Wednesday, September 4, 2013

Such Things Just Don't Belong In Our Arsenal


First of all, the word arsenic is odd. Just seeing arsen juxtaposed with "Greek" makes me clench.
The form of the Greek word is folk etymology, literally "masculine," from arsen "male, strong, virile" (cf. arseno-koites "lying with men" in New Testament) supposedly in reference to the powerful properties of the substance. link
Arsenic is called the "King of Poisons" and the "Poison of Kings" due to its long history. Lesser known is arsenic's more recent role in our own poison gas warfare program. I mentioned Lewisite here, but a more formal introduction is in order. Even a non chemist can recognize arsenic's central role in Lewisite's structure. Here it is:


Lewisite

We made a lot of Lewisite shortly after WW I but we never deployed it as far as I know. Ridding our stockpiles has taken forever and an old cache was recently (2010) found in Washington, D.C. Link

Arsenic just can't doff its nasty reputation, even cloaked in disguise.

38 comments:

bagoh20 said...

Look, nothing is perfect. The important thing is does it give you nice buzz.

Icepick said...

Somewhere around the house I have an old US Army manual on Chemical warfare. The things one finds at used books sales....

edutcher said...

It looks nice with old lace.

bagoh20 said...

If anyone ever just keels over and dies in the middle of a chess match, I'm calling the cops on you people.

Icepick said...

Actually, I walked right back to one of the hall book cases (of which there are three) and pulled it right off the shelf.

Gas Warfare: The Chemical Weapon, its use, and protection against it

by Brigadier-General Alden H. Waitt, Chemical Warfarre Service, US Army, published in 1942.

(I have the second printing.)

The table printed on the inside of the covers lists chemical warfare agents, of which Lewisite is number 2, after mustard. That chart includes the following categories:

Symbol, Name, Class (gas, smoke, incendiary are the types given), Bands/Color (this seems to be how the storage containers would be marked), Loading (types of delivery), Odor, Tactical Class, Physiological Effect, Protection, First Aid, Color & State (Loaded & Released), Persistence, Tactical Uses and Field Neutralization.

Icepick said...

From the How to Tell the Gases part near the start:

M-1
Grandma smelled geranium,
Started feeling kind of bum.
Sure, you guessed the trouble right -
Grandma whiffed some Lewisite.

HS
Never take some chances if
Garlic you should strongly sniff.
Don't think Mussolini's passed,
Man, you're being mustard-gassed!

chickelit said...

Poetry or Mnemonics?

Icepick said...

Poetry or Mnemonics?

I'm assuming mnemonics. There are five listed (M-1, PS, CG, CN and HS) and they're attributed to Fairfax Downey, Major, Field Artillery.

Icepick said...

A measure of how fast things were changing in 1942. Alden Waite is listed as a Colonel on the cover, but is a Brigadier-General by the time the actual title page was printed.

Icepick said...

The M-1 poem is listed first. HS is last.

Actually, I'll just post them all.

M-1
Grandma smelled geranium,
Started feeling kind of bum.
Sure, you guessed the trouble right -
Grandma whiffed some Lewisite.

PS
Don't you find my odor sweetish?
Said flypaper to the fly.
I smell just like chlorpicrin,
And you'll think you'd like to die.

CG
Maud Muller on a summer day,
Smelled the odor of new-mown hay.
She said to the Judge who was turning green,
"Put on our mask! That there's phosgene!"

CN
Apple blossoms, fresh and dewey?
Normandy and romance? Hooey!
For the charming fragrance then known,
Now is chloracetophenone.

HS
Never take some chances if
Garlic you should strongly sniff.
Don't think Mussolini's passed,
Man, you're being mustard-gassed!

Fairfax Downey,
Major, Field Artillery

Icepick said...

I'm going to put the book back for now. I'm already reading two of the fifteen volumns of Morison's history of US Naval actions during WWII, as reference material while reading MacArthur's Reminiscences.

chickelit said...

Thanks for the gas passages, Icepick!

Icepick said...

Passing gas is my middle name!

deborah said...

What is the process to deactivate it?

Arsenic and Old Lace? I prefer The Ladykillers :)

chickelit said...

@deborah: Just treat it with a little bleach and dump it in the Gulf Of Mexico. That's what we did in the 1950s. Nowadays, it's probably incinerated, sending plumes of As2O5 into the air.

Evi L. Bloggerlady said...

It is funny how words are formed in science. It is not just in chemistry.

The Douglas Fir's scientific name is Pseudotsuga menziesii. So the first name is a combination of Greek and Japanese (tsuga is Japanese for hemlock). Menziesii is for Archibald Menziesii who was a Scottish naturalist who was the first European who documented the tree in the late 18th century.

Yet the common name is for a later naturalist, David Douglas. And they added fir to further confuse people, even though the tree is not a fir (which is of the genus Abies).

Evi L. Bloggerlady said...

My bad, Archibald Menzies. They added "ii" just to make it look good.

Palladian said...

The geranium thing interests me. Perfumery "geranium" is a plant called Pelargonium graveolens. It's a highly important essential oil in the industry and has a green/rosy /minty smell. Is this what they mean when suggesting that Lewisite smells of geraniums? Or do they mean the smell of other "true" geraniums?

