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Author: Subject: The Stupidity of Certain Chemical Bans
Sauron
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[*] posted on 20-1-2007 at 05:54
The Stupidity of Certain Chemical Bans


In another thread we touched on thionyl chloride which is a useful chlorinating reagent, now politically incorrect. Why?

Because the leaders of two nations who were at war with each other in the 1980s decided to make sulfur mustard and hurl it at each other. More specifically their technocrats decided to use the old "German metod" and make sulfur mustard (bis(2-chloroethyl sulfide) from thiodiglycol (bis(2-hydroxyethyl)sulfide) and thionyl chloride.

This is a great way to make this stuff on a lab scale but a vastly unnecessarily expensive way to do so on industrial scale. If one insists on using the German method, concentrated HCl works just fine and costs a LOT less than SOCl2.

Furthermore, the process the US and UK developed to counter the Germans was much cheaper still and much more efficient, it is called the Levinstein (or sometimes Lewistein) method, and is simply the bubbling of ethylene gas through sulfur chloride. The result is a complex mixture of mostly sulfur mustard itself but also containing more complex compounds many of which are even more powerful vessicants than the main component.

Given that both Iraq and Iran were and are in the oil business one would have thought that ethylene gas would hardly have been a problem for them to obtain. Whereas they had to purchase vast quantities of thiodiglycol from Europe, USA and Japan. Go figure!

SCl2 and S2Cl2 are readily obtained from the elements and also are produced in large quantities as byproduct of the manufacure of carbon tetrachloride. (Chlorination of CS2.)

So it remains a mystery to me why the "German method" was insisted upon.

Had it been otherwise one supposes that the authors of the CWC would have diligently tried to ban sulfur, or perhaps seatater (which chlorine is made from by electrolysis) or table salt (likewise) or maybe natural gas (source of ethylene) or ethanol (likewise.)?

So from the CWC standpoint is iit not fortunate that Saddam and the mullahs employed two tractible compounds?

Thiodiglycol is a component of inks and a solvent for printing processes and is also used in the textile industry.

We chemists did not have a sufficient lobby to stop the ban of thionyl chloride, unfortunately.

I suppose we should be grateful they left us with hydrochloric acid.

And we have a few tricks up our sleeves still.

It was the Hill & Bill SHow that hurriedly signed off on the stupid CWC in the last gasp of their presidency. Bush would never have signed it.

Does anyone REALLY believe that a piece of peper will prevent any national effort to manufacture a simple compound?
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[*] posted on 20-1-2007 at 06:09


Thionyl chloride can be used for far more dangerous CWs than only mustard gas.
Specifically in one of the steps of Sarin synthesis (Chlorination of methylphosphonic acid to the dichloride). But in this synthesis it can also be replaced by oxalyl chloride...

Of course it is stupid to ban it.


[Edited on 20-1-2007 by garage chemist]




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[*] posted on 20-1-2007 at 06:39


Divulged syntesis are Unreliable, when dangerous stuff is involved.This explain it.



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[*] posted on 20-1-2007 at 06:56


@GC, thechlorination of methylphosphonyl diesters is usually done with phosgene.

Rather than trying to replace only one alkoxy group is it better to replace them both, affording THE key intermediate for all the G-series except GA, that intermediate being Dichlor or methylphosphonic dichloride.

Of course you can also make Dichlor by other routes, often much more easily.

If you are curious I'd rather explain in a PM as I'm not wanting to write a How To manual here.

Dichlor is generally converted to Difluor. At this point one has 1 of the 2 components of a binary agent. You can probably fill in the blanks for the other half, it is trivial and depends on which specific G-agent is desired.

In thirty years of study on this subject this is first time I have ever seen the proposition advanced that SOCl2 has any specific utility in the preparation of any G-agent. That is not to say it is not true. However, it is hardly the only potential chlorinating reagent and it isn't the reagent of choice.

