From: Subject: PowerLabs Nitro Starch Synthesis Date: Sat, 15 May 2004 22:07:03 +0200 MIME-Version: 1.0 Content-Type: multipart/related; boundary="----=_NextPart_000_0035_01C43AC8.F446D710"; type="text/html" X-MimeOLE: Produced By Microsoft MimeOLE V6.00.2800.1165 This is a multi-part message in MIME format. ------=_NextPart_000_0035_01C43AC8.F446D710 Content-Type: text/html; charset="Windows-1252" Content-Transfer-Encoding: quoted-printable Content-Location: http://www.powerlabs.org/chemlabs/nitrostarch.htm PowerLabs Nitro Starch Synthesis

PowerLabs NitroStarch = Synthesis

3D"All

 
 
 

 

 

 Yet another POWERLABS=20 exclusive!

 Nitro starch Laboratory=20 synthesis:

  •  INTRODUCTION:

 Nitro starch, is actually a = mixture of=20 several nitrate esters of starch with the formula=20 [C6H7(OH)x(ONO2)y]= n=20 where x+y=3D3 and n is any whole number from one on up. The exact = composition=20 depends on the reaction conditions during the nitration. Nitrostarch = found a use=20 as a filler in hand grenades back in WWII, and also in mining explosives = It was=20 first made when H. Barconnot nitrated cellulose and starch back in 1833. = At that=20 time nitrocellulose and nitrostarch were thought to be one and the same. = Then A.=20 B=E9champ applied various methods of separating them in 1862. The US = first began=20 to produce nitrostarch in 1888 under the name Volney Powder. Various = companies=20 produced nitrostarch throughout both world wars, but the US emerged as = its sole=20 manufacturer.
 It was after being enquired by a British Chemist = as to=20 the manufacture of this compound that I realized that the Internet did = not yet=20 have a source of information as to how its synthesis may be performed. = Knowing=20 the similarities between it and nitrocellulose, and having performed the = synthesis of nitrocellulose numerous times before, it was realized that = nitro=20 starch could be made in a similar way, and so experiments were performed = to find=20 out exactly how. The first batches suffered from nitration runaway, = excess=20 un-nitrated starch, and decomposition during acid neutralization. After = 5 failed=20 attempts which included anything from dumping the reaction halfway to = having to=20 evacuate the room to flee a cloud of billowing nitrogen dioxide vapor, a = somewhat effective procedure was devised, which is shown below for = informational=20 purposes.
 As with any other nitration, this procedure is = hazardous and=20 involves the use of highly corrosive acids. The final product is toxic = and=20 dangerous. This should only be attempted by experienced=20 chemists!


 

  •  MATERIALS:

 Reactants:

 Glassware:

98% Concentrated Sulfuric Acid=20 (H2SO4(l))

150mL Glass = beaker.

68% Concentrated Nitric Acid=20 (HNO3(aq))

Pipette

Starch

Stirring = Rod 

Ethanol (C2H6O(l))

Funnel/filter = paper

Distilled Water (H2O(l))

Ice = bath

=20  Here all the chemicals used in the synthesis are seen, from left = to right,=20 back to front: Sulphuric Acid (98%), Nitric Acid (68%), Distilled water, = corn=20 starch, 150mL pyrex beaker, thermometer, spatula.

 

 

 

 

 

 


 

  •  PROCEDURE:

 

A solution of 65mL Sulphuric Acid (98%) and 35mL Nitric Acid = (68%) are=20 mixed in a 150mL beaker and allowed to cool (the dehydration of the = nitric acid=20 produces enough heat to warm the solution by as much as 60C, so it is = very=20 important to start off with the acids at no more than room temperature, = and to=20 cool the mixture down to 10C or so prior to the addition of = starch.

 

 

 

 

Starch is than added slowly whilst the mixture is stirred = vigorously=20 until all of the 18cc have dissolved. During the addition the = temperature rises=20 and it is important that it does not go above 35C. Once all of the = starch has=20 dissolved the mixture is placed on a hot plate and heated to 40C for one = and a=20 half hours, with occasional stirring. It forms into a white precipitate = with a=20 consistency similar to honey.

 

 

 

 

 Once the heating period is complete the nitro starch = and acids=20 mixture are added to 400mL of cold distilled water and stirred. Once = stirring=20 stops the nitro starch can be seen precipitating in the bottom of the = beaker. As=20 with nitrocellulose, the nitrated version of starch looks no different = from what=20 was started out with. Filtering this acid solution presents a special = problem,=20 however: It will weaken the filter paper and cause it to rip. Attempting = to=20 neutralize it with a carbonate will require very large amounts of it and = cause=20 everything to foam out of the beaker. Neutralizing it with ammonium = hydroxide=20 causes it to boil over and decomposes the nitrate. My solution was to = use a=20 micropore nylon filter which was not attacked by the acid, and filter = the=20 solution through it, with considerable loss of the final product. = Decantation=20 might prove worthwhile if one is willing to wait the long time required = for all=20 of the nitro starch to precipitate at the bottom.

 

The final product of any nitration will always contain some = residual=20 acid and oxides of nitrogen which can make it extremely unstable and = prone to=20 self decomposition when stored over time. It is thus necessary to = neutralize=20 this acidity. The industrial method calls for washing with Ammonium = Hydroxide=20 solution, however I found that my nitro starch decomposed when treated = that way.=20 I decided to boil it in sodium bicarbonate solution instead, and add = some Urea=20 to the final product so as to take up any nitrogen oxides produced (this = is=20 essentially what is done to nitrocellulose).

 

 

 

Here you see the final product, after 5 failed attempts. It = consists=20 in a fine powder that is mostly white but due to some decomposition = during the=20 acid neutralization phase (it seems as though nitro starch is highly = temperature=20 sensitive) acquired a brownish tint. It dissolves in acetone much in the = same=20 way nitrocellulose does.

 

 

 

 

 

  •  RESULTS!

 

The product deflagrates with a very hot flame in exactly = the same=20 way as nitrocellulose, as can be seen on the picture to the left. = Clicking on=20 the picture will show a video of this particular burn test (146kb). It = was=20 concluded that nitrocellulose is a much more worthwhile starting product = for=20 nitrations.

 

 

 Questions? Comments? = Suggestions? E-mail me!

Back ] Home ]=20 Up ] Next ]=20

  Hits since=20 23/05/01.

 Last updated = 30/01/04=20

 Copyright =A9 2000 - 2002 by Sam Barros. All = rights=20 reserved.
 Removing any material from this site for = display=20 without consent from its author consists in an infringement of=20 international copyright laws and can result in fines up to $50000 = per=20 infringement, plus legal costs. So ASK ME before you remove = anything from=20 here.
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