Regulatory quirks
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In an effort to limit the availability of various hazardous chemicals or to limit their impact, various laws have been passed over the years with the purpose to restrict or regulate various chemicals or lab equipment with various degrees of success. However, very often, due to a variety of reasons ranging from badly phrased text, laws written without consulting experts in the domain, bad science or simply a desire to have the laws passed for political gain, many such laws are either incomplete, cannot be properly enforced, or have loopholes that often allow for the restriction to be circumvented with little inconvenience. This page will present examples of various regulatory quirks found for many chemicals and lab/scientific equipment in the laws of many countries, as well as the unforeseen or negative effects of said legislation.
Contents
- 1 Chemicals
- 1.1 Acetyl chloride
- 1.2 Ammonium sulfamate
- 1.3 Benzaldehyde
- 1.4 Benzyl alcohol
- 1.5 Binary explosives
- 1.6 Chlorates/Perchlorates
- 1.7 Ethanol
- 1.8 Ethers
- 1.9 Hydrogen iodide/Hydroiodic acid
- 1.10 Hydrogen peroxide
- 1.11 Iodine
- 1.12 Methanol
- 1.13 Nitric acid
- 1.14 Pentaerythritol tetranitrate
- 1.15 Phosphorus
- 1.16 Phosphorus triiodide
- 1.17 Pinacolyl alcohol
- 1.18 Potassium permanganate
- 1.19 Prussian blue
- 1.20 Sulfuric acid
- 2 Chemistry equipment
- 3 Other
- 4 References
Chemicals
Acetyl chloride
Although acetic anhydride is classified as List II Drug precursor in most of the world, and its sale is strictly regulated or restricted, it can be very easily made by distilling a mixture of anhydrous sodium acetate (easily prepared) and acetyl chloride. Unlike acetic anhydride, acetyl chloride is not generally classified as drug precursor, so there are fewer restrictions to it (may still be classified as hazardous chemical due to its ability to release harmful HCl vapors in presence of moisture). However, acetyl chloride itself can be used instead of acetic anhydride in the manufacturing of many illicit substances, with various success. Only in some countries, like Australia, Russian Federation, acetyl chloride is also classified as drug precursor, and it's not easy to acquire.
Ammonium sulfamate
Ammonium sulfamate is no longer an accepted herbicide in the EU since 2008[1] due to the Irish Rapporteur not receiving testing on dogs for said chemical and thus the compound did not receive the license to be allowed as herbicide.[2] However, ammonium sulfamate is still legally allowed to be used as compost accelerator. Since both products are found in the same section of most stores (gardening) or online stores just a click away, nothing will stop anyone who knew that the compost accelerator can also be used as herbicide to, well, use it as herbicide.
Benzaldehyde
Although benzaldehyde is classified as List I precursor in many countries, not all countries classify this substance as drug precursor, even though toluene, which is usually a precursor for making benzaldehyde, is classified as List II precursor in those countries's legislation. Likewise, bitter almond oil, which is essentially crude benzaldehyde, is not covered in all countries as drug precursor. In US for example, bitter almond oil is classified as drug precursor, while in Canada is not. In most of EU countries, benzaldehyde is not classified as drug precursor.
Benzyl alcohol
Although benzaldehyde, benzyl chloride, toluene are classified as drug precursors of different types in most countries that enforce the United Nations Convention Against Illicit Traffic in Narcotic Drugs and Psychotropic Substances, benzyl alcohol, which may be used as precursor to synthesize all the three mentioned compounds, is not classified as drug precursor in any country, and is readily available without any restrictions.
Binary explosives
In US, under ATF regulations, binary explosives are not classified as explosive materials, when kept as separate components. However, the moment they are mixed, the resulting mixture is considered explosive material.[3] This means that one can potentially have a "just add water" bomb-making material without breaking the law.
Chlorates/Perchlorates
In EU, the sale of sodium and potassium chlorate/perchlorates is forbidden to private persons and only companies are allowed to handle them, and must obtain an explosive permit for working with these 4 compounds. However, the restriction does not seem to cover the other chlorates and perchlorates, at least at directive level, meaning that all the other metal chlorates/perchlorates can be acquired without a problem, unless the member country specifically restricts said compound. This also seems to include perchloric acid (which can be used to make any perchlorate), unless local laws classify it as explosive precursor, and, unless classified as explosive material, ammonium perchlorate (explosive on its own) is exempted from the EU-wide restriction. Other energetic compounds like guanidinium perchlorate also seem to fall in this issue.
