Glycine nitrate process (nanometer oxide particles)

[DeAdFX]

Glycine nitrate process

 

While bumbling on the internet about ammonium nitrate glycine double salt I stumbled

upon another interesting use for glycine, the glycine nitrate process. By mixing

A metal nitrate or multiple metal nitrates one can produce a metal oxide or a mixture

metal oxides. Supposedly other metal salts can be used like acetate. The resulting metal oxides are

extremely small (nanometer sized). Smaller = more surface area = faster rxn...

 

I am interested in applying this process to produce copper chromite. THis chemical is important

as a catalyst in speeding up the burn rate of rockets. Typically copper chromate is produced

by mixing a dichromate salt (ie K or Na). Copper chromate being insoluble is percipitated, isolated

and then decomposed into copper chromite. WHile I have not done this process and would not know if

it is an easier method it has the possibility to be a different method. For those that are concerned

about dichromate toxicity this could be useful in the sense that one could use Cr (III) instead.

I do not have Cr(III) and will have to make Cr(III) from Cr(VI).

 

 

Conversion of Cr(VI) --> Cr(III)

Mumbles mentioned that a metal (must be strong reducer) or organic compound can be used to do the reduction.

Other "methods" can be used such as bubling in SO2 gas, HCl (generates Cl2), or using H2O2. H2o2 and metal

reducing agent would probably be the safest. The Cr(III) can be percipitated with NaOH or any other strong base

 

 

Cr(III) --> nitrate

This is dependent on what sort of chemicals you have. Nitric acid or ammonium nitrate will make this fairly easy.

If not then you will have to use your chemical knowledge to figure out a solution.

 

Cr(NO3)3 --> Cr2O3

Dissolve Cr(NO3)3, Cu(NO3)2 and glycine in water and heat.

 

 

I have yet to do the experiment as I am still in the planning phase. I have Cr(VI) in the oxidization state and this will

make the experiment slightly less straight forward. I will use SO2 reduction as my first attempt just to make things a little

more interesting. If this fails then I will use H2O2 which should work nicely. From there everything should be easy.

 

Producing Cu(NO3)2

Most people should have access to copper sulfate. Others might have access to the oxide, basic chloride, carbonate and so forth.

Pottery grade chemicals like copper oxide tend to be less reactive in my experince. For instance I tried dissolving copper oxide

in HCl and I ended up with sludge. Double displacement is probably the best way to isolate copper nitrate. Calcium, strontium

or Barium nitrate would be good options. KNO3 can work but I don't know how the K2SO4 will interfere (midly soluble @ 0c).

 

 

Over time I will clean up this post, add more info and possibly do some other experimentation...

Edited November 10, 2010 by DeAdFX

[Mumbles]

The peroxide/dichromate reaction is a pretty violent one if everything is not carefully diluted. Also be careful because excess hydrogen peroxide can reoxidize Cr(III), thus it's not a very clean reaction unless you do it in an electrochemical cell.

 

As far the the more traditional copper chromite preparation. I don't know if it's important, but I've always returned the dichromate to chromate first. Most of the time it's not deliberately mentioned, but it happens when ammonia is added.

[DeAdFX]

The k dichromate and SO2 reaction worked to an extent. The k dichromate turns from orange to a very murky orange. Even with a 5 molar excess of SO2 it isn't enough:/. I feel retarded that I cannot get Cr(VI) to Cr(III) as I am lacking some important chemicals. Bah if I had sulfuric acid right now that would make reduction with an organic compound so much easier. I'm gonna check my chem stash hopefully I have something useful....

[DeAdFX]

Dichromate + cupric ion =/= percipitate.

 

I made a crude percipitate of copper chromate from potassium chromate and cupric sulfate. The percipitate dissolves in glycine making a greenish(? hard to tell) looking solution... fuck yeah! When i added ascorbic acid next the color changed to a bluish hue(i will try and investigate this later).

 

Perhaps I don't need Cr in the third oxidization state... Since glycine can dissolve the copper chromate I will try making a small ~1-3 gram test batch of copper chromate/ammonium nitrate/glycine

I will also try copper nitrate/ammonium dichromate/glycine/ammonium nitrate.

