Note to self never do thishttp://www.nbcchicago.com/news/local/Chemical-Explosion-Reported-on-West-Side-Chicago.html
It's what you learn after you know it all that counts.
Don't forget to add the Fuming Nitric Acid with the Sulfuric Acid and Glycerin.
There is another chain about the Chicago Fire.
For those who are not familiar with that combination it is the formula for nitro glycerine, but in it's extremely unstable form. Performing this combination is greatly discouraged as a health/life risk.
Why would sulfuric acid cause glyerine to explode..?
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Concentrated nitric acid and concentrated sulphuric acid mixed together form "nitrating mixture".Nitrating mixture is an extremely powerful oxidiser and is the precursor to some of the most powerful explosives-trinitro toluene (TNT) and nitroglycerine,among others.
It is extremely dangerous to mix any organic material(alcohols and glycols included) with nitrating mixture as an explosive can easily be the result-and these explosives can be very unstable and self detonate-1ml of nitroglycerine yields 12000ml of gas in a fraction of a second.
Personally I would avoid using nitric acid in any form in any bio process.
So, we've discussed that nitroglycerin is pretty gnarly stuff. And, I think that is the key to everything.
Unfortunately, my chemistry is a little rusty, but here is a shot.
What is unique about nitroglycerin (as well as Trinitrotoluene (TNT)) is that they can spontaneously decompose without any additional chemicals, and it is a very exothermic (produces energy) reaction.
So... our reagents/reactants:
Glycerin (H2C-OH)(HC-OH)(H2C-OH), or C3H5(OH)3
Nitric Acid (HNO3)
Sulfuric Acid (H2SO4)
Sulfur Trioxide (SO3)
Note, SO3 + H2O ==> H2SO4 (sulfuric Acid) in what is an exothermic reaction.
Nitroglycerin (CH2NO3)(CHNO3)(CH2NO3) or C3H5N3O9
And, "fuming Sulfuric Acid" lacks some water, and thus is a mix of H2SO4 and SO3. And, it reacts with water in an exothermic reaction (produces heat and energy)
So, to make nitroglycerin, we essentially take:
(Glycerin) + 3 (Nitric Acid) ==> (Nitroglycerin) + 3 (Water)
(H2C-OH)(HC-OH)(H2C-OH) + 3HNO3 ==> (CH2NO3)(CHNO3)(CH2NO3) + H2O
As mentioned above,
Nitroglycerin (CH2NO3)(CHNO3)(CH2NO3) or C3H5N3O9 will spontaneously decompose into its constituent parts in a highly exothermic reaction (and no air or anything else is required, just a little energy to touch it off).
2(C3H5N3O9) --> 6CO2 + 5H2O + mixture NO, NO2, N2, O2, CO, etc. + LOTS OF ENERGY
The point is that we didn't add any nitric acid...
The mix was just glycerin (probably wet) and sulfuric acid (possibly fuming sulfuric acid).
But, I believe essentially the same thing will occur:
(Glycerin) + 3 (Sulfuric Acid) ==> (glycerin-hydrogen-sulfate) + 3 (Water)
(CH2OH)(CHOH)(CH2OH) + 3(H2SO4) ==> CH2(HSO4)CH(HSO4)CH2(HSO4) + 3H2O or (C3H8S3O12) + 3(water)
Now, this beast doesn't seem to have a lot of info about it on the web... but, it should spontaneously decompose into it's constituent parts as above.
(C3H8S3O12) ==> 3CO2 + 4H2O + mixture of CO, Sulfur, SO, SO2, O2, SO3, and H2SO4.
There has been a discussion of rocket fuels.
We all know about Hydrogen Gas (H2) + Oxygen Gas (O2), is commonly used by NASA. But, keeping them in liquid form for easy storage requires very low temperatures and high pressures, and is very difficult to handle.