Chlorates are a decomposition product of hypochlorite salts aka bleach. Thus, any old bottle of bleach will contain a significant (though not large) amount of chlorates, specifically sodium chlorate. The directive does not mention any exception for accidental/side production of chlorates/perchlorates in any form.
Ethanol
In almost all countries, food-grade distilled ethanol is subjected to taxes (excise duty on alcohol), which drives up the cost of liquors and rectified spirits. To avoid these taxes, concentrated ethanol is denatured (turned poisonous, bad-tasting, foul-smelling or nauseating) by adding various additives, making it unfit for human consumption. This practice is also done for lab-grade ethanol, while non-denatured lab-grade ethanol has a similar price to the food-grade rectified spirit. Some countries, like Bulgaria, Hungary, Romania allow the production of small amounts of home distilled liquor up to a limit or sometimes said practices are ignored by the authorities if the deed is not worth pursuing legally due to low resources, willful ignorance, nepotism or more often local tradition regarding cultural alcohol production.
Ethers
All drug precursor lists (DEA List e.g.) list diethyl ether as List II precursor (used in the manufacturing of controlled substances). However, no other ether is present on the list, even though for this intended purpose (organic extractions), other ethers are just as good. Diisopropyl ether, while extremely hazardous on its own since it rapidly builds up explosive peroxides over the course of a few months, can be easily made from isopropanol, which, unlike ethanol, is easily and cheaply available in high concentration at most hardware stores.
Tetrahydrofuran can also be used instead of diethyl ether for many reactions (including Grignard reactions) and in most Western countries there aren't restrictions on its use or possession, though in a few countries, like Russia, it's possession and use are restricted. However, there is no mention of THF derivates being included on the drug precursor list in Russia or other countries that regulate THF, meaning that unless specified in another list/annex, 2-methyltetrahydrofuran could be used instead, and is also suitable for Grignard reactions (though it's a bit more expensive compared to regular THF).
Hydrogen iodide/Hydroiodic acid
Hydrogen iodide/Hydroiodic acid are classified as List I precursor in US by the DEA, meaning their sale is regulated. However, HI can be easily made by adding conc. phosphoric acid to an iodide salt, both readily available reagents and not classified as precursors. Also, since HI is unstable in the presence of air and or light, the acid itself can be stored separately in the form of salt and acid, without breaking any laws, essentially as a quick DIY HI kit.
Hydrogen peroxide
In the EU, all hydrogen peroxide in concentrations higher than 12% is forbidden to be sold to private individuals. However, sodium percarbonate, which contains 32.5% H2O2 by weight is not restricted at all. Granted, extracting the peroxide from the percarbonate is not easy, but it does appear that the restriction only covers liquids containing H2O2.
Likewise, the directive does not place a limit on the amount of <12% hydrogen peroxide one can acquire, meaning one can concentrate the 10-12% peroxide to a more concentrated solution (though naturally the resulting volume is smaller).
Iodine
Iodine is classified as List I precursor in US by the DEA, meaning its sale to private individuals is restricted. However, elemental iodine can be easily made from any iodide salt (which are not classified as drug precursors) by simply reacting the iodide with a mixture of sulfuric acid and hydrogen peroxide, or just with Oxone (while sulfuric acid is List II precursor and conc. hydrogen peroxide may be classified as explosive precursor, Oxone is not classified as any precursor in US or any other country).
Likewise, given that elemental iodine is not easy to store, keeping the iodide salt and the oxidizer/acid separately is also a good way of storing iodine for long term and will also ignore any legal problems associated with the possession of the element.
In most countries outside the US, iodine is not classified as drug precursor.
Methanol
In many countries, like Italy or Austria, methanol is classified as poison and the sale of the compound is regulated or restricted to private individuals. However, methanol-based fuels, which consist mainly of methanol with a few additives added, do not appear to be subjected to the same restrictions. RC fuels containing methanol also don't appear to be restricted. Occasionally, some technical alcohol products used for cleaning are also almost pure methanol (with some dye added) and such products are sometimes sold in auto part shops or sometimes even hardware stores, depending on the country.
Nitric acid
In the EU, the sale of nitric acid in concentrations above 3% without a license/permit is forbidden, as per Regulation (EU) No 98/2013. The reason as to why this concentration was chosen is not given, and such diluted acid is unsuitable even for basic chemistry reactions, as one would need very large amounts of 3% nitric acid to obtain any useful amount of reaction product, and extracting the nitrate/nitrating product from such a large volume of water is very intensive and time consuming, even for small amounts, never mind the possibility of hydrolysis of product during the extraction process, which may contaminate the final product, requiring further purification, and thus a lower yield.
