quicksilver - 7-8-2006 at 07:05
I couldn't find the source for this proceedure nor any background......and it seems so familiar. 
Ethylene Glycol Dinitrite.
*procedure:
Sodium nitrite is dissolved in water to form a near-saturated solution, and added to a slight excess of ethylene glycol. The mixture is cooled to 0*C,
and concentrated hydrochloric acid is added dropwise, while stirring and keeping the solution at or below 0*C. The amount of hydrochloric acid added
is theoretical.
The dinitrite forms as a yellow oil, which sinks to the bottom of the vessel. It can be dried over anhydrous sodium sulphate. Density at 0*C,
1.211g/cm3.
N2O3 (a mixture of NO and NO2) can also be employed; it is bubbled through the aqueous alcohol.
Question: Does anyone know the origin of this specific lab and any related info? All the background I remember was that it was used for the
nitrosation of hydrazine but for such a simple synth, could it have other uses in energetic chemistry?
- Thanks
[Edited on 7-8-2006 by quicksilver]
Rosco Bodine - 7-8-2006 at 07:27
That sounds like one of my proposed syntheses rather than an actual experimental report , as the product which I did get was was a very pretty emerald
green oil , a sample of which has been kept in a glass stoppered bottle in a freezer for several years .
IIRC I did write the actual experimental procedure details later ......but I am not certain . Some of this stuff I may have posted either here or at
E&W so you should check both places . A search for dinitrite should zero in on it quickly . There was a patent reference also .
Glycerin also forms nitrite esters but I haven't tried these .
See this thread for quantities and the patent #
The last post has most of the information . I never tried
microteks suggested method but it may be superior for
this as it involves no water in contact with the nitrite ,
and the nitrite is water sensitive , which causes losses
and a need for separating the product quickly when it is precipitated from an aqueous system where it decomposes
steadily even in the cold , if it is in contact with water .
https://sciencemadness.org/talk/viewthread.php?tid=544#pid52...
[Edited on 7-8-2006 by Rosco Bodine]
chemoleo - 7-8-2006 at 09:42
Interesting you mention the polynitrites.
Given the ease at which butyl or amylnitrites form, I always thought, yes, glycerol should be an interesting one. Another one that is on my list is
inositol hexanitrite, where the OB should be better. Nitrites are not supposed to be explosive, but i.e. in the case of the inositol, I can't see how
it couldn't be! But then, the CO bond is already present, so this energy-yielding step already drops out from the final energy balance.
Regardless, there's nothing special about the procedure, it is the same that is used with butylnitrite.
PS rosco you were using the EG-dinitrite for the production of azide from hydrazine, rather than the more commonly used isopropylnitrite? Did it work
ok? Did you ever test flammability etc of EG-dinitrite?
Rosco Bodine - 7-8-2006 at 15:34
Yeah I used the EG dintirite a couple of times in Azide
syntheses because it is a lower volatility ester than the ether like isopropyl nitrite , and easier to handle . But the disadvantage is that it is
harder to make and after its use in a nitrosation you are left with the glycol which
is nonvolatile and oily , which wont simply evaporate from your filtered azide like isopropyl alcohol will . So the isopropyl nitrite just gives a
cleaner synthesis , but the
glycol dinitrite does indeed work as would probably glycerin nitrites as well , though I never tried them .
I think I read somewhere that some of the nitrite esters are indeed explosive , but I never used them for anything except intermediates and ignition
of them is the last thing I wanted because I believe them to be explosive ,
or at the very least at warm temperatures they are capable of pyrophoric ignition in air ....whether it goes to detonation or not , the vapors are
explosive something
like ether would be . Ethyl and probably Methyl nitrite
are this way , and the rest are probably the same to varying degree , so I would not assume them to be benign substances at all . They are
phsiologically active
and they attack polyethylene and polypropylene or other common plastics other than teflon . Polyethylene will
for awhile look okay following exposure , but then in hours will discolor and become opaque and crumble to dust as it degrades by some unknown
mechanism .
