Author Topic: Hg and how much of the problem it realy is!?  (Read 253 times)

Oerlikon

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Hg and how much of the problem it realy is!?
« on: April 07, 2011, 03:54:43 PM »
You all know about Hg hysteria in last 10yrs or so since scientists proved that
even minisclue doses in body can b pretty dangerous.

I know that better equipment and techniques allow us to detect previously undetectable amounts
and this combined with fear and ignorance created eko hysteria.

Anyway...I wanted to ask:In Al/Hg reductive amination,where does the Hg from HgCl2 goes?!
Well,I was pretty convinced that it goes away with multiple washes of water and brine but...
I cleaned my Liebig condenser after Al/Hg red.amin. well and stored it until I used it again
to distill (recycle) toluene that was used multiple times for freebase extraction.
I was in hurry so I didn't clean Liebig after distillation,on my big suprise,after more than 2 week
when I looked down the condenser there were droplets of ELEMENTAR Hg!!! :o :o :o
It was not much,but here it was! I don't use more than 400mg of HgCl2 per reaction and darn thing
was left for two weeks after that,God knows how much evaporated!

Only ting where that could originate is from Hg salt I used for amalgation.
Any thoughts!?
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psychexplorer

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Re: Hg and how much of the problem it realy is!?
« Reply #1 on: April 07, 2011, 05:27:10 PM »
If your only use of Hg is for reductive aminations, then that is where it had to have originated. The high vapor pressure of Hg explains why it made it to the condenser.

If you were cleaning with aqueous brine, that might not have washed out all the elemental mercury.

You definitely want to get that Hg out in the future. Try washing your glass with concentrated HNO3 or H2SO4, preferably HNO3 if you have it. That will produce a soluble salt which is easily washed out and won't be sticking to the glass.

It's a shame the underground doesn't pay as much attention to Hg safety and Hg alternatives as is warranted.

DopeBee

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Re: Hg and how much of the problem it realy is!?
« Reply #2 on: April 07, 2011, 07:19:16 PM »
After years of doing Al/Hg in my home and even having a spill I got tested for mercury. It was in the low range of 1-2 mcg/L but I guess that doesn't show the levels that are already trapped in the organs. Still it calmed some of my fears. Plus since I was a kid my mouth has been full of mercury amalgam fillings.

Oerlikon

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WHAT THE FUCK!!!
« Reply #3 on: April 07, 2011, 09:55:43 PM »
Now THIS is seriously fucked up!!!

This is what I got after TWO dH2O and TWO brine washed(serious shaking and all) few minutes after addition of Na2SO4 to dry toluene!

When I add brine and shake,nasty "emulsion" froms,actually thin but persistent
white snow-like membrane scum that wont go away and makes deformed bubbles
in white skin that stick to the glass.VERY hard to remove w/o losing much toluene.
I use a little bit of that scum from brine wash and will try to dehidrate it with Na2SO4 under touene.
If Hg appears that must be Hg salt!
If it appears,that means that water washes are TOTALY pointless.

Since Hg is very dense this is not neglible ammount on the picture!
What do you folks think!?
« Last Edit: April 07, 2011, 10:12:33 PM by Oerlikon »
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jon

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Re: Hg and how much of the problem it realy is!?
« Reply #4 on: April 07, 2011, 10:12:27 PM »
aqua regia will wash it off.
sodium polysulfides absorb mercury spills.

Oerlikon

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Re: Hg and how much of the problem it realy is!?
« Reply #5 on: April 07, 2011, 10:18:56 PM »
I know it will work for cleaning,but I wont use damn HNO3 and aqua regia to to wash tolene!!!
Problem is why it is there in the first place!!!

I have idea how to clean tolene after extraction in the future:
Omit H2O and brine washes totaly,heat toluene to get rid of the methylamine and just use mix of elemental sulphur
(it absorbs HG too,but wont give off SO2 like polisulfide might) and Na2SO4 (for drying) over night.
Will that work!? What lse can be used to absorb Hg and its salts!?
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Tsathoggua

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Re: Hg and how much of the problem it realy is!?
« Reply #6 on: April 07, 2011, 11:18:56 PM »
Hg (I) salts (mercurous) are less soluable in H2O than mercuric (II) salts, and less bioavailable as such. Mercurous chloride, or calomel, as it used to be known in medical practise was often used as a laxative, or emetic, and as a component of teething powders for babies(!)  and by the 1800s was recognised as less toxic than Hg (II) chloride, known then as corrosive sublimate was well known to be a virulent poison, although still used as a purgative, stuff was even injected as a treatment for yellow fever and syphilis. Both oxidation states make for nasty compounds but corrosive sublimate was by far responsible for more sickness and fatality.