Furthermore I am not aware anyone makes Sarin, Dichlor or anything else in this family from methylphosphonic acid. That is to me a nonstarter. A prep sketched by someone who does not know practical phoisphorus chemistry well, or at all. Looks fine on paper to the non-specialist. But. The devil is in the details.

The main bedeviling detail is: where do you get the methylphosphonic acid? The usual prep is hydrolysis of a methylphosphonyl diester, but if you have the ester you can go directly to the Dichlor and skip the acid.

The acid is notoriously difficult to esterify. It's a rather placid compound.

[You can pretty well figure the practical routes to GB etc from the CWC schedules of controlled chemicals. And the lists of additional items proposed by the Australia Group. Methylphosphonic acid is on none of those.

The impractical routes are those that require too many steps for no good reason, or require reagents/precursors difficult to make or procure. In short they are without advantage. Sometimes the road less travelled just leads to nowhere.

Always remember: the Aum nutballs in Japan spent $11 Millions of USD on their lab, and for all that how many people did they kill with their high priced GB?

Hell they could have paid as many people to commit suicide and daved a lot of money, time and trouble. If they are the paradigm for supposed "chemical terror" then it is not as my friends who wrote the book "The Poor Man's Atom Bomb" thought. It is rich lunatic's ineffectual pretense. $11 Million! what a joke.

[Edited on 20-1-2007 by Sauron]
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[*] posted on 20-1-2007 at 07:04


New glasses needed,methink.
Divulged Syntesis are unreliable.Sawron.
Are you talking teory?




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[*] posted on 20-1-2007 at 07:16


@GAMESH I am not talking "teory" or even theory.

Published procedures may or may not be reliable, depending on who published them and when and where.

What unreliable preparations are you talking about?

I would say, many of the so called preparations I have seen on certain web sites are bogus. Many I have seen in certain black books for masturbatory wannabe's a la The Anarchist's Cookbook are bogus.

Published articles in long established peer reviewed journals like JACS, JOC, JCS, not to mention the 19th century literature like Ann. and Ber., are not bogus. Books like men like Saunders and Schrader are not bogus, Org.Syn. procedures are not bogus.

Chemical science does not advance by publication of non-reproducible experimental results. That is what peer review is all about. Only scorn and derision are in store for those whose results are not reproducible. Remember COLD FUSION?

The patent literature, well, is sometimes reliable and sometimes less so.

But I am not talking "teory" and if you want to dance with me you'd best know the steps before the band begins to play.

[Edited on 20-1-2007 by Sauron]
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[*] posted on 20-1-2007 at 09:57


i cant help to say that Sauron must have ate some spicy tie food because your not taking any slack from the band this session
tune up that oboe section, it sounds as if a seagull swallowed an I-pod playing 50 cent.


But in seriousness, it seems you have the interest in some type of protein research and indeed epitope prediction and folding methods are of great intrigue to me. Im more of a grunt in the operations, but over lapping TOCSY and COSY nmr scans, one can begin to assign chemical shift values and ascertain structure in a given ionic strength, solvent, and temperature. There are a lot of nasty chemicals to work with like TFA in cleaving peptides, but the point im trying to make is…
Any government or business would be silly not to give you a key to a full lab, a fellow of your credentials and experience.

I mean I can see a chap from NewJesey or California complaining that they cant get chucky peanut butter anymore but is this just a peeve that you have to voice….

Resources it all about the restriction and distribution of limited resources…
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Sauron
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[*] posted on 20-1-2007 at 10:13


It is indeed a pet peeve of mine. It seems the proscribed lists are multiplying. Can't have these things because of the WOD, can't have those things because of the WOT (category A Mad Bombers and category B imaginary chemical terrorism.) Then throw in what we can't have because it might harm wildebeasts in Rwanda and pretty soon we have no solvents, no reagents, and so on. It's already at the stage where one can hardly pick a prep at random from Org.Syn. without finding something that is required that is now proscribed.