It is similar as the effect of d1.5 nitric acid only slower .
And these nitrite esters fume similarly in air , lots of
red fumes especially in moist air . They are extremely reactive materials .
Erythritol Tetranitrite and Pentaerythritol Tetranitrite ,
and all the rest Sorbitiol , Maltitol , ect. of the polyol
series could have interesting nitrites which may have value
as nitrosation reagents .....but this is one of those obscure
kinds of areas where I haven't seen any references ,
so it might make for some interesting experiments to
examine these nitrite esters . These nitrites could have usefulness as intermediates useful in Diazotizations and similar reactions , formation of
nitrosamines , ect .
[Edited on 7-8-2006 by Rosco Bodine]
chemoleo - 7-8-2006 at 16:22
Which brings me to another question- are there easy ways from organic nitrite to nitrate?
Nitration may be difficult at times (i.e. high level nitrated NC), so if there's an easy way to oxidise the nitrite, this may prove a way for
otherwise impossible to synth nitrates.
Yes they are physiologically active but you are incorrect on their magical effect on PP. I kept amylnitrite in a PP tube for a month, with no visible
or physical change. Some of the AN diffused out, but that is to be expected from almost any volatile solvent. Also I never noticed any fuming, and a
slight NOx smell (which wasn't visible) could be noticed after weeks at RT only when the nitrite wasn't dry. When it was dried by shaking with 4M
NaCl, no decomposition was observed.
Rosco Bodine - 7-8-2006 at 16:40
I am not sure about conversion of the nitrite to nitrate .
Because of the instability and reactivity of the nitrite ,
its use as an intermediate in a nitration does not fill me with enthusiasm .
I haven't made the amyl or butyl nitrites but the
attack of plastics is there for ethyl and isopropyl nitrites
I am positive , and also for the glycol nitrite IIRC .
After seeing the effect I just avoid using anything
but teflon and glass whenever any long exposure
like storage is involved .
You will see what I mean when you observe the
isopropyl or glycol nitrites .
quicksilver - 8-8-2006 at 06:26
Somehow I THOUGHT it was Roscoe.....
and that was just what I was thinking in the context of this prep -> the oxidation of the nitrite to a nitrate; making an end-run around a "mixed
acid" synth.
Or it's subsitute (the EG Nitrite) for a dry solid...yielding a energetic which has a higher density. Just a thought.
Rosco Bodine - 8-8-2006 at 07:10
My main interest in these organic nitrites is that they
could have usefulness as nitrosation / diazotization
reagents which are soluble in non-aqueous systems ,
unlike the usual nitrite plus acid nitrosation schemes
which are done in aqueous systems .
Rosco Bodine - 8-8-2006 at 12:48
Another idea of mine sort of related to the idea of further oxidizing the organic nitrite esters , involves a possible
reaction between the organic nitrite esters and triacetone triperoxide , in a non-aqueous solvent ....
perhaps chloroform . Something similar was tried by Axt
but it involved reacting the TATP dissolved in xylene , using gaseous N2O3 for the nitrosation , which seemed
to most definitely react ....but the reaction was not investigated further but to determine the xylene itself
was also reacting . See the thread
https://sciencemadness.org/talk/viewthread.php?tid=3033
I was thinking that a different solvent like chloroform and different nitrosation reagent like one of the organic nitrites could be a further
investigation along the same
line .
chemoleo - 8-8-2006 at 14:37
Rosco, do you have the mechanism for these nitrosations you mention, and the general procedure for it?
Rosco Bodine - 8-8-2006 at 17:22
There were a couple of different scenarios which I thought might occur there with the acetone peroxide trimer , * speculating * there is a chance of
introducing nitro or nitroso groups indirectly where the peroxy groups are located ....but I think decomposition is about as likely as that sort of
unconventional
" nitration " or nitrosation occurring . Another possibility considered is that the MEDNA compound which Axt was experimenting with using N2O3 could
be gotten from the reaction of an organic peroxide and an organic nitrite ester .....this was just a thought , I never even took a pencil and paper to
draw out the reaction for either , so it well may be that it's just not going to be happening that way .
