Sciencemadness Discussion Board » Fundamentals » Beginnings » Alcohol 99,9% Select A Forum Fundamentals   » Chemistry in General   » Organic Chemistry   » Reagents and Apparatus Acquisition   » Beginnings   » Responsible Practices   » Miscellaneous   » The Wiki Special topics   » Technochemistry   » Energetic Materials   » Biochemistry   » Radiochemistry   » Computational Models and Techniques   » Prepublication Non-chemistry   » Forum Matters   » Legal and Societal Issues

Author: Subject: Alcohol 99,9%
Blunotte
Harmless

Posts: 49
Registered: 2-4-2015
Member Is Offline

Mood: No Mood

Alcohol 99,9%

Goodmorning everyone

These days I bought a bottle of 99.9% alcohol in a paint shop (see first image)
I then tried to distill a small part of it, to eliminate the denaturants present in it.
The result is the following: out of about 100 ml of the original product, almost half is distilled at a temperature of about 65 ° C (so I assume it is methanol), and only afterwards a distillation above 75 ° is started (therefore ethanol, see second image).
What amazes me is that the label says "99.9% ethyl alcohol, denatured with general denaturing".
Wow, half of it is pure poison! If someone accidentally tries to drink it, I don't want to think about it!

Antigua
Hazard to Others

Posts: 145
Registered: 27-9-2020
Member Is Offline

rockyit98
National Hazard

Posts: 283
Registered: 12-4-2019
Location: The Known Universe
Member Is Offline

Mood: no mood is a good mood

the 99.9% probably means 0.01% water +dye + bitter chemicals and almost all are alcohol whether methanol or ethanol.
from wiki "Denatured alcohol (also called methylated spirits, in Australia, Canada, Ireland, New Zealand, South Africa, and the United Kingdom; wood spirit; and denatured rectified spirit)[1] is ethanol that has additives to make it poisonous, bad-tasting, foul-smelling, or nauseating to discourage its recreational consumption. It is sometimes dyed so that it can be identified visually. Pyridine and methanol,[2] each and together, make denatured alcohol poisonous; and denatonium makes it bitter."
and no one can drink 200 proof Alcohol going glug , glug.

"A mind is a terrible thing to lose"-Meisner
Prepic
Harmless

Posts: 31
Registered: 23-4-2019
Member Is Offline

I noticed the small degree symbol ° where it states 99,9°.

Be aware this may mean 99.9 degrees proof equating to 49.95% Alcohol (ethanol) by volume (ABV). This may explain why there's so much methanol.

[Edited on 8-4-2021 by Prepic]
Fery
International Hazard

Posts: 690
Registered: 27-8-2019
Location: Czechoslovakia
Member Is Offline

 Quote: Originally posted by Blunotte Wow, half of it is pure poison! If someone accidentally tries to drink it, I don't want to think about it!

The poisonous are oxidation metabolites of methanol - formaldehyde and formic acid. They are formed in liver by alcohol dehydrogenase enzyme. Your product contains mixture of methanol and ethanol and both alcohols would compete on alcohol dehydrogenase. So the poisoning would be weaker than when drinking pure methanol. Antidotum for methanol poisoning is ethanol. Anyway 1:1 mixture is still lethal. Few years ago stupid greedy small alcohol producers in CZ (e.g. "Likerka Drak" and others) added methanol into alcohol bottles, they used too much of methanol, circa the same ratio as in your product 1:1, a lot of people died or at least suffered permanent health disabilities.

If there is a heaven, it seems not to be materially based. Does chemistry exist there and if yes, how does it look like? Are there good souls well supplied with laboratory equipment, glass, chemicals and information?
Fyndium
International Hazard

Posts: 1162
Registered: 12-7-2020
Location: Not in USA
Member Is Offline

Afaik methanol should be always labeled as poison, so selling a product that contains more than 1% or something is outright off the standard.

