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Preparation of liquid nitrogen dioxide - Video Tutorial

here we've got some old foreign currency left over from an exotic vacation


sadly we will be unlikely to return to the beautiful country for a while


but the coins are made of cut pro nickel


which is seventy percent copper so we'll have to put them to a chemical use


let's first do a quick test


this is 68 percent concentrated nitric acid


and a coin


and a coin


yeah this works


the brown fumes are nitrogen dioxide with a boiling point of around 20


degrees


see it should be possible to prepare liquid nitrogen dioxide so we rigged up


a special apparatus we've got the 500 mil to neck flask and we've got the


large neck stopper and the small neck leading to an adapter the large neck


will fit our coins


the adapter then leads to a tube and condenser


and then we've got the receiving adapter and a small flask sitting in a bowl


we've also got a takeoff using an old nasty bit of plastic tubing and this


leads up to our extractor and means we hopefully won't die of nitrogen dioxide


poisoning use ventilation this stuff is very toxic and unpleasant we've got some


loose cotton and a coin inside the bottle this process is extremely difficult to achieve a


We'll open the adapter, and we've covered this with a few centimeters deep of anhydrous calcium chloride.


This will hopefully absorb moisture and stop any acid aerosol from getting into our product.


We've got the condenser hooked up to ice water for cooling.


And we've got the receiving flask in a bath of ice and water.


Okay, so that's our setup. Not too complex.


Here's our large-scale acid. 100 mils of 68% concentrated nitric acid.


Let's get this into the flask.


And now we're just waiting for the temperature to drop.


Okay, so, here we are in our ice bath to drop nicely and level out.


The reaction is exothermic, so we've got the reaction flask sitting in a bowl of water to moderate the temperature a bit.


Okay, let's get on with the show.


The reaction kicks off fast with lots of brown nitrogen dioxide gas coming off.


At the other br…


we've initially got a lot of brown gas escaping and being drawn away by the


extractor and we then start to see the gas escape die down and a dark colored


liquid is condensing into our receiving flask


the reaction in the flask is vigorous and produces quite a lot of heat the


liquid collection starts to slow down after a few minutes


it looks like our drying setup is working as well


and our ice baths are still nice and cold


distillation has stopped so we're going to add a couple more coins to the flask


again


as before we've initially got some brown gas


emitted and then we're going to add a couple more coins to the flask again


but then soon after we start receiving the liquid again this is rather


interesting and we'll come back to this later on nitrogen dioxide actually


exists in an equilibrium between the single nitrogen dioxide species and the


timer species which is known as di nitrogen tetroxide at lower temperatures


and the timer species which is colorless his favorite and you can see hearing our


apparatus as the gas passes through our image we can see that our brown gas is


into the chilled condenser it changes to a paler color.


We've also got a little of the liquid condensing at the top here.


You can see it's actually got a blue color to it.


The reaction with nitric acid also produces some nitrogen monoxide, or nitric oxide.


Although it's not supposed to happen except for at low temperatures, we seem to have some


of the nitric oxide reacting with the brown nitrogen dioxide to form dinitrogen trioxide,


which is then obviously soluble in the liquid nitrogen dioxide.


Although liquid nitrogen dioxide contains a lot of colorless dinitrogen tetroxide, when


pure it's still a dark brown color.


Dinitrogen trioxide however is blue.


You can see the blue color quite clearly in the receiving adapter.


We added two more coins, making six in total, and continued to collect the blue colored


distillate.


The temperature of the reaction has raised our water bath temperature a bit, but it's


under control.


No more distillate coming off now, so it looks like we're done.


We quenched the reaction by adding 100 mils of cold water.


This reduced the gas evolution down to virtually nothing.


We then prepared a solution of sodium carbonate in water, on adding some of this a little at


a time, and restoppering the flask.


We then added a little bit of sodium carbonate in water.


We were able to purge most of the browned gas out of the apparatus.


This is a little safer and easier to dismantle now!


Here's our product.


About six or seven mils of a dark blue liquid which we think is mostly nitrogen dioxide,


but with some dioxide present.


nitrogen trioxide dissolved in it it seems to be fairly stable when cold


and we didn't notice any pressure buildup in the flask with the white


background you can see the blue color a bit more clearly okay now let's do some


experiments first dripping some onto a glass dish at room temperature it


creates producing heavy brown nitrogen dioxide fumes


and soon disappears without a trace


here's some cool water


it doesn't stick around for long as it reacts with the water it heats up


causing it to boil off


as brown fumes again.


The resulting solution containing nitric and nitrous acids is strongly acidic as you can


see here.


If this forms inside your lungs, you are in whole worlds of trouble.


Now for something more exotic.


Here's some solid hypoxylamine hydrochloride.


It's a very vigorous reaction.


We decided not to add the solid to the liquid as it could well be explosive on a larger


scale.


Now some ethanol.


Very pretty miniature explosions.


The liquid remaining has a very strong aldehyde aroma.


That was pretty so let's do it again.


Next, here's some benzyl alcohol.


Not as vigorous as ethanol, but the liquid heats up and there's a very strong almond


aroma of benzaldehyde produced.


Not a very practical synthetic method though.


Finally, ice cold potassium hydroxide solution.


Very vigorous and it looks like most of the product escaped as gas.


Well that's all our experiments done and our product used up.


But it was a very interesting experiment.


We're intrigued by the way that the brown nitrogen.


Too much nitrogen.


Nitrogen dioxide gas comes off the reaction at first but doesn't condense.


Even when the condenser is already ice cold it takes about 10 to 15 seconds and then the


blue liquid is seen.


Maybe somehow it takes the generation of nitric oxide to get the product to actually condense.


Although nitric oxide has a much lower boiling point, perhaps it forms some sort of a seatrope


or abduct with nitrogen dioxide and dinitrogen dioxide which is what we end up with here.


We're interested to hear your ideas and theories.


Thanks for watching.