Sciencemadness Discussion Board

Peculiar smell remains in nose

woelen - 13-8-2010 at 06:00

I received a bottle of 200 grams or so of PCl5 and this bottle is in horrible condition with a swollen and blistered cap and labels completely rotten away. So, I decided to repackage it in a brand new bottle with a cap having a teflon liner. As the material was one big lump, I had to crunch this with a thick glass rod and scrape this out of the old bottle. This little job took a few minutes and then I quickly transferred the pale yellow powder to the new bottle with a dry plastic funnel. All went well, but this was a really nasty little job. PCl5 gives off dense white fumes and has a very pungent smell (acrid and stinging like HCl but also some very peculiar spicy smell as well). I have done my best not to inhale these fumes, but it could not be avoided completely.

Now, almost 20 hours later I still have that strange spicy smell in my nose. I do not have any other effects, no irritation or other bad things, just that very special smell. During the day, the effect slowly decreased, but still it is there.

Has anyone of you similar experiences with chemicals? Is this effect real, or does it only exist between my ears. Or is this an effect, specific for PCl5?

hissingnoise - 13-8-2010 at 06:49

Quote:
Now, almost 20 hours later I still have that strange spicy smell in my nose. I do not have any other effects, no irritation or other bad things, just that very special smell. During the day, the effect slowly decreased, but still it is there.

That smell, woelen, could possibly be from phosphoric acid deposited from inhaled phosphorus oxychloride.
And likely harmless. . .


Paddywhacker - 13-8-2010 at 14:57

Proteins that have been chlorinated slowly release chlorine. Think of the smell of skin that has been in contact with bleach. Your persistent smell could be something like that.

chemrox - 13-8-2010 at 19:39

or your olfactory nerves said, "tilt!" Get a respirator Woelen! Your eyes will thank you as well.

psychokinetic - 13-8-2010 at 23:05

Quote:
I received a bottle of 200 grams or so of PCl5 and this bottle is in horrible condition with a swollen and blistered cap and labels completely rotten away.


I'm not surprised... doesn't this stuff melt concrete?

len1 - 14-8-2010 at 00:23

Yes. I wrote this very thing a few months ago (not in this forum). PCl3, POCl3, and PCl5, in this decreasing order of severity due to volatility cause major respiratory irritation, despite minor initial effects.

My experience was with the former two (PCl5 I never smelled as its vapor pressure is too low ordinarily). The odor takes a few seconds to register, and is very similar to HCl, there is a slight difference - and spicy is a possible descrption. In any case, unlike HCl the smell persists after the source has been removed. It is particuarly noticeable when breathing in deeply, and response to other odors is dulled, and their smell is even altered somewhat. I found the effect wears off after 6hrs or so (obviously its a function of exposure).

The real danger is that POCl3 is structurally and thus functionally similar to phosgene, and thus just like the latter delayed pulmonary edema is listed as possible.

Formatik - 14-8-2010 at 01:20

Nitrogen trichloride does something similar, it is very persistant, and stays in the breathing organs for a long while. I had to inhale ammonia mixed with air (doing this for PCl5 inhalation may not be a good idea though), because heavy air breathing didn't get it out after several minutes.

Mr. Wizard - 14-8-2010 at 07:20

I second the suggestion of getting a respirator. I transferred a small amount of copper acetate a few years ago, and even being careful, managed to get some of the dust in my throat, causing a nasty flavor and a sore throat. Try transferring some fluorescein while being 'careful', and then get a good UV light out and see how successful you were. My bet is on epic failure, and fluorescent urine. Only half joking about the urine.

Sandmeyer - 14-8-2010 at 07:58

Quote: Originally posted by woelen  


Has anyone of you similar experiences with chemicals?


I had similar experience, not after smelling but after tasting less than a miligram of a chemical, initially it got me nervous about being permanent, but I thought even if it would be permanent, which is impossible -- not even life is permanent, I would develop tolerance, i.e I would get use to it. The taste was there whole day, then it went away. :)

woelen - 14-8-2010 at 09:01

For me the smell is gone now. I had no adverse effects. I only had a few not too strong whiffs of the vapor, otherwise I would have been caughing and sneezing like hell, but nothing like that. I just was curious about that phenomenon, it never happened to me before with other chemicals.