Given how low the 3% limit set by said regulation is, there is no mention of any exceptions or other legal effects for any accidental or side production of more concentrated acid solution. Hydrolysis of copper(II) nitrate, which can be easily done by simply heating a concentrated solution of said salt will produce lots of nitric acid, and for concentrated solutions, the 3% limit can be easily exceeded. This is also possible for other transition metal nitrates. Capturing nitrogen dioxide fumes in water (aka scrubbing a very toxic gas in a liquid), usually from various oxidation reactions or even decomposition or other nitrates/nitrites will produce a diluted nitric acid solution, which can very easily be concentrated above 3% by simply injecting more NO2 in water.
Pentaerythritol tetranitrate
Pentaerythritol tetranitrate (PETN) is a common explosive material used in both military and civilian applications due to its great performances. Although the commerce of PETN explosive materials is strongly regulated, PETN is also used as vasodilator drug to treat certain heart conditions, such as for management of angina. The drug Lentonitrat is described as being "pure PETN", and it is sold in many countries, under different brand names.[4].
Phosphorus
Except for the US and a few Asian countries, the sale of red phosphorous is usually not restricted (though regulations on its transport or storage may exist given its flammability hazard). White phosphorous on the other hand is almost always strongly regulated, restricted or outright banned in most countries due to its pyrophoricity/fire hazard and toxicity. White phosphorous however can be easily made from the red variety by simply heating it in a tube, in an oxygen-less atmosphere, meaning that potentially one can store the white form as the red form without any fire risk normally associated with the former. However, turning the white form into the red one is much harder than the other way around.
Also, if one were to produce elemental phosphorus from phosphates by carbon or metal powder reduction in a kiln, the product obtained is white phosphorus, meaning that it's much easier to obtain the more dangerous form of phosphorous than the safer one, which also has the bonus of allowing you to skip any blocks in acquiring the white variety.
Phosphorus triiodide
Although it's made from two DEA List I chemicals (phosphorus and iodine) and upon hydrolysis (which can also occur by simply leaving the compound in open air), PI3 releases another List I chemical (hydroiodic acid), phosphorus triiodide is curiously not listed in the DEA List of chemicals. However, PI3's status is covered by the same legislation that covers phosphorus halides and individuals normally cannot purchase it.
Pinacolyl alcohol
Despite displaying low toxicity, pinacolyl alcohol is included in the List of Schedule 2 substances of the Chemical Weapons Convention, since it's a binary precursor for the nerve agent Soman. Even though the way this class of nerve agents are produced is by simply mixing methylphosphonyl difluoride with an alcohol, pinacolyl alcohol is the only acyclic alcohol included in this category and no other alcohol involved in the production of nerve agents is included (like isopropanol, which is used to make sarin). This is possible because pinacolyl alcohol, unlike isopropanol, has very little uses in chemistry and industry, so basically it "drew the short straw".
Potassium permanganate
In most Western countries, this salt is rarely a controlled substance (in US it's DEA List II chemical), but in some former Soviet block countries and the Russian Federation it is included in the lists of drug precursors in because it is sometimes used to make methcathinone. In Russia, it can be sold freely as a low grade chemical, with the concentration of potassium permanganate below 50% (the rest being either inert or potassium ferrate). Higher grade potassium permanganate is regulated. Obtaining pure potassium permanganate from the impure grade can be easily done via recrystallization from water, though this requires one to purchase relative significant amounts of impure potassium permanganate, which may draw attention.
Prussian blue
Although Prussian blue is not classified as illegal compound, hazardous, poison or even precursor, assuming it's even included in any classification, its use in many common products has declined over the years, since it's "cyanide". As such, overzealous authorities may consider it true cyanide salt/poison and treat it as such, even though the compound is inert to most reagents and even stomach digestion.
In many places where cyanides are regulated or restricted, there is a mention in the text of the law that ferrocyanides are exempted from the restrictions. However, this doesn't stop overzealous or incompetent authorities from mistaking ferrocyanides with cyanide salts, especially if said persons enforcing the law are poorly trained or corrupt.
Sulfuric acid
In many countries, concentrated sulfuric acid is a controlled substance or otherwise unavailable, and sulfuric acid based drain openers are unavailable as well. Dilute (36%) sulfuric acid, on the other hand, is often over the counter as battery acid. Therefore, concentrating this acid in home conditions is required. This resulted in the practice of boiling the Bat.