But the nitrosation capability of the organic nitrite ester in a non-aqueous system is well established simply by the sodium azide synthesis where the
organic nitrite is reacted with hydrazine , and there are probably quite a few other reactions where the organic nitrite ester could be similarly
useful . This possible reaction with an organic
peroxide was just one that occured to me when I read
about Axt's experiment with N2O3 and propylene oxide .
It just occurred to me that an organic nitrite ester could
function as a source of nascent N2O3 , or NO2 , or NO
simultaneously.... contributing any of the three which
might react .
quicksilver - 9-8-2006 at 06:43
Where would there be a application for a non-aqueous diazotization? The concept certainly seems workable (and I understand the curiosity) .....but
then I guess we are talking about something quite un-conventional....perhaps an energetic binder? It does bring to mind a "liquid azide" or something
similar which could be stable w/ long shelf life, or a plastic which does not seperate, etc.
This is certainly "thinking out of the box" and is worth some money to the right firms. I'll bet this whole concept gets plagerized anyway. A quick
test with a sep-funnel showed this to a very workable and satisfactory method!
Rosco Bodine - 9-8-2006 at 09:12
This would possibly be useful for some reactions where the thing wished to be diazotized or nitrosated is not water soluble . There are sometimes
reactions too where the products are very different from an aqueous system or a nonaqueous system , involving the same reactants .
BTW what sort of test did you do there ? I haven't worked at all with the use of nitrite esters except in the azide syntheses and I am curious what
you observed .
Oh and when I said that some of these nitrite esters are highly reactive , an example I have seen other than the depolymerization / crumbling of
polyethylene , is that exposure will even change the polymerization level of halocarbon grease for ground glass joints . What was a greasy lubricant
will be changed to a rubberlike consistency by the exposure to isopropyl or glycol nitrite and halocarbon grease is one of the most inert materials of
this sort which can be found . Solid flourocarbons seem to fare better and are not attacked .
[Edited on 9-8-2006 by Rosco Bodine]
quicksilver - 10-8-2006 at 07:28
Not a big deal frankly. I was cleaning up my little lab and had the materials ready to go when I was reading through a notebook with the synth in one
of the pages. Often you fellows post little asides which I copy and save -> this was one of them. It was actually started me writting this thread.
I set up the sep funnel and proceeded noting if seperation took place, what manner, how long to achieve same, etc. I worked on a small scale with
100ml of saturated solution. I made damn sure it was saturated to it's highest extent as I was concerned about the solubility of EG in water. Upon
introduction of the EG it appeared to dissolve but within a short time (minutes) it formed up as small globules far more yellow than green but not
bright by any means. The seperation was distint and easy to drain off. However I allowed for approx 1.5 hours of movement within the solution (by
hand) continuing to break apart the seperate EG to see if the material altered it's viscosity. It appeared to get "heavier" as time went by. Colour
did not alter to the best of my poor eyesight but it might if longer time went by as the viscosity DID alter.
Obviously I don't have the notes as I write this but the temp did not rise appreciably (I started with a frozen funnel) and the amount of HCl I
thought was low but that's what I got when I wrote it out. My methods were to keep the funnel draped in a frozen cold pack for sprains and such and
use a little program on a laptop for the math. I think I was OK.