Other preparations in use then (calomel was, I believe, used up until the 1950s) were metallic mercury in a finely divided state, mixed intimately with chalk, grey powder, blue pill was a similar preperation to the latter, both used again as teething powder, and for fever. Iodides, the nitrate were used and thought to stimulate the liver, particularly also to stimulate the action of the bile duct/gall bladder.

Ointments of the red oxide used to be used for styes, and inflamed eyelides (I forget which compound the red oxide, as the term was used at the time of the source for this info is, most of the names for these preparations are antiquated, and ointments of the nitrate, and oleate were used for disinfecting infected or slow healing ulcers and other sores.

To quote, 'many persons are more liable to the actions of mercury than others, even a single grain (60mg) of calomel has been known to produce in an adult all the marked symptoms connected with the mouth. Persons cannot therefore be too careful in dosing themselves with mercurials'

Referring to some initial signs of Hg toxicity, including excessive salivation and swelling of the salivary glands, or mercurial ptyalism, apparently it was known to cause, in severe cases, necrosis of the jawbone, which reminds me of the toxic effect of white phosphorus, paticularly nasty for inducing jaw necrosis, and massive, purulent abscesses, in some cases completely destroying the jaw.

Source for the above three paragraphs: The Household Physician, by J.Mcgregor Robertson, volume II, date published, 1890.

Salts of Hg tend to produce mainly peripheral symptoms, including the above, G.I tract irritation, general physical muscular weakness, joint pains and heart trouble, due to limited BBB penetration. Organomercury compounds are the devil incarnate, highly lipophilic, and penetrate the skin in seconds to minutes, the alkylmercury compounds are some of the worst, and one of the relatively few things that I refuse to work with absolutely, for any reason, such as nickel carbonyl, F2, most organic peroxides, and the likes of nasty unstable stuff that would like nothing better than to explode and take off one's face.

Dimethyl mercury for example, is about the worst thing that can come of mercury, or for that matter, anything else, volatile liquid, goes straight through latex, butyl rubber, nitrile gloves, it apparently smells, faintly, but that is no good as a warning, save to warn 'you just died horribly several months down the line' due to the low lethal dosage. To handle it, and most organizations now forbid its use completely, sealed vials and syringes are used, in combination with a full face shield, an outer layer of a special glove with an internal metal lining, and arm-length pair of inner gloves.

There was a case of a researcher using it, I think as an internal standard for NMR analysis of Hg, who spilled perhaps a hundred microliters on her latex gloves, and rapidly took them off, wikipedia states she reported removing the gloves in as little as 15 seconds. A couple of months later neurological symptoms were notices, ataxia, difficulty speaking etc, six months post exposure, despite going all out to remove the mercury via chelation, she went into a coma and died.

So clearly, the toxicity of mercury is highly dependent upon the form it takes, as does the dose taken, route and duration of exposure. AlkylHg compounds, are ones to avoid completely, one fuckup and you are ankle deep in shite from the neck up.

Interestingly, ethylmercury does not appear to show the same degree of lethality as Me2Hg, although it is still a most obnoxious compound. And what is particularly shocking really, is that it hasn't been completely banned from use in medicine, it is a metabolite of thiomersal, a preservative/adjuvant used in some vaccines. Imfamously blamed for causing autism by an wanker by the name of andrew wakefield, an A+-grade son of a syphilitic gutterslut, who was later forced to retract his paper, after he was shown to have fraudulently published false reports, and worse pulled off some sickening shit on some of our young ones including colonoscopy and even spinal taps, not to help support our health mind you, but solely to back up his bullshit 'research' data.

Guy sued a reporter who investigated him and made some claims about his being full of shit, tried to cover up his crimes, and was eventually convicted of multiple counts of child abuse and dishonesty, as well as being found to have been paid to spit up a report finding a link between autism and ethylmercury/thiomersal, and struck off the register.

Not good enough for me, personally I think the bastard should be jailed, for a long time. Abusing special needs kids deserves a good arseraping by big black, HIV+ bubba in the showers for a few decades.

After that, he slithered off with his tail between his legs to crawl over to the US, where autism awareness and rights are primitive, compared to the UK to brown-nose an child abuse promoting ex-playboy slag and extreme porn actor by the name of jenny mc'carthy, partner of a nasty organisation called 'talk about curing autism' and spokeswhore for another such organisation, generation rescue.
 