Other two-liquid fuels include Glycerin and strong acids (nitric acid or sulfuric acid) for the reasons discussed above. They are difficult substances to handle, but don't require the extreme pressures and temperatures that the H2 and O2 require. And, thus are better suited to amateur enthusiasts.
Solid rocket fuels are somewhat like dynamite and are essentially substances like nitroglycerin contained so that it decomposes rapidly, but in a controlled fashion.
Very nice explanations that should be filed under a "don't try this at home" heading. Not that any of us should ever need to redo Alfred Noble's research, but for the reason that accidental mixing of chemicals can lead to such results.
My first thought was to go check what acids I've used in the past to unclog a floor drain that may have some raw glycerin in there. Glycerin works great at cutting that sticky oil residue off the concrete, but washing the floors and cleaning the drains on the same day might ruin your weekend...
My guess is that you are ok with the floor drain as you are probably using dilute mixtures of acids (weak Sulfuric or Hydrochloric). Lots of water, dirty glycerin, etc.
I was actually wondering why doing an acid wash of WVO apparently is "safe".
My guess is that it all depends on concentrations, and perhaps the quantity of water.
I'm sitting here wondering if you could create a similar reaction with:
Sulfuric Acid with high concentrations of Sulfur trioxide (SO3),
Quite dry, high titrating WVO
Does one add a glycerin prewash to an acid esterification?
Anyway, I mentioned in the other chain about the Chicago Fire.
Don't guess what is in the containers. Label them.
And, if you have incompatible chemicals, for example ammonia (or ammonia containing cleaning chemicals), and bleach (or bleach containing cleaning agents), label them as incompatible.
And, we now know that strong acids (Nitric, Sulfuric, and probably hydrochloric) and glycerin byproduct should also be labeled as INCOMPATIBLE.
In case anyone is wondering I do offer this warning in The Guide on making soap with the glycerine layer.
"the MSDS should always be referenced and well studied before adding a substance to the glyerine layer."
What applies in the shop also most suredly applies with soap making as the glycerine is in an even more concentrated form and therefore subject to careful considerations before adding "stuff" to it to get a desired result. Some people just don't think, and in this case that could have a rather unfortunate effect, and the novelty of it will have the various medias crawling all over each other to get a piece of it.
I've split the crude glycerine into it's respective layers using Sulfuric acid with no ill effects at all. The only reaction occuring there is the neutralizing of the base and acid. How do you create nitroglycerine without nitrogen?
I did not know you could. I thought it was Nitric Acid, not Nitrogen.
AFAIK, it is normally a mixture of sulfuric acid and nitric acid that are mixed with the glycerine, not nitrogen.
Yeah I was reffering to the element Nitrogen being present in a molecule not just adding nitrogen(g).
But what in the world would a biodiesel plant be doing with any nitrating compound in the plant?
Nitrogen gas (N2) is a component of air, and is relatively inert, and is commonly used to displace air to make an anoxic environment.
However, One of the problems with internal combustion engines is that it can be oxidized to make NO, or NO2... which is not inert (which probably isn't relevant here).
Looking on the internet at explosives and rocket propellants, I'm not seeing many notes of using just sulfuric acid and organics (or alcohols). However, there were some notes of using metal-sulfates... copper sulfate, magnesium sulfate, zinc sulfate, This also includes Sodium Sulfate and Potassium Sulfate.
Anyway, I think I will assume that giving the correct temperature and pressure, sulfuric acid will work as an oxidizer. But, perhaps it takes effort to start the reaction, and it may be slower than using Nitrates.
My question now is what made the workers decide to start RUNNING, and why was it serious enough that they set off alarms and ran rather than trying to remedy the situation?
Did they notice a rapid temperature/pressure spike?
Bulging of the tanks?
Pressure relief valve whistling?
Perhaps, had they actually made nitroglycerin, they would have had too little time to react.
Keelec I am certainly no chemist but I always thought that sulfuric acid was a catalyst and dehydrator in nitration reactions.
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