[Edited on 10-8-2006 by quicksilver]
Rosco Bodine - 10-8-2006 at 08:53
One thing you have to consider when synthesizing the
organic esters is the order of addition of the acid and
whether it is introduced at the surface or at the bottom of the mixture containing the nitrite and the alcohol to be esterfied , governed by the
density of the precipitating ester which will either accumulate in a layer after a rise to surface or sinking to the bottom . This is because the
incoming acid will decompose the ester on direct contact with the ester to the extent that there is surface contact
between the two . For this reason there should also be only gentle swirling of the mixture and not violent agitation or vortexing , which would
result in greater decomposition of the product after it is formed . Whether
the alcohol is mixed with the acid and the mixture added to the sodium nitrite solution , or whether the alcohol is added to the nitrite solution and
then to that mixture is
added the acid , can also have bearing on the way the precipitation proceeds and the yields .
It is these effects along with the tendency for some organic nitrites to more slowly be decomposed in contact with water alone , which complicates
this method , and commends the alternate approach reported by microtek where N2O3 is simply bubbled through the alcohol to be esterfied until
esterfication is substantially completed , in the absence of water or acids . I haven't tried microteks
method but he reports it works very well for isopropyl nitrite , and I would suppose it should work for other
organic nitrites also . Additionally the method could be used for producing alkali or other inorganic nitrites in aqueous or non-aqueous reaction ,
or used for diazotizations directly when no nitrite reagents are
on hand , but nitric acid and starch is available .
Another interesting reaction for the organic nitrite esters
is the effect called " transesterfication " which occurs
when a less volatile nitrite ester is added to an alcohol
which will form a more volatile ester . For example if
you add a glycol nitrite to methanol , they react and
methyl nitrite is evolved as a gas , leaving glycol behind
as the byproduct of the transesterfication .
quicksilver - 11-8-2006 at 07:15
The mixing was obviously too vigorous in this instance as I only realized after you mentioned it. If one has ever had a swimming pool and added HCl to
it to adjust the Ph the acid drifts into the water in a cloud-like manner, disapating quickly. In this saturated solution it does not. Thus the desire
to swirl the fluid at too great a rate. (good point), my temp control was not that great either.
Has the process of " transesterfication " been utilized with other esters? I have always wanted to find a consistent method of working with solid
alcohols which did not require distilled acids for certain materials such as mannitol. The only time I found the final product (of MHN) to be
appropriatly high in N was with 90% and above. Are there patents you have seen on this issue of transesterfication? For that matter is it possible
that this whole concept in some manner be utilized in (solid) polyol nitration?
Chemoleo mentioned inositol as a nitrite concept....and you stated in regard to the solids that they may be used as intermediates useful in
diazotizations and similar reactions and the formation of nitrosamines. -> did you have a specific experiement in mind?
Rosco Bodine - 11-8-2006 at 08:07
IIRC the one patent in the other thread mentioned the transesterfication producing methyl and ethyl nitrites
from reaction of heavier organic nitrites with methanol
or ethanol , but I don't remember any other examples .
There are aromatic compounds which form nitroso intermediates which can be further nitrated to trinitro
compounds under less extreme conditions than is required for trinitration via the sulfonation intermediates .
I am sure this has been done for picric acid and for styphnic acid , where the nitroso intermediate is simply
heated in d 1.42 nitric alone to complete the nitration .
I believe these intermediates which are stable to further nitration were called " nitrosites " and are structurally different from nitrite esters .
Whether or not the organic nitrite ester could also be used as an intermediate in nitration to a further degree
to form a nitrate ester , I don't think it would work since
the nitrite ester is decomposed on contact with acid .
So it would seem to me that some indirect scheme would
have to be used as with the aromatic nitroso compounds
in order to form something else that could be further
nitrated without decomposition . I just don't believe
that an organic nitrite ester would be a valid intermediate in any usual scheme of further nitration to
form a nitrate ester .
There were a few situations where I thought it may be interesting to use an organic nitrite ester for a nitrosation reagent , and DDNP was one of the
diazotizations where getting a good crystallization of
the DDNP from an aqueous reaction system has been problematic . A thought which I had was to attempt the diazotization of picramic acid dissolved in
alcohol using
an organic nitrite for the diazotization reagent . If this worked then it could lead to a more satisfactory product .