Assuming that Lewisite smells of P. graveolens, then I'm wondering why it smells like that. According to my friend Luca, it perhaps smells like geraniums because the molecular vibrations of Lewisite are similar to the frequencies of the major constituents of geranium essential oil (citronellol, geraniol, linalool, citronellyl formate, p-menthone).

I would think that the sulfur atom in there would make Lewisite smell sulfuraceous. I have some arsenic green pigment (copper(II) acetoarsenite) but I've never smelled it (thankfully) so I don't know what it smells like. Those chlorines would also make it stinky I would think. There aren't many perfumery materials with sulfur, and none with chlorine I don't think.

Palladian said...

Luca says that boranes smell like sulfur (yes, he snelled one of them), even though they have no sulfur bonds, so who knows about Lewisite.

That borane smell test was one of the keys to his development of the theory of odor perception as molecular vibration.

Evi L. Bloggerlady said...

Don't geraniums ward off mosquitoes?

You all prompted me to do a A Big Tree Douglas Fir post.

chickelit said...
This comment has been removed by the author.
chickelit said...

@Palladian: There isn't any sulfur in Lewisite. I did google into its making and its typical impure, having 1, 2, or 3 acetylenes inserted into its As-Cl bonds.

Having never smelled it, I couldn't say whether it has an authentic geranium odor.

Why do seemly disparate molecules smell alike? Why does aspartame taste "sweet"? Why does BeCl2 taste sweet? (beryllium's original name was glucinium -- named after it's alleged sweet taste).

All very good questions.

Palladian said...

Hmm, I don't know why I thought Lewisite had sulfur. I guess I should have looked at the Wikipedia page. I think that "sulfur mustards" were in my head (not literally, thankfully).

Palladian said...

Disparate molecules smell alike because of molecular vibrations!

Luca once told me that "pure", single elements theoretically wouldn't smell to humans, but I don't remember why.

ken in tx said...

Chlorine bleach mixed with ammonia will burn your nose and throat and is potentially lethal. I think it creates phosgene. Anyway, in small doses it smells very sweet.

chickelit said...

@Ken: Mixing bleach (NaOCl) with ammonia makes chloramine, NH2Cl, which is probably what you smell:

2NH3 + Cl2 → 2NH2Cl

Phosgene is Cl2CO, is supposed to smell like freshly cut grass (see Icepick's mnemonic). Phosgene is made from chlorine gas + carbon monoxide. The name is confusing because it has nothing to do with phosphorus. It was originally made by using sunlight as a catalyst (phos = light + gen = forming).

The Dude said...

Back in my days working around IC foundries we were told that arsine was something one should avoid. They said it smells like garlic. Who smelled it and survived long enough to relay that information?

The Dude said...

It seems that every tree that produces aromatic wood is called a cedar. Cursory reading indicates there are only 4 true cedars in the world.

Here in the east Juniperus virginiana is called a cedar. It's not. So-called white cedars around here are actually Atlantic White Cypress trees.

Western red cedars are in the arborvitae or Thuja genus.

Spanish cedar - neither Spanish nor a cedar.

And so on and so on.

I work with eastern red cedar quite often - the aromatic overtones are fascinating - some logs actually have a peppermint smell to them.

But on the other hand, I can smell vanilla in some white oak logs - so there you go.

I have no idea what chemicals are involved in these different species of trees, but it is always a treat to work with good aromatic wood.

Red oak with bacterial infection - not so much. It's like sawing horse manure only not as pleasant.

chickelit said...

@Sixty: You're probably whiffing aromaticity

The Dude said...

Got a whiff of bullshit from Rit Mo's comments. He believes in AGW you know.

deborah said...

Will chlorine neutralize lewisite?

chickelit said...

Chlorine (Cl2) will neutralize Lewisite by cleaving off the acetylene portion, making AsCl3 and a polychlorinated organic species. AsCl3 will react with water to eventually make the pentoxide, As2O5. As2O5 is the most common arsenic species and is still poisonous. Its solubility in water is pH dependent. Arsenic needs to be sequestered to be completely neutralized.

On the other hand, humans have always lived with trace amounts of the element in the environment. I've read that there are real problems with naturally occurring arsenic in water wells in India. You've probably seen traces of arsenic as the greenish tinge imparted by chromated copper arsenate which used on pressure treated lumber. It kills termites.

deborah said...

Thanks, chick.

The Dude said...

I have inhaled plenty of the old pressure treated sawdust.

Now they use copper. Yay!

deborah said...

When did they stop using arsenic? Copper's still not great, right?

Methadras said...

I read that poster to say, "Smells like Germaniums" and I was like, whoa, Germanium has an aroma and it stays solid at room temperature now? :D

The Dude said...

Wiki is one's friend - "wood industrially pressure-treated with approved preservative products poses a limited risk to the public, but should be disposed of properly. On December 31, 2003, the US wood treatment industry stopped treating residential lumber with arsenic and chromium (chromated copper arsenate, or CCA)."

I burn my pressure treated scraps - let Sweden deal with the fallout is what I say.

deborah said...

Maverick.