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EU1920xy

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Re: Hg and how much of the problem it realy is!?
« Reply #7 on: August 14, 2011, 05:47:18 AM »
Would a Na2S wash of thr NP help?

newbiechem

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Re: Hg and how much of the problem it realy is!?
« Reply #8 on: September 05, 2011, 10:58:16 PM »
bring topic back....
 i also believed that dh2o wash would clean the mercury from freebase, thats not true? or the mercury will react with aluminium leaving not much to worry about?
so.... the mercury will make it to final hcl salt? if thats true al/hg doesnt seem a very nice aproach ... unless you like poisoning people...
any recomendations to clean glassware and product?
thnks

Oerlikon

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Re: Hg and how much of the problem it realy is!?
« Reply #9 on: September 05, 2011, 11:14:38 PM »
I solved it by putting  one spoon of dry bisulfite and anhydrous Na2SO4 mixture in my tolene extract and let it overnight.
Zn powder will work too for mercury but I guess that fine metal powder in tolene might be messy.
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lugh

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Re: Hg and how much of the problem it realy is!?
« Reply #10 on: September 06, 2011, 01:50:45 AM »
Further solutions can be found in:

http://127.0.0.1/talk/index.php/topic,520.msg5666.html#msg5666

and more can be found elsewhere by following the link posted in:

http://127.0.0.1/talk/index.php/topic,2133.msg22398.html#msg22398

 8)
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newbiechem

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Re: Hg and how much of the problem it realy is!?
« Reply #11 on: September 06, 2011, 03:00:54 AM »
i knew i saw something like that somewhere about disposing hg salts. i had a kinda of p2p-tor old hive kind of thing on the internet with the complete forum till jun-2000, i loved so much  but now its offline :( thats probely why i didnt find it, and my hive archive its from exact 2001-2004 ... now im missing first and BEST part.  :-[
THANKS for that link lugh!!!!
seems so simple to dispose hg :) i mean
"While alternative procedures should always be explored, the reality is that mercury will always be used by some of the bees. As one of the wisest bees recently stated: "personally i believe one must take responsibility for their own waste products... there are numerous books on the safe disposal of lab waste available thru flu/ald/sig et al ......amazon.com etc.... come to think of it ordering books is a good way to START an account with said multi-national corpos.....get one today and bee eco tomorrow....." Mercury containing solutions are easily demercurized by agitation with a 3/1 mixture of copper, nickel or zinc for about 60 minutes, forming an amalgam. When a sufficient quantity of amalgamated metal is accumulated, the metal is solidified in a plastic container for disposal in a landfill [JKTK JP 03 39427 (1991)]."
i would definitly rather doing that than letting go into the oceans :) i saw sedit may disagree hehehe but still... i think both will do us lot of harm, in the oceans or in the enviroment. but at least when its up here we manage somehow, i dont know send it to space every hundreds of year or so hehehehe the oceans its limited one day will "clog" everything, and our kids would be eating :( china is much closer today, i think the world is like the internet hehehe or the other way around :) its all conected definitly, and information spread fast... :) does anyone knows how the companies that makes disposal of these materials handles it? they probely recicle right?

its that simple making a almagun  to dispose? if so, should spread the word out :) detailed process?
im still a newbie.  :-\
thanks
peace!!







 

Sedit

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Re: Hg and how much of the problem it realy is!?
« Reply #12 on: September 06, 2011, 06:22:35 AM »
i saw sedit may disagree hehehe but still...

No not completely, I am honestly a big advocate for one cleaning up after themselves properly but I really wanted to emphasis how very little Hg the typical home chemist uses and how much of what we feel about it is typical government fear mongering embedding visions of armless still born two headed babies into our heads.

 Mercury is not good, but it is not as lethal as it is made out to be. The maya used Mercury sulfides as red paint.... and they used ALOT of red paint.... The Chinese drank large quantity of  mixtures containing the same chemical because it was in fact more then likely the source of the philosophers stone myth and they felt it would give them eternal life. It will make you nuts well before it kills you and this is an accumulation thing. The odds of home chemist using enough Hg to upset the local/global ecosystem is just to low for me to ignore anymore.
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Oerlikon

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Re: Hg and how much of the problem it realy is!?
« Reply #13 on: September 06, 2011, 02:16:24 PM »
Sedit is on the money with last comment. :)
Comparing impact of our (combined) mercury waste on enviroment with some average factory is like comparing fart to Chinese annual greenhouse gas emission!
Just make sure it doesn't end up in your final product.

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