For this I was thinking dissolve the picramic acid in denatured alcohol and then introduce the " nitrous gas "
or perhaps glycol nitrite to accomplish the diazotization .
The isopropyl ester would not be used since DDNP reacts with some solvents and isopropanol is one of these .
It could be that the glycol is reactive with the DDNP also ,
and not work either , but simply gassing the mainly ethanol
solution of picramic acid in denatured alcohol should work fine , the idea being that ethyl nitrite could form in situ as an
active reagent , continuing the diazotization in the same
direction as any direct reaction between the N2O3 and the picramic acid . Two routes would then be present for the diazotization and the product
would be more soluble in the
alcohol so it would crystallize out more slowly than in an aqueous reaction mixture , likely forming better crystals .
R-salt is another material which I thought might be producible by some alternate reaction scheme using an organic nitrite for the nitrosation and a
different solvent system for the reaction .
Tetracene is another material where this may be useful ,
as well as many similar reactions ....just about anywhere
a more classical nitrosation is performed it would seem there is an adaptive method which could be performed using an organic nitrite and a solvent
system instead
of an aqueous system . This would also have application
in those sorts of materials which Axt was disclosing in the other thread .
The problem of not having any sodium nitrite on hand is also resolved since microtek has shown the original method of Griess for generating the "
nitrous gas "
from ordinary nitric acid and starch , so this becomes a very fundamental interest as a tool for work in a range
of nitrosation / diazotization reactions .
These reactions also have application in the chemistry of energetic hydrazine , cyanamide , tetrazole derivatives
where crystal form of the products of synthesis could
be altered by use of nonaqueous reaction systems .
I haven't written down a specific experiment which I intend to do exploring this , but the idea is plain enough
that anyone should be able to formulate a method
using an organic nitrite which is parallel to the more
usual method for the aqueous reaction .
Did you have a particular reaction in mind ?
[Edited on 11-8-2006 by Rosco Bodine]
quicksilver - 12-8-2006 at 06:29
I have some aminoguanidine carbonate that I made from guanidine nitrate just sitting around. I have never experimented w/ tetrecene (tetrazene) but
that a simple thing to make as well using this mechanism. I haven't worked with tetrazene to any great extent but it seems like the best candidate
I enjoy nitrated phenols as they are very utilitarian and styphnic acid is quite versitile but they don't appear to fit the bill for this concept.
As for Styphnic Acid it seems that I once either saw a patent or some material that mentioned it in the context of this discussion. The resorcinol was
prepared with a very dilute nitric acid and exposed to sodium nitrite for nitrosation. The exact mechanism varies from source to source but I even saw
one written by Ladgard (Prep Man. of Explos) I used one some years back (it worked very well) and I forgot all about it. But I remember it was
scalable. I thought nothing of it back then but now I wonder if many diazotizations / nitrosations are indeed scalable. In addition I wonder if SOME
of the concepts would work for phenols. And the unique thing about that particular synth was that is was inexpensive to make up a usable bottle
(500gr) of reagent. What I wanted to do was really take more notes this time -> working to get a nitration with a MP that meets the temp for a
tri-nitration with little or no impurities. My friend's son is an undergrad at our local Univ and has access to a melting point machine that is quite
expensive and goes unused. MP is the best method I have to deterime if I an successful. I'll bet the tetrazene is right on the money. I tried it with
some various PA I made and even though some samples looked ligher than others they had di-nitrated phenols within the sample.
[Edited on 12-8-2006 by quicksilver]
Rosco Bodine - 12-8-2006 at 07:50
We talked about this patent attached once before in another thread but the file I had then was too big to upload . This is so straightforward simply
using sodium nitrite if you have it , that it would be entirely useful as written . Example 12 and also example 15 on page 4 is what you are looking
at I am sure , and there really is no requirement for d1.5 nitric , as it is diluted to a much weaker strength , so different ratios using d1.42 acid
could easily be applied to produce the same reaction conditions .