May be I am a typical old has-been pining for the Good Old Days, but, god damn it, they WERE the Goold Old Days. And deserve to be pined for.
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[*] posted on 20-1-2007 at 10:23


I honestly think that the legislators are confused (and their scientific advisory committee should be shot in the face repeatedly (in an allegorical way)--they should know better). It seems to me that they choose to ban a chemical which can be used (but is not ideal) so as to avoid the banning of a commodity level chemical, like HCl (whatever would they do without HCl?). The addition of the mustard reference only serves to scare the votes out of the legislative assembly (it's used to make war gas, we must ban it).

A recent and interesting experience:

In two separate *legitimate* purchases from a well known chemical supplier (of which I am a legitimate client, registered, licensed, all that) I purchased 1L SOCl2 and 100mL of ultradry, ultrapure benzaldehyde (not cheap). I was not questioned about the SOCl2, but had to fill out forms declairing that I was not making drugs or chemical weapons (which the dept. director also had to review and sign).

Odd that, no chemical weapons from benzaldehyde (cherry bombs? bad joke, I know).

Go figure :/,

O3




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[*] posted on 20-1-2007 at 10:47


Full marks, @O3. Re the benzaldehyde remember that tear gases (non lethal, police type, riot control agents) are covered by the same bullshit as full bore lethal agents. And that the standard prep of CS (2-chlorobenzalmalononitrile) tear gas is from 2-chlorobenzaldehyde and malononitrile.

As to the "ban this/don't ban this" rigamarole, CWC has several dozen countries as signatories and they started with a list of 200 or so, and by the time all the chemical sacred cows had been excluded they banned what, less than 30 or 40?

Should we be grateful for such hypocrisy?

In effect they threw some chemicals to the wolves, but only if they were insufficiently economically important. Great example: pinacolyl alcohol. Does it have any use? None I can think of. Terribly east to make by a series of preps from acetone that used to be standard undergrad instructional lab fare, prep of pinacol and rearrangement to pinacolone. So given that they haven't banned acetone (yet) and to do so they'd have to ban 2-propanol, which appears unlikely, why are we to believe that CWC would prevent the production of pinacolyl alcohol?

Furthermore if this alcohol is banned why is 2-propanol (used to build GB) not banned? Reason: it's too useful, and pinacolyl alcohol is EXPENDIBLE.

Well what's expendibe now may be of some importance later, you never know.
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[*] posted on 20-1-2007 at 11:03


Thanks,

That is precisely where I was going. It'a all a horse-trade and it follows the golden rule: He/She who has the gold makes the rules.

To make it worse, we do not get to vote on anything that directly effects us (in the U.S.)! Anything that the hairbrained gophers think up that they suppose will be shot down in public vote is made an act of legislature. We are informed of the date when it will go into effect. Democracy? No.

Say it's not so,

O3

@roamingnome--off topic, but is COSY cool, or what?!

[Edited on 20-1-2007 by Ozone]




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Sauron
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[*] posted on 20-1-2007 at 11:07


But @O3, the green check suckers will always provide for a 60-90 day period for public comment before they cut our balls off.

I think the rationale is, let them squeal before, maybe they will make less noise after.

Vox populi and all that.

[Edited on 20-1-2007 by Sauron]
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[*] posted on 20-1-2007 at 11:15


Yes, but it is posted in the news rag in very small font, embedded in 45 (arbitrary) other notices, and written in legalese that is difficult (even for me) to understand. The average person has no idea or care. Frequently, these go unnoticed until you go to a restaurant and find that smoking has been banned everywhere (an example).

Legislation on chemicals is far more intentionally obfuscate. It seems to require ACS and a herd of lawyers to translate these, and by the time the legislative action network is notified, it is frequently too late.

They are obligated to notify us, but they are not obligated to be intelligible; doing that would minimize their chances of success.

One nut left:(,

O3

[Edited on 20-1-2007 by Ozone]




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Sauron
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[*] posted on 20-1-2007 at 11:32


Let me assure you, if you think US legalese is undecipherable, you haven't seen EU legalese upclose yet.

