LEL. No matter how small the darkroom is, volume of the air there is several cubic meters, so good air movement should be enough to keep the room safe from ether explosion. As the ether vapors are rather heavy, without a forced air movement they will have tendency of getting low and increase the concentration near the floor.

Doesn't mean there are no other risks.

[billnotgatez]

@Archer

You also have distilled water in your formulation so don't waste money on expensive anhydrous ether and then add water to it.

Just being the Devils Advocate here
Would you get better control over how much water is in the process if you knew that you started with ether that had no water.

@anyone else
Do we have to worry about what the ether fumes do to humans.
I think it was used as an anesthetic at one time.

Could a homemade small fume handler be enough to remove fumes
I am thinking of a scoop at the end of ducting that has a fan to move fumes outside.
http://www.sentryair.com/solderingapp.htm

[Archer]

@Archer

You also have distilled water in your formulation so don't waste money on expensive anhydrous ether and then add water to it.

Just being the Devils Advocate here
Would you get better control over how much water is in the process if you knew that you started with ether that had no water.

Good point, 50 ml of ether could hold between 0.60 - 0.75 ml water but the grain alcohol will be much more variable in the amount of water present so I don't think that control of water content is an issue here.

[Hiernst]

Thanks for the help.  Some of it gets chemically more in depth than I can respond to, but hearing that "good air movement should be enough to keep the room safe from ether explosion" is very encouraging. Sounds like I could probably forgo pouring outside as long as I kept a fan running and air circulating.

However, if I play it extra cautious in the beginning and pour the plates outside, where I imagine most of the vapors would dissipate, then bring a slightly wet plate inside and work in my small darkroom with a fan running, I think most of my worries may dissipate as well! 

And thanks for the temperature information. Seems like storing outside in spring, fall and winter would be just fine.  I'd just have to figure out another solution for the summer months, where 95 degrees plus is possible in NY.

(And just as an aside - the distilled water is for mixing the bromides and iodides into a Part A solution, then it is combined with the Part B solution - the ether and collodion - to make the actual working solution.)

Again, thank you everyone for all the information!

[Borek]

However, if I play it extra cautious in the beginning and pour the plates outside, where I imagine most of the vapors would dissipate, then bring a slightly wet plate inside and work in my small darkroom with a fan running, I think most of my worries may dissipate as well!

That's exactly what I was aiming at.