In some countries where concentrated sulfuric acid is either monitored or restricted, there doesn't appear to be any regulation over the drain cleaner type, even though there are conc. H2SO4 drain cleaners that can be >95% and have no additives or dye added.[5] Such products can be used as lab-grade conc. sulfuric acid, while the concentrated form, but with dye added, can be cleaned very easily by just heating the acid to almost near the boiling point of the acid, which causes all organic material to break down.[6] Any regulations seem to cover mostly lab-grade sulfuric acid, with drain-cleaner types being less monitored.
Chemistry equipment
Erlenmeyer flask (CORRECTED)
In a ridiculous decision to limit drug manufacturing, Texas has restricted the sale of Erlenmeyer flasks and a permit is required to purchase them.[7] The restriction does not appear to cover flasks with a similar function and appearance, like Florence flasks, fleakers or side-arm flasks.
As of late 2019, there is no more need for a permit and it appears that restrictions on glassware have been loosened.[8]
Heating mantle
In the United States, the sale of all heating mantles with a volume of 22 liters (5.8 US gallons) are monitored, as these devices are placed in the DEA Special Surveillance List, in the equipment section. There are no mentions if heating mantles with a volume smaller or larger are also included nor is any explanation given as to why this exact volume was selected for special surveillance by the DEA.[9]
Other
Distillation
In most countries, as well as US, it is not required to posses a permit for owning a distillation still or apparatus. It is also permitted to distill almost any liquid, like water, essential oils, hydrocarbon solvents, etc. While it's legal to distill alcohols like methanol, propanol, iropropanol, butanol, etc., distillation of ethanol requires a distillation permit. However, while this is true for distilling food-grade ethanol, distilling denatured ethanol is a complicated matter, as in some countries there is no distinction between the distillation of food-grade ethanol and the denatured variety, while in others there is. In the US, for distilling ethanol fuel, a Federal Fuel Alcohol Permit is required. This permit however, does not cover the production of food-grade ethanol.[10] For distilling consumable alcohol, a Federal Distilled Spirits Permit is necessary.[11] Neither permits can be used to distill the other type of ethanol, so if you need to distill non-food grade ethanol and you have the Federal Distilled Spirits Permit, you will have to apply for the other permit to legally distill the technical alcohol, and if you want to distill both types, you will need both type of permits. It's unclear what happens if the resulting food-grade distilled ethanol ends up unfit for consumption due to an accident during the distillation or intentional denaturation after, as when that happens, the ethanol can only be used as as solvent or as fuel. However, since the distillation permit only covers the distillation activity for which the permit was released after filing the necessary paperwork and passing whatever inspection or certification is required, failed distillations should be classified as business loss and not penalized.
In many countries around the world, there are legal rules regarding the use and ownership of alcoholic beverage distillation equipment, which do not cover other form of distillation equipment, mainly since such items are not certified for alcohol distillation. As such, the following alternative distillation equipment are classified as:
- Chemistry distillation glassware parts, either acquired as separate pieces (boiling flask, condenser, etc.) or as full distillation kit are legal to acquire, posses and use without restrictions, though you may not legally distill food-grade ethanol.
- Rotavaps are legal to own and use, but you may not distill ethanol with it.
- Although commercial water distillers can be used for distilling alcohol, it is still not legal to do so, since it's the distillation activity that's regulated by the law, and not a specific distillation apparatus. N̶o̶t̶ ̶t̶h̶a̶t̶ ̶a̶n̶y̶o̶n̶e̶ ̶w̶i̶l̶l̶ ̶a̶s̶k̶.̶.̶.
- A supersimple distillation still can be made by simply taking a large pot, placing the desired liquid inside, then placing a jar or flask in the middle of the pot, covering the pot with its lid turned upside down. The resulting liquid condenses on the inside of the lid (works better if you add some ice on its outside curve), which then pours in the receiving flask.[12] Since this isn't a distillation apparatus in its official sense, and it's basically just a simple hack of a typical kitchen pot (which works by refluxing its volatile liquids), it's unclear how this would be legally classified, though since you can collect the resulting distilled liquid, it may be still classified as distillation.