Styphnic acid is also very easy by a method which I devised which involves the classical route via the sulfonate , using optimum ratios for a small
batch method
that is pretty foolproof for 20-30 gram amounts of TNR .
It is another one of the collection of Rosco's good old fashioned country recipes you won't find in the books ,
but is about as simple as it gets if you have on hand a small amount of d1.5 nitric .
Nobody but me that I know of has mentioned it but styphnic acid also makes a satisfactory base charge in compound detonators , only slightly less
powerful than picric acid , but a little more easily initiated . Perfectly stable in long term storage too just like picric acid , 2.5 to 3 grams in
a 3/8"
column diameter would be entirely adequate even for those
hard to intitiate secondaries like urea nitrate . Only disadvantage really is that it is a bit more expensive to make than picric acid because
resorcinol isn't as cheap or OTC as is aspirin . An advantage is that the TNR is easier to crystallize
from boiling water in a very uniform free flowing and dense
form suitable for loading .
As for tetracene , well it is most interesting only as an intermediate in the schemes for tetrazoles . IIRC , simply
on keeping in a bottle in a warm place for a week or so ,
tetracene will decompose completely to a useful tetrazole
intermediate , or it can be modified directly by chemical means to form different products , right there in the pot
where it first appears .
[Edited on 12-8-2006 by Rosco Bodine]
Attachment: GB1278576 Nitrophenols via nitrosophenols.pdf (569kB)
This file has been downloaded 892 times
quicksilver - 13-8-2006 at 13:31
********off topic remark*******
You really should consider writing a bit. I have gotten so much from the contributions you've made over the years...I'm not kidding. -> I just got
Jerad Ledgard's book The Prepretory Manual of Black Powder & Pyrotechnics, (a scan is also on the FTP) which makes 4 of his books I've bought and
frankly I think you might be able to do a better job. In this one however his sources are documented a bit better. But there is little originality. He
is an able chemist, I'm sure. But what he really did was creativly gather together some unique info. I, personally, think you could do a more
original work and make a damn interesting read. He just seems to bunch together tid-bits of information with no "flow" to them. Plus he goes to the
same place we all do for source material. but you found clathrates, etc. He should have been able to find more orginal stuff than he did.
********off topic remark*******
Interesting stuff there....I have found that there are two styphnic acid salts possible: being normal and basic. One yellow and the other red. The red
needles having a degree more initiating power than the yellow. In both experimentation and reading I have found that the red in a large quanity (one
gram +) will initiate PETN / ETN. Not great, but it will funtion. The same may be true for lead picrate; I have not personally worked with it to a
degree to be sure. When I was experimenting with crystal shape in picrate salts I found that the more well shaped the crystal the more sensitive and
perhaps the more powerful the released energy.
In terms of secondaries I found that ETN can be re-crystalized with methanol to form very well shaped crystals which are extraordinarily sensitive and
seemingly powerful. Like you I have no problem with stability with that compound.
Tetracene, I have heard has a lead salt which may have more initiating power than the base material itself. I welcome the chance to experiment with
milligram amounts, should I find a method of developing the lead salt.
Rosco Bodine - 13-8-2006 at 17:42
Are you talking about the normal *lead*styphnates there as needles ? There are denser forms by various methods
and I think I have listed a bunch of the patents here in another thread . I have a whole patent folder on various methods . The hexagonal plates
which are formed from
a gel intermediate are a very interesting form , but getting the gel to form is a trick since it is a fickle reaction , sometimes it works and
sometimes the rate of addition or temperature or pH is not exactly right and the gel doesn't form . It is really neat when it works ,
it gells just like a bowl of orange jello as thick as glue ,
and then just as suddenly the gell matrix implodes into
hexagonal plates all almost exactly the same size sitting
there in an absolutely clear and watery thin supernatant .
I have never seen a phenomena quite comparable .