So, apparently it is something specific for PCl3, POCl3 and PCl5. I don't have PCl3 and POCl3, so I cannot say how they smell. I can indeed imagine that POCl3 is particularly dangerous to breathe and I certainly will not try it. It can be made by mixing P4O10 with PCl5 and heating this mix. According to literature, this reacts giving POCl3. With water, PCl5 forms H3PO4 and HCl. I can imagine though, that when only a very little amount of water is used, then some POCl3 is formed as well, but I do not think that happened when I had the smell of PCl5 (under those conditions of course there is a large excess of water).

Of PCl3, POCl3 and PCl5 I think that PCl5 is safest to handle. It is a solid, which can easily be handled with a plastic spatula. But still, handling this kind of stuff certainly is not like handling e.g. copper sulfate, potassium nitrate or sodium sulfite. The material is really noxious!

[Edited on 14-8-10 by woelen]

len2 - 15-8-2010 at 00:42

I had resublimed PCl5 from a stores bottle recently and found this did not lower the phosphite peak in the ionic chromatograph spectrum (PCl3 hydrolyzes to H3PO3) below the 10% mark. So despite this being claimed as a purification procedure for PCl5 in various literature sources it seems disproportionation is inevitable. The equilibrium

PCl5->PCl3 +Cl2 is about 0.04 at 190C, giving about 10% PCl3, so my results are not surprising.

At room temperature I believe a noteable vapor pressure also exists and due to its greater volatility it could well form a substantial part of the odor.

Panache - 21-8-2010 at 08:40

For very dense gases (cf air), like cl2, they have a tendency to remain in the bottom of your lungs due to gravity, getting slowly absorbed and exhaled. Standing on your head or lying down on the couch with your head tilted backwards means that instead of hours it only takes a few deep breaths, exhaling completely, to remove the dense gas.
Have no idea if this explanation pertains to this circumstance, breath in some more and see if the smell persists whilst standing on your head.

Len which forum did you converse on regarding the phosphorous halides?

unionised - 21-8-2010 at 13:25

"For very dense gases (cf air), like cl2, they have a tendency to remain in the bottom of your lungs due to gravity, "
Last time I looked, one of the defining properties of gases was that they spontaneously mix.

This is why, even though hydrogen sulphide is rather denser than air, you notice if someone farts in the lift (elevator for those across the pond).

entropy51 - 21-8-2010 at 13:33

Quote: Originally posted by unionised  
"For very dense gases (cf air), like cl2, they have a tendency to remain in the bottom of your lungs due to gravity, "
Last time I looked, one of the defining properties of gases was that they spontaneously mix.
Diffusion. When you open a bottle of Br2 in one corner, you very soon can smell it all over the room. It's not exactly a stagnant tank down there in the alveoli either. The near constant air movement due to breathing mixes things up pretty well.

But I vote to give Panache extra credit for a novel idea anyways.

Magpie - 21-8-2010 at 13:49

Although I fully understand and support gaseous diffusion to complete mixing, time is involved.

Direct observation will show you that colored heavy gases like NO2 and Br2 appear to just sit in the bottom of vessels. That is why I always displace the gas in a vessel with water in my hood before presuming it is just air.

I have heard that if you fill an aquarium from the bottom half full of argon you can float an air-filled balloon at the midway for quite some time, but I don't really know for how long.

len1 - 21-8-2010 at 14:40

I can only assume from the tone of the post that Panache is pissed after the election result.

It'll be interesting to see how Abbott leads a minority govt. - should be as easy as solving a problem in general realativity for him.

Panache - 22-8-2010 at 06:22

its going to be a shambles however i am the proud resident in the first Green lower house electorate, ha! Mr Bandt won on a platform of 'more love' is needed in politics.

As for the mixing of gases in your lungs, you're not serious are you in thinking that gases mix instantaneously. The suggestion i made has been twice used by myself to great effect. Both were incidences of cl2 inhalation, the nausea that ensues in awful and persistent, until i laid upside down. It does require much cl2 to remain in the lower part of your lungs or diaphragm to have a noticeable unplesant effect. I recall smoke inhalation people being respirated, if it was just a matter of a couple of deep breathes then why would they bother?

if you want to draw an analogy with solutions, perfectly miscible solutions can remain separated for decades if undisturbed and the fact that you can smell bromine across the room or a fart in a lift does not mean significant mixing has occured only that enough mixing for your olfactory sense to register, which is very little.

len1 - 22-8-2010 at 19:16

Central Melbourne hey, uh.. you could be mistaken for thinking youre in China. More love in politics? Good luck to him, its like getting pirahnas to become vegetarian.