I face this phenomenon almost every time I distill some mixtures: stuff does not always have a boiling point, but a boiling range instead. For some stuff the bp range is even reported, and it is common to distill something under vacuum for example between 120-140C, and the product comes out pure and produces expected yields in further use.
zed
International Hazard

Posts: 2265
Registered: 6-9-2008
Location: Great State of Jefferson, City of Portland
Member Is Offline

Mood: Semi-repentant Sith Lord

Totally unreliable. I have priced such products here in the USA. The standard products available in the general marketplace, are usually loaded up with methanol. I'm assuming, because methanol is dirt cheap, whereas Ethanol is not. If I wanted methanol, I would buy straight methanol.

Now, being in an "Everclear" state, I can buy 95% Ethanol, over the counter here. Sadly, because some people drink the stuff, there is a hefty "Beverage Tax" everywhere in the USA.
Fyndium
International Hazard

Posts: 1162
Registered: 12-7-2020
Location: Not in USA
Member Is Offline

Production of both isn't expensive at all, ethanol is used as fuel as well.

I'm surprised if it's not available in North America as well. In Europe, ethanol is basic constituent of all kinds of alcohol based products. Methanol is not sold for consumers at all anymore, only for technical use, like fuel or solvent. I buy my ethanol as car product, it's sold in various sizes between 1 and 200 liters and contains ethanol, detergents and denaturants. Makes straight azeotropic with simple distillation. Methanol as a fuel, or professional car product or solvent.

Fair price would be between 2-4€ per liter.

I never buy those small bottles, the price is a runaway. Paying over 30€ per liter for ethanol as solvent would make me stop this hobby at once.
zed
International Hazard

Posts: 2265
Registered: 6-9-2008
Location: Great State of Jefferson, City of Portland
Member Is Offline

Mood: Semi-repentant Sith Lord

Methanol can be produced industrially from petrochemicals.

Ethanol is generally produced by fermentation of corn, followed by distillation. It's much more expensive to produce than methanol. I suppose it might be available here as fuel grade. I'll check.

I can buy Methanol for less than 10 bucks a gallon. Ethanol? No way!
Fyndium
International Hazard

Posts: 1162
Registered: 12-7-2020
Location: Not in USA
Member Is Offline

Really?

Ethanol 1.91 USD per Gallon

Methanol USD 1.56/Gal*

The price difference really does not relate to any remote degree to what the small buyer/consumer is used, and it appears that even if you buy 100kT tanker-load, even small fluctuations will balance out the difference, so other factors like toxicity and local availability affect more.