It is something like the " replicators " on stargate ,
which are assembled into a large transparent orange goo , and then suddenly collapse into a pile of small
hexagonal plates of reddish brown color in an almost
instant transformation , it's over in ten seconds or less ,
which is a *rapid* precipitation for relatively large crystals . But that is exactly what it does . You have to see it to believe it . US2150653 is
where I got this and confirmed the information , but it is a fickle reaction .
quicksilver - 14-8-2006 at 06:57
Speaking of fickle reactions, I had been fortunate enough to get my hands on a large amount of phloroglucanol and was facinated by the above PDF file!
I was sure that the only way I was going to work with it was the use of super excess of same with H2SO4. I was very let down when all of the labs I
had seen with phloroglucanol dealt with such a vast amount of sulfuric acid that it appeared wastful. So I shelved the product and did not attempt to
nitrate it. It was very tough to find as it is no longer used in photography or other technical grade application. [ It's still available, I
believe if you find one of those photo chemical distributers.] I stumbled on it and kept it. Now I can see what it can do without feeling
like I am wasting acid. - 
In the other thread I believe I also found various (patent) methods of controling crystal shape and the needle in styphnic acid is a common
one....the addition of a slight bit of Al IIRC. A dense form that I have worked with aside from platlets are the near cubiod crystals which seem to
result from a higher pH.
The "gell-concept" is something I have not ever tried to form but in my attempts to control pH I believe it may have happened accidently! Some years
back I made some styphnic acid and thought I could bring the pH higher from what I had (it was normal, in a sense; but I really don't remember the
conditions) when I managed to get a goo which I thought was a ruined batch. I think it started when I added drops of sodium hydroxide after all the
recorsinol was in. But this was a long time back...Lowering the temp (I was going to shut down the whole experiment) the goo seemed to condense over a
few minutes - the time it took me to get another pair of gloves and start to put away some bottles. I came back to see what looked like a "tile floor"
on the bottom of the beaker and I drowned it in ice chips / water. The crystaline product was differnt than I had seen and I don't think I could ever
reproduce that experiment as the "little things" were unfortunatly not documented.
I have learned that pH, and especially temp control has an enormous effect on nitrophynols. Depending on how they cool or are drowned not only effects
the crystal shape but I BELIEVE can effect the yield itself.
[Edited on 14-8-2006 by quicksilver]
Rosco Bodine - 14-8-2006 at 09:49
Yeah that gel intermediate is a damn strange effect to see . As I recall when the gel formed it was a clear transparent but brightly colored yellow
orange and viscous gel , about like when you are stirring together
two part epoxy resin using a popsicle stick , and there
are no suspended particles of any sort , it is just like clear jello . And then the jell suddenly collapses to
a layer of perfectly uniform dense hexagonal plates ,
it goes very fast about like when an electrostatic particle precipitator is switched on in a dust and smoke filled chamber , poof its suddenly changed
in form almost
like magic . You are looking at it in one form and thinking wow this is strange , and a few seconds later it is like
a switch was flipped and now there is something else there entirely different .....really wierd as precipitations go . I sort of think there probably
is an electrostatic tension which occurs in the hydrated gel , which gradually
aligns the gel structure into a sort of expanded macrocrystalline matrix in which water is held something
like a " hydro-clathrate " macro structure composed of
smaller units which have only one stable range of numbered units , and when these subunits are aligned
into stable groupings , the water is suddenly expelled , and the crystal electrostatic forces cause a sort of instant condensation for each subunit
crystal , collapsing the gel
all at once . It is very damn peculiar , almost as if the
system is " alive " and knows where it must go on cue ,
with everything marching together at the same time ,
like someone snapped their fingers and said " now "
to give the signal " crystallize " and that is just what happens . I have watched a few crystallizations ,
but this one is the strangest thing to see that I have ever seen . Definitely one for the books .
[Edited on 14-8-2006 by Rosco Bodine]