 

If the glycine ends up getting oxidized by the chromate prematurely I will probably have to by chromium sulfate :/.

Edited November 23, 2010 by DeAdFX

[Mumbles]

Unexpected, but very good to know.

 

Let us know how it works, and take a video of the reaction if you can. I bet it's quite cool looking.

[DeAdFX]

Ok I'm almost ready to make a 21.7 gram copper chromate run. I have my chemicals all mixed up in a beaker ready to go. HOWEVER.... I'm expecting the combustion to be fairly hot and slow. I don't think that a glass beaker will be able to handle the reaction without failing. What over the counter material will be able to contain the reaction without being destroyed or contaminating the product?

[Mumbles]

How about a stainless steel drink shaker or measuring cup?

 

BTW, I sent you something that might be helpful.

[DeAdFX]

minor update....

 

So i transfered the chemical mixture to a stainless steel drink shaker and heated the mixture up in a VWR lab oven. After a couple hours in their i pulled it out to examine the drink shaker. The vessel smelled strongly of ammonia and I noticed some slightly colored blue and green gunk on the walls. I placed the drink shaker in the oven again and applied the same amount of heat(from ~10am to 1pm). the contents looked about the same as last time but didn't have any ammonia smell. I tried igniting the mix inside of the container but only ashes and a slightly nutty smell resulted (possibly cyanide gas?). The reaction wasn't sulf sustaining. From this I believe that I added to much glcine or didn't add enough oxidizer.. I am going to place the reaction vessel inside of the oven again but this time jack up the heat some more. I will do this for 1-2 hours min and try igniting the mix again. If this fails I will wait till tomorrow apply a little more heat and try igniting the mix again.

 

If this plan fails I'm kinda doubtful I will continue as I have some other stuff going on in my life but I will try to add a semi clean version of my procedure to give on an idea of what I did and what they can do if they are interested in continuing.

 

edit: actually I think I might add potassium nitrate, chlorate or some other sort of oxidizer to the chemical soup ignite and collect the ashes.

 

edit again: Ok so cranking up the heat worked. Now my oven is filled with black crumbly shit which will be a pain in the ass to clean...

 

another edit: Also I won't have any pictures as my camera ran out of batteries and I can't find the charger:/. I'll try and ask my dad for his

Edited December 7, 2010 by DeAdFX

[Mumbles]

I'm glad to hear it worked out. I hope that article helped some.

 

Have you gotten a chance to examine the powder? Does it seem as fine as they make it out to be, or is it more on the order of clumps of nanoparticulate material? Either way, it's certainly exciting to hear the method worked out for you.

 

Are you going to get a chance to test out the powder as a catalyst before you move on to other things?

[DeAdFX]

I'm glad to hear it worked out. I hope that article helped some.

 

Have you gotten a chance to examine the powder? Does it seem as fine as they make it out to be, or is it more on the order of clumps of nanoparticulate material? Either way, it's certainly exciting to hear the method worked out for you.

 

Are you going to get a chance to test out the powder as a catalyst before you move on to other things?

 

the ashes produced from the reaction formed clusters of clumps that were easily disintigrated by touch. these clumps can be easily pulverized into powder w/ a motar and pestile. Whether or not this powder is nano meter sized I can't say. I have an intel microscope kicking around the house somewhere. I honestly doubt it will give any sort of definite answer but I could look at it.

 

I put the powder under a blow torch to see what would happen. Part of the mass glowed for a split second and powder was sent flying away. I tried adding some KNO3 to the powder and the KNO3 beaded up. There doesn't appear to be any residual carbon/oxidizable material present. When the powder is added to water there is a slight chromate color which is easily removed by a small addition of ascorbic acid. SO some of the chrome wasn't completly reduced.

 

I will now start mixing up some Na-Sally and KClO4 and report back. I don't have the proper technology to measure pressure/burnrate/thrust produced/etc so I will only be able to provide a "it burned faster to me" analysis.