For example, IPA costs $1300/MT, but you will pay several times the price of ethanol or methanol as consumer. Why? I have no idea. Some asshole apparently labels it special and charges multitudes. For the record, the cheapest otc IPA bottle I was able to find was 12€/L, which is hefty. Quick search indicates that 25L can costs 100€. I actually once dug up similar prices when a salesman told that the "special" product is very expensive to make. Of course, he can't affect the price, but I'm really not buying a single word someone says if he's trying to sell something. draculic acid69 International Hazard Posts: 1308 Registered: 2-8-2018 Member Is Offline I have seen a product labelled "specially denatured alcohol" which is 95%etoh 5%methanol. Different to the regular denatured alcohol around here zed International Hazard Posts: 2265 Registered: 6-9-2008 Location: Great State of Jefferson, City of Portland Member Is Offline Mood: Semi-repentant Sith Lord I bought 99% IPA at a local market, for ~12 dollars US per gallon. Dirt cheap. Methanol is also dirt cheap. Ethanol, is not dirt cheap. It is expensive. Expensive, and highly regulated. The USA Ethanol Fuel price, is deceptive. It is government subsidized. Your idea of refining fuel Ethanol, is excellent. Guys claim, adding a gallon of water to a gallon of E85, will cause the gasoline to separate off. Thereafter, distillation and/or chemical methods. will produce a decent facsimile of useable ethanol. I have a reference, nearby. I'll fetch it. https://www.dudadiesel.com/choose_item.php?id=methdrum https://www.dudadiesel.com/choose_item.php?id=55gethanol Apparently, I can buy just a few gallons of E85, at a gallon price comparable, to what I would pay when buying a 55 gallon drum. [Edited on 9-4-2021 by zed] draculic acid69 International Hazard Posts: 1308 Registered: 2-8-2018 Member Is Offline I'd rather use regular denatured alcohol for any rxn than risk using ethanol refined from petrol with who knows what kind of shit leftover in it.just sounds nasty Fyndium International Hazard Posts: 1162 Registered: 12-7-2020 Location: Not in USA Member Is Offline Well, you ain't gonna drink it, and you will eventually extract your product with petroleum based toluene, so what's the big deal? zed International Hazard Posts: 2265 Registered: 6-9-2008 Location: Great State of Jefferson, City of Portland Member Is Offline Mood: Semi-repentant Sith Lord Ummm. Most denatured Ethanol formulations are useless for me. Useless AND expensive. The adulterants interfere with chemistry, and as we previously discussed, there may be excessive amounts of Adulterants present. Denatured Alcohol should be Ethanol + a small amount of denaturant. 50/50, ain't kosher, but it is not uncommon. Fyndium International Hazard Posts: 1162 Registered: 12-7-2020 Location: Not in USA Member Is Offline Of course it's another matter if you need pure ethanol, not just technical ethanol. If reagent grade is needed, one should be very vary of OTC products anyway. In that instance, extracting one with effort, or buying potable ethanol is an option. My feedstock ethanol consists azeotropic ethanol, MEK, detergents and some high bp additives which can be easily separated by distilling, and second run can be made with NaOH to condense MEK, and if extra purity is required, stirring with activated carbon overnight gets rid of most residual crap. Someone even managed to make it potable that way. All mixtures are different, though, but in EU methanol is not used for denaturing ethanol, it's sale for consumers as blend mixture product is prohibited. Btw, ethanol is practically always fermented, I'm not aware it's produced in large amounts from petroleum feed. Deathunter88 National Hazard Posts: 473 Registered: 20-2-2015 Location: Beijing, China Member Is Offline Mood: No Mood In the US the green label Kleenstrip Green Denatured Alcohol is 95% ethanol. The regular red label is about 60% ethanol and 40% methanol. Just buy whichever suits your needs the most, I don't get what all the fuss is about. draculic acid69 International Hazard Posts: 1308 Registered: 2-8-2018 Member Is Offline  Quote: Originally posted by Fyndium Of course it's another matter if you need pure ethanol, not just technical ethanol. If reagent grade is needed, one should be very vary of OTC products anyway. In that instance, extracting one with effort, or buying potable ethanol is an option. My feedstock ethanol consists azeotropic ethanol, MEK, detergents and some high bp additives which can be easily separated by distilling, and second run can be made with NaOH to condense MEK, and if extra purity is required, stirring with activated carbon overnight gets rid of most residual crap. Someone even managed to make it potable that way. All mixtures are different, though, but in EU methanol is not used for denaturing ethanol, it's sale for consumers as blend mixture product is prohibited. Btw, ethanol is practically always fermented, I'm not aware it's produced in large amounts from petroleum feed. Most petroleum feedstock of 2carbon length is almost surely always used for making ethylene. Methane gas (natural gas) is a thing,propane is a thing, butane is a thing but not ethane. I suspect that all ethane goes directly to ethylene for plastic. I guess some might go to ethanol production but who knows for sure. Blunotte Harmless Posts: 49 Registered: 2-4-2015 Member Is Offline Mood: No Mood  Quote: Originally posted by Deathunter88 In the US the green label Kleenstrip Green Denatured Alcohol is 95% ethanol. The regular red label is about 60% ethanol and 40% methanol. Just buy whichever suits your needs the most, I don't get what all the fuss is about. I was just amazed at the difference between the contents of the bottle and the declaration in the label, so I created the thread However, when the new glassware arrives I will do a more detailed analysis (for now I can only distill small quantities at a time, and therefore inaccurately) Bedlasky International Hazard Posts: 949 Registered: 15-4-2019 Location: In Turgon's hidden city Member Is Offline Mood: Unavailable In Europe is ethanol cheap. 3€ for 1 liter bottle. I once did GC analysis of this commercial stuff and it contained: 91,93% EtOH, 1,11% i-PrOH, 1,41% MEK, 5,45% H2O and denatonium benzoate. Praxichys International Hazard Posts: 1063 Registered: 31-7-2013 Location: Detroit, Michigan, USA Member Is Offline Mood: Coprecipitated 5 gallon bucket, 14 pounds of white sugar. Top off with hot water, stir to dissolve. Add$4 packet of turbo yeast from Amazon. Slap a lid on it, make an airlock with a bit of hose and a soda bottle. Maintain less than 100°F.