Gases indeed mix slowly, thats why Cl2 sinks to the bottom, but as I wrote elsewhere once mixed, they'll remain so. Trouble is they are absorbed into lungs through narrow pathways with much mixing turbulence - which is why O2 is absorbed. Cl2 is absorbed by moist tissue much better. So unless you inhaled conc. Cl2 - in which case you are dead, the Cl2 is mixed and absrobed after the first few breaths

Panache - 22-8-2010 at 20:07

I have never been to china so i'm unaware of how it would compare

ok that seems sensible enough, it doesn't however explain my observations, but it may have simply been coincidence that the symptons cleared up around the time i upended myself. When i examined the dangers of cl2 inhalation it appears the main pain comes from hcl forming on your muchous membranes, perhaps hcl sits in the lungs. What's it density, surely must be higher than air with that bulky halogen.
i always wondered how much of a pure gas like cl2 one could inhale before your body stopped you, i imagine very little, that you would essentially suffocate to unconsciousness before taking significant breaths thereby finishing you off. I guess if you built up slowly you could get tolerant to it, lol, like a 40 a day smoker, who sculls 100C coffee by the gulp.

unionised - 23-8-2010 at 10:52

I should, of course, point out that farting in lifts is wrong on many levels.

woelen - 27-10-2011 at 08:03

I distilled some POCl3 a few hours ago and now I have the same experience again. The smell is exactly the same as the smell of PCl5. I have no irritation, I only breathed a few minor whiffs of the POCl3 vapor, but again the smell persists hours after exposure.

plante1999 - 27-10-2011 at 08:42

Iodine seem to do the same effect as you on me , after several hour later than the exposure there is still a kerosen smell.

IrC - 27-10-2011 at 13:53

Quote: Originally posted by Mr. Wizard  
I second the suggestion of getting a respirator. I transferred a small amount of copper acetate a few years ago, and even being careful, managed to get some of the dust in my throat, causing a nasty flavor and a sore throat. Try transferring some fluorescein while being 'careful', and then get a good UV light out and see how successful you were. My bet is on epic failure, and fluorescent urine. Only half joking about the urine.


I have Fluorescin Dye (530-580 nm) (50 gm) as I love building lasers, no, no brightly colored ponds near me ever. Really. Thanks to you I will now always carry a mini blacklight flashlight to the toilet whenever I go. I will let you know.

bahamuth - 27-10-2011 at 14:46

Quote: Originally posted by IrC  
Thanks to you I will now always carry a mini blacklight flashlight to the toilet whenever I go.


Urine has a natural reddish/yellowish/greenish fluorescence so a UV-light would give a false positive.. That or I've been contaminated with fluorophores over quite some time...

AndersHoveland - 27-10-2011 at 14:57

If it had been phosphorous trichloride, I would have immediately called the hazardous waste management department and not gone anywhere near the glass container!

[Edited on 27-10-2011 by AndersHoveland]

woelen - 27-10-2011 at 22:44

Now, afer almost one day, I still have that peculiar smell in my nose, but only if I inhale air through it. The effect also is stronger in cold air outside. Compared with yesterday the effect is weaker now.

@AndersHoveland: I also have a small quantity of PCl3 and this smells like PCl5 and POCl3. I think that you exaggerate the toxic properties of this chemical. It is toxic, but it is comparable to POCl3. Both are a nuisance to handle, due to the highly irritating fumes and the easy hydrolysis to HCl.

White Yeti - 5-11-2011 at 14:17

Interesting...

Are you sure it's a smell, rather than an irritation of some kind? I don't know about you guys, but habituation cases the olfactory nerves in the nose to become increasingly insensitive to compounds they are continuously exposed to, if that makes any sense.

The cause of the "spicy smell" is most likely the hydrochloric acid gently stimulating the pain nerves in the nose.

I can't say anything with 100% certainty because I've never handled phosphorus chlorides before.

You should edit wikipedia and mentioned the "spicy smell":)

Seriously though, I think wikipedia is lacking a lot of safety info. This is all they have for PCl5:
PCl5 is a dangerous substance as it reacts violently with water.