 

Edit: hard to tell which burned faster... I think if you want a good answer this is something you will have to try for yourself. At least this experiment shows that the process is viable and possibly worth investing time/money into.

Edited December 7, 2010 by DeAdFX

[DeAdFX]

The reason why I am using odd numbers is that I had a batch of copper sulfate solution left over from a previous experiment and I based my synthesis off that.

 

 

Synthesis of Potassium chromate --> K2Cr2O7 + K2CO3 --> K2CrO4 + CO2

I made a solution of Potassium dichromate in water (18.24 grams in 100 mL H2O). I basified this solution w/ a stiochmetric amount of potassium carbonate ( 6.50 grams of K2CO3). The solution was still orangish so I gradually added (.6 + .5 + .5 + 1 + 1 +.5)grams of carbonate. The solution yellowed up.

 

Synthesis of Copper chromate

I had 148.5 mL of Copper sulfate solution that was stored at 5C. I extrapolated the solubility of copper sulfate @ 5C to be 15.8g/100mL or (23.46g in solution total). I mixed the potassium chromate solution (.094 mols) w/ the copper sulfate solution (.094 mols) which resulted in a red percipitate. This percipitate was collected, washed and then filtered. The percipitate weighed 21.7 grams which translates into .12 mols of copper chromate. So either I screwed up extrapolating the solubility or I picked some other junk in the filtrate.

 

Mixing the chemicals together....

II found this http://books.google.com/books?id=6T9q40K5XWwC&pg=PA83&lpg=PA83&dq=glycine+nitrate+process&source=bl&ots=Vr6o3yOd5x&sig=0HZ0PeOWQLIp5BWQ7GXi3BXm7LU&hl=en&ei=SKD-TO-uO5LmsQPG7P2vCw&sa=X&oi=book_result&ct=result&resnum=8&ved=0CEcQ6AEwBzgK#v=onepage&q=glycine%20nitrate%20process&f=false . In this document it stated that the researchers mixed the metal nitrate and glycine in a ratio of 1:2. I used this to base my ratios off of. To simplify things I mixed chromate in a ratio of 1:2 w/ glycine and ammonium nitrate to glycine 1:2.

I stated that I had .12 mols of copper chromate. To a beaker containing 100 mL I added .12 mols copper chromate, .12 mols ammonium nitrate and .24 mols glycine. The copper chromate began to dissolve once the temperature was cranked up.

 

I boiled a majority of the water off and added it to a stainless steel drink shaker. The drink shaker was then placed inside of a motar. The lid and a covering of aluminum foil was added to the shaker to prevent the powder from going all over the place. In reality this measures didn't help that much. This setup will now be refered as to the rxn vessel. The rxn vessel was placed inside of lab oven (heat settings 1-10). Since I am an idiot and din't write down the time spent in the oven I can't give any exact numbers. The 5 setting didn't provide enough heat but the 8 was able to provide enough. Don't be afraid to add a little extra heat to get the rxn going. The rxn vessel spent bout 1.5 hours in the oven @ the 8 setting.

 

Once finished collect the powders.

 

 

Stuff to keep in mind for improvements

In hind sight it would be a good idea to lubericate the drink shaker and drink shaker lid interface as these portions will stick very tightly to each other once the reaction is done. Boron nitride or Molly sulfide would be a good start for high temp lube.

 

Using Ammonium dichromate or Chromium nitrate as a chrome source would be a better option. Ammonium ions decompose into water and nitrogen. CHromium nitrate is probably better as it is already in the 3rd oxidization state. Synthesizing copper chromate introduced to many stray ions (Potassium and sulfate). Less crap = cleaner reaction

[Mumbles]

In order to remove a lot of the residual ions, you could filter off the initial crude precipitate and wash it a bit. From there you can add it to the glycine and AN to be left with a reasonably pure product.

[kaurgagan9960]

I have read fair enough about the role of glycine in the literature in Glycine Nitrate Process.............I want to know the exact role of nitrate?

Nitrate is an oxidant definitely but I want to know about it in detail....can anyone please help me?