With all due respect to our European members, EU lawyers appear to be specialists in blue smoke and mirrors. I tried to make sense out of some EU liquor laws a few years ago, I still have a serious headache from the effort. And never did get to the bottom of it.

A good friend is an Ozzie govt type who is embroiled in trying to harmonize food and beverage and pharmaceutical regs between Australia and New Zealand and he reports that even this bilateral matter is a frigging minefield.
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[*] posted on 20-1-2007 at 12:03


well if you could walk into Chem-Mart and grab every conceiveable chemical at will, maybye chemistry wouldnt be as film noir. the rabbit and the hat.... i wish i was blowing my own glass and making jupiters net, Those were the good ole days!

at the end of this thread .. where are you left,,, still without your Thionyl

well maybye Sauron isnt working with protiens
i was lucky to be working with hyperintelligent pre-med students who handled all the FTIR stuff, and after a few Dr. Peppers you could get into it like a game of tetris. gather data then interpret later.... you can really milk HPLC method development for all your career goals.

yes the under rated secondary structure the beta hairpin..... the alpha helix and beta sheet gets all the prestige... but take away a hair pin and your protien no worky
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[*] posted on 20-1-2007 at 12:07


I don't understand how the CWC has had such an impact on organic synthesis workhorses like phosphorus trichloride and thionyl chloride. These are Schedule 3 under the CWC, which means "Plants which manufacture of more than 30 tonnes per year must be declared and can be inspected as per Part VIII of the 'Verification Annex', and there are restrictions on export to countries which are not CWC signatories." The occasional verification tour and export restrictions to non-signatories don't sound that onerous. Thailand's a signatory, too, so I don't see how it's harder to get CWC-listed chemicals there than in other signatory nations. How did these reasonable measures mutate into "end users have to fill out paperwork for every gram of PCl3, and thionyl chloride will simply vanish from Thailand"?

I know I can buy triethanolamine from half a dozen suppliers of cosmetic/personal care raw materials, who aren't even general chemical suppliers, with no trouble at all. That's supposed to be CWC Schedule 3 just like POCl3 and SCl2. Such discrepancies make me suspect that there's a lot of controls implemented by additional legislation that's more restrictive than the CWC, or even by no legislation at all, just cover-your-ass instincts on behalf of middleman suppliers (who may pretend that the law requires such of them, since then they can deflect their customers' anger with "the <strike>devil</strike> government made me do it!")

For an example of extreme ass covering, the Photographer's Formulary declared on their website a few years ago that they required a "DEA form" (statement of use plus copy of photo ID) to sell hydrochloric acid and several other chemicals, only a handful of which the DEA actually cares about. That's leaps and bounds beyond the requirements of the law; I don't know if it was intended as a giant ass-covering move, a way to encourage clandestine chemists to shop elsewhere, or a combination of the two. If you just glanced at their order page and saw "DEA form", you might wrongly think that the government has imposed this ridiculous requirement -- not that it hasn't imposed plenty of its own ridiculous requirements.




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Sauron
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[*] posted on 20-1-2007 at 13:20


How CWC is implemented on a national level is left to the discretion of the signatory nations. In the case of Thailand, not only the CWC scheduled chemicals but a much broader list compiled by the Thai Defense Ministry require a license from the Permanent Secretary's office in the MOD to import, or manufacture. PCl3, POCl3, elemental P (red and white) and PCl5 are all on the list. SOCl2, SO2Cl2, SCl2, and S2Cl2 ditto. Bromine and chlorine, too, as well as fluorine. Chlorosulfonic acid (probably because it was a component of a military smoke agent.) SO2. It's a long list and some items make little sense.

Triethanolamine despite being on CWC and the Thai MOD list seems to be readily available.

Bromine also, as long as you don't buy too much. Maybe 1-2 Kg a month is okay.

HF gas is restricted as is SO3. (But oleum is not.)

There's a lot of obscure arsenicals on the list.

The net effect of this is to bring things to a screeching halt.

I am quite sure the same is true in many newly industrialized nations or in the remnants of the Third World.