19% ethanol solution is ready in 6 days. I add some SparKleen clarifier to flocculate the yeast and cause it to settle over a day or two. Distill as needed; there are around 3.5 liters of recoverable ethanol in there. (Pro tip - they make 5 gallon pressure cookers for canning. It's trivial to drill a hole in the lid and fit a coil of malleable copper tubing with a compression fitting)

Salt the water out of the distillate with K2CO3, redistill, store. Save 2.5 liters for the lab and the rest for orange juice screwdrivers.
Blunotte
Harmless

Posts: 49
Registered: 2-4-2015
Member Is Offline

Mood: No Mood

This is what I got from distillation:
- About 250cc of methyl alcohol
- About 500cc of ethyl alcohol
- A residue starting to boil at 82 ° C, which I don't know what that could be. Some idea?

(98% for ethyl is presumed, because the alcohol meter gave a value of 100%, but it seems unlikely to me )

[Edited on 8-5-2021 by Blunotte]
Texium

Posts: 3779
Registered: 11-1-2014
Location: Salt Lake City
Member Is Offline

Mood: Triturated

It is likely that your ethanol contains some methanol, and vice versa. A simple distillation won’t effectively separate substances with such a small difference in boiling points. Depending on the source, you’ll see anywhere from 25 to 100° C as the minimum difference in boiling points for fractional distillation to be effective. I think it’s usually closer to the lower end of that, but even so, a difference of only about 13° C isn’t going to give you very good separation, especially not without really accurate temperature control. I would recommend trying a fractional distillation.

Come check out the Official Sciencemadness Wiki
They're not really active right now, but here's my YouTube channel and my blog.
Blunotte
Harmless

Posts: 49
Registered: 2-4-2015
Member Is Offline

Mood: No Mood

You're right, I think...
S.C. Wack
bibliomaster

Posts: 2419
Registered: 7-5-2004
Location: Cornworld, Central USA
Member Is Offline

Mood: Enhanced

 Quote: Originally posted by Fery Your product contains mixture of methanol and ethanol and both alcohols would compete on alcohol dehydrogenase. So the poisoning would be weaker than when drinking pure methanol. Antidotum for methanol poisoning is ethanol. Anyway 1:1 mixture is still lethal.

Such is widely quoted but AFAIK has little factual basis for exposure to mixed alcohols...pretty sure that very little of much less than 1:1 is required for bad things to happen, such as permanent degradation of sight, etc.

The most popular brand was similarly deceptive in their MSDS years ago, then they changed it to being clear that it was about 50/50...that must have been bad for business because they're back to deceptive.

 Quote: Originally posted by Deathunter88 In the US the green label Kleenstrip Green Denatured Alcohol is 95% ethanol. The regular red label is about 60% ethanol and 40% methanol.

Do you know this or are you going by the high end of the deceptive SDS? (trade secret...like it would be so hard for a competitor to analyze...pure and unadulterated consumer deception) People expect the banned DCM to be toxic, but they're not expecting ethanol to be 30%...I hope they get sued J&J style and the owner ends up on the street, but it won't happen; they're doing it because they can.

A drum of denatured costs twice as much as a drum of methanol, it would not make sense to expect SDS ranges to favor high ethanol. I'm not sure that denatured ethanol sold for fuel blending costs the same (to anyone) as the same product from the same USA plant sold for other purposes. (BTW it's almost impossible to find gasoline without ethanol in it locally; only one chain sells it AFAIK, for 30 cents a gallon more)

"You're going to be all right, kid...Everything's under control." Yossarian, to Snowden

 Sciencemadness Discussion Board » Fundamentals » Beginnings » Alcohol 99,9% Select A Forum Fundamentals   » Chemistry in General   » Organic Chemistry   » Reagents and Apparatus Acquisition   » Beginnings   » Responsible Practices   » Miscellaneous   » The Wiki Special topics   » Technochemistry   » Energetic Materials   » Biochemistry   » Radiochemistry   » Computational Models and Techniques   » Prepublication Non-chemistry   » Forum Matters   » Legal and Societal Issues