Hazardous chemicals
Many countries will classify various chemicals that are proven to cause harm as "hazardous" and may even be restricted if they're deemed too harmful. However, the exact term "hazardous" is itself poorly defined, and varies from country to country. While some definitions include phrases like "proven to cause immediate harm" or "recognized to be dangerous to health and environment", many definitions will rely on various lists of reagents deemed hazardous, like the EU's REACH list or chemicals. This however, leads to the problem of following the law too literal and only considering the substances that are included on the list as being hazardous, and often tends to ignore substances that are very similar, yet similar or even more harmful than the listed substance. Occasionally it might lead to cases of ignoring obscure harmful substances from being identified since they didn't raise certain red flags at a glance.
Expired reagents, even those that are non-toxic substances, are often lumped together as hazardous chemicals, mainly since lab wastes are all treated as hazardous, even when their only "crime" is that they passed their expiration date.
Reagent expiration
Most reagents have noted an expiration date on their label, which is often encountered on many organic reagents, and even on inorganic ones. This is because many chemical compounds will undergo chemical changes over time, either on their own, or after prolonged air/sunlight exposure, or may absorb moisture or carbon dioxide from air. The role of the expiration date is to provide a reasonable time period in which the reagent can be used safely without causing anomalies during the chemical reaction or even spoiling the reaction altogether. However, many reagents that normally do not suffer any changes in most storage conditions (like most common salts: NaCl, K2SO4, EDTA, etc.) also come with an expiration date, even though they should remain practically unchanged from when they were added in the bottle in the supplier's warehouse. While it's possible for some reagents to absorb water from air and thus become damp over time, this is more likely to happen if the reagent is not kept in proper storage conditions (after all, one can keep said reagent bottle in a desiccator far longer than its expiration date and it won't absorb any moisture and thus remain unchanged, while keeping it a few weeks in a very damp place is sufficient to turn the reagent into a mushy paste or a solid block). Once a reagent has passed its expiration date, it can no longer be used in professional labs, even though it didn't suffer any changes or wasn't contaminated, and even if it wasn't open since it was purchased. This is very much true for analytical reagents, which can no longer be used in chemical analysis once they've reached the expiration date and have to be disposed of, even if they weren't open or have shown any signs of degradation/contamination. This leads to a hoarding problem, since the expire reagents, even though they're still technically good, can no longer be used (at least for that purpose), so if you used, for example, small amounts of reagent from a 1 kg bottle, and after the expiration date you still have >900 g of unused reagent, you end up discarding much more than you used, which translates in lost money and resources.
For reagents used in synthesis, this can be avoided, by simply recrystallizing the salt from a concentrated solution, or for liquids a simple distillation is sufficient to generate a "fresh" reagent, since the resulting product is no longer the old one, and it's usually more pure. However, while this method is widely used by "poorer" labs, in some circles it's looked down upon, since there are concerns about contamination during the preparation of new product. Likewise, most reagent labels show the value of traces present in the product, which, in the event of a recrystallization or distillation, will change. While this isn't a problem for reagents used in synthesis, this practice is not allowed for reagents used in analysis, since, while one would have to reanalyze the traces present in the new product, an official certification is required for the newly produced analytical reagent to be valid.
Waste disposal
Most regulations forbid the release of lab-grade reagents down the drain or in the municipal sewage system. The laws are written in such way, that even dumping certain harmless lab-grade reagents, like acetic, citric, tartaric acids and their salts, sodium hydroxide, various alcohols and esters, that not only encountered as OTC products but are also disposed of by being poured down the drain, may be considered illegal. However, so far nobody has been prosecuted for doing this, so there is no clear answer (so far) what is legal to pour down the drain and what is not.
References
- ↑ https://www.allotment-garden.org/garden-diary/1989/ammonium-sulphamate-weed-killer-banned/
- ↑ https://web.archive.org/web/20091113071628/http://www.pesticides.gov.uk/garden.asp?id=1997
- ↑ https://www.atf.gov/explosives/binary-explosives
- ↑ https://www.ndrugs.com/?s=lentonitrat
- ↑ http://richenza.cz/de/professionelle-reinigungsprodukte/371-cleamen-420-sanitaerabfall-1-liter.html
- ↑ https://www.youtube.com/watch?v=4DUGRWjdNLI
- ↑ https://www.dps.texas.gov/RSD/Precursor/Laws/index.htm
- ↑ https://legiscan.com/TX/text/SB616/2019
- ↑ https://web.archive.org/web/20110420054619/http://www.deadiversion.usdoj.gov/chem_prog/advisories/surveillance.htm
- ↑ https://www.ttb.gov/industrial/fuel-alcohol-faqs.shtml
- ↑ https://www.ttb.gov/spirits/spirits-permits.shtml
- ↑ https://www.youtube.com/watch?v=ZZyzpDJtK5s