Worse, bureaucracies in these countries are often corrupt. I am not saying that is true of Thailand in this instance but in many places I bet the bottom line is "Want a license? Pay up."

Which makes the entire enterprise obstructive and dysfunctional, as well as arbitrary and capricious.
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[*] posted on 21-1-2007 at 01:29


How is the law enforced in Thailand? Is the paperwork important, or is there nobody who really cares? I can imagine the South Thailand insurgency at least can create a few difficulties. And the situation in bordering Combodia and Laos?



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[*] posted on 21-1-2007 at 03:44


What situation in Laos and Cambodia? We have a bridge across the Maekhong River linking Nong Khai and Vientiene. People cross freely in both directions. Peace and quiet. Cambodia is also at peace, all along the frontier there are casinos where Thais go to gamble on weekends. The major ones at Hat Lek, Pailin, Poipet. There is no "situation" and hasn't been for about 15 years since the UN sponsored elections.


The southern problem is confined to three border provinces that used to be the single Sultanate of Pattani, and the ousted and exiled former aristocracy of that sultanate were the original instigators of unrest a century ago. Moslems in all the other 71 provinces, have zero common cause with those people. The King names a Chularajamontri to be leader of Thai Moslems and the Thai Moslems are loyal to the King and to the Chula. No Chula has ever been named from Pattani, Narathivat or Yala, and the people there do not respect the Chula.

Anyway things were quiet 1975-2000 due to the policies of Field Marshall Prem. Upon the election of Thaksin in 2000, he dismantled Prem's CPM43 apparatus and the trouble started immediately. Escalated for 6 years. Now Thaksin is ousted at behest of the Queen, precisely over the southern issue, and we expect that the three provinces will quieten back down once again.

Thailand has a strong security apparatus but it is not antithetical to the populace not oppressive, the people love the King and Queen and the security agencies and the military serve the Monarchy. Thakin came from the Police and there, alas, things are not always so straightforward. He was corrupt and very disloyal. But very rich and succesful as a result of his corruption. (A US$ billionaire.) He set himself in direct conflict with the Palace and once he did that his money could not save him. He is in exile.
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[*] posted on 21-1-2007 at 06:46


Sorry, I now realize that my question wasn't formulated clearly. I am curious about the situation in Cambodia and/or Laos when it comes down to running your own private lab, whether this is an enterprise or your garage.



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[*] posted on 21-1-2007 at 07:09


Well, the government of Laos is still communist, and deeply involved in the heroin traffic (aminly, the army.) So, if you were allowed to set up a lab, the main risk would be that they would at some point ask you to do them some favors. If you take my meaning. Given that you could hardly say no, this is unacceptable to me and I would advise against siting a lab of any sort in Laos.

Very similar situation in Cambodia where reportedly there are quite a few labs cranking out viagra/cialis etc. and god knows what else. You would be assumed to be just another drug lab and as such would be squeezed for protection by Hun Sen and his merry band of ex-Khmer Rouge gangsters. Look sideways at them and you are dead.

You want a report on Burma maybe? Worse.

In Thailand, if you have the right connections, and are a known person, and are NOT in the drug trade, and NOT making explosives or weapons, and you dot your Is and cross your Ts and so on you will be ignored, and tolerated. I've been here for damned near twenty years, am very connected to the Thai military and police, am not doing anything naughty as listed above. I have been buying lab equipment and chemicals for 7-8 years now locally as well as importing and I have never been visited, questioned, interviewed, audited, and certainly not harassed. I do have a registered business and am considering the formation of a non profit research and educational foundation. This is for real and is not a front or cover for something else. At some point I expect to apply for permanent residency and perhaps Thai citizenship some day if I live that long.

Bear in mind that the Thai prisons are full of unhappy white guys who came here and thought the Thais would tolerate their dabbling in drugs. Not so. Very long sentences are handed down. Very long. Just a word to the wise. The DEA, Interpol, the UNDC are all very active here and their Thai counterparts are kept busy. There's a huge amphetamine problem here and amphetamine dealers are often summarily executed by the Thai police. Anyone who has that in mind, should just go somewhere else.
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[*] posted on 21-1-2007 at 07:48


Quote:
Originally posted by Sauron
I do have a registered business and am considering the formation of a non profit research and educational foundation.


That is an excellent idea. The concept of coupling real research with outreach is always win-win. People learn something, employees are grown, and the granting institutions and industrial partners suddenly find you quite attractive for collaboration.

Here, there are some new initiatives set fourth by several Universities; these are referred to as Research and Business incubators. Here, private researchers (or groups) can incorporate, and in return for a (surprisingly small) piece of the intellectual property and local economic growth (outreach is key to this too) they are provided with laboratory space, seed money, and patent protection (defending an infringment is usually where the private citizen goes four-legs-up; they simply do not have the resources to fight a large company). And...Blue-Sky is actually encouraged!

Good stuff, but an attorney is absolutely required (to remain half-way sane) to negotiate the bureaucracy that is required to set it up.

Cheers,

O3

[Edited on 21-1-2007 by Ozone]

[Edited on 21-1-2007 by Ozone]




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[*] posted on 21-1-2007 at 08:19


That is positive news.
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[*] posted on 24-1-2007 at 05:23
Ban DHMO


Dihydrogen monoxide is colorless, odorless, tasteless, and kills uncounted thousands of people every year. Most of these deaths are caused by accidental inhalation of DHMO, but the dangers of dihydrogen monoxide do not end there. Prolonged exposure to its solid form causes severe tissue damage. Symptoms of DHMO ingestion can include excessive sweating and urination, and possibly a bloated feeling, nausea, vomiting and body electrolyte imbalance. For those who have become dependent, DHMO withdrawal means certain death.

Dihydrogen monoxide:
- is the major component of acid rain
- contributes to the "greenhouse effect"
- it can cause severe burns in its gaseous state
- contributes to erosion
- accelerates corrosion and rusting of many metals
- may cause electrical failures and decreased effectiveness of automobile brakes
- has been found in tumors of terminal cancer patients

Despite the dangers, dihydrogen monoxide is often used:
- as an industrial solvent and coolant.
- in nuclear power plants.
- in the production of styrofoam.
- as a fire retardant.
- in many forms of cruel animal research.
- as an additive in certain "junk-foods" and other food products.

Companies dump waste DHMO into rivers and the ocean, and nothing can be done to stop them because this practice is still legal.


http://www.petitiononline.com/h2o/petition.html :D :D

[Edited on 24-1-2007 by Levi]
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[*] posted on 24-1-2007 at 08:26


Old hat, but the sad thing is some politicians believed it. Maybe in 20 years - shit five - the hysteria will reach THAT level. Some thoughts:

All train station are made non-smoking here one by one. I have no problem to refrain from smoking in a public building where others are forced to inhale the shit too.
But 4 out of 5 'stations' they converted lately *have no buildings*. There is just some pavement under open skies next to where the train sometimes stops (if it's not delayed or cancelled)!

I tried for weeks to buy 100g sodium nitrite, nobody sold it to me. Most said it was forbidden because of children making black-powder-and-such from it. I say "that's nitrate not nitrite" but in vain. Others refused becaus it is *toxic*. It is in every f*cking salami! Did I mention they had OTC rat poison and weed killer on the shelves?

I cannot buy more than 250ml of 96% alcohol, it is illegal to sell more to an individual within a month. For health reasons of course. I can however buy gallons if it contains methanol. Plus, ever heard the work liquor store?

No chem supplier sells petrol ether to individuals without lots of paperwork. Becaus it is 'highly flammable' (F+). Have these people ever seen a gas station?

Recently had to sign an *end-user-agreement* to get H3PO4 because it is a strong acid and 'might cause severe burns'. I assume the 96% sulfuric and the solid NaOH from the drug store don't hurt me then?

to be continued...
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