Dec 15, 2013

Hexamine is not the Smoking Gun

If this is your first time here, I recommend starting from the conclusion page.

In his recent analysis, Dan Kaszeta provides some interesting chemical analysis of the recent UN report, and also suggests Hexamine could be the smoking gun of the Ghouta attack, going so far as describing it as "very damning evidence of government culpability".

The reasoning could be summarized as follows:
  1. Hexamine was reported by the OPCW as part of the Syrian chemical program. This implies it had a purpose in the program, rather than being used for explosives manufacturing etc.
  2. Hexamine can be used to bind the HF generated during the sarin binary process.
  3. No one else is known to use Hexamine for this purpose.
  4. Hexamine was found in multiple samples taken by the UN in Ghouta (both Zamalka and Moadamiyah).
  5. It is unlikely the opposition will choose the same HF binding chemical as the government, implying government culpability.
I believe there is a much more plausible explanation for these findings:
  1. As Dan notes, the standard chemical for binding HF in the sarin binary process is isopropylamine. It was used by the US for this purpose, it was declared by the OPCW (in the same report), and it was ordered by Al-Nusra in Turkey. There is no reason to believe Syria decided to replace it with Hexamine.
  2. So why was it part of Syria's chemical program? This is easily explained when remembering Syria produced not only sarin, but also mustard gas. Hexamine is a well-known stabilizer for mustard gas, discovered in 1945 and adopted by the US Army's Chemical Warfare Service.
  3. Which now requires us to explain the Hexamine findings in the field. These are not surprising given the many uses and high accessibility of Hexamine. Specifically of interest are its uses in explosives (which were used to disperse the sarin) and as heating tablets for camping stoves, which are probably widely used in these neighborhoods under siege.
    This conclusion is further strengthened when considering that (a) Hexamine was reported in several samples that did not contain any indications of sarin, and (b) some samples contained other explosive-related chemicals such as TNT and trinitro triazine.

Update

Dan Kaszeta has referred me to this US Army publication, which states on page II-38 that "a small amount of degradation occurs when stored in steel ton containers for over 50 years". It should be noted this refers to the pure form of mustard gas (HD), which is different than the Levinstein Mustard (H) mentioned in the patent above (70% purity). Dan claims H is an obsolete agent, and since "pure HD is quite stable on its own", Hexamine could not be a mustard gas stabilizer, as previously claimed.

This is an important correction which requires revisiting the analysis.

First, we should confirm that Syria indeed stores HD and not H. There is no direct evidence that this is the case, but given that Iraq's inferior program reached purity levels of 90-95%, it is fair to assume Syria does have HD.

Second, we need to confirm that HD does not require stabilizers. The above US Army publication seems to imply it doesn't, but this one states "The stability of Levinstein mustard which has been purified by various methods is also improved by the addition of 1 per cent hexamine" (p. 42), and this patent discusses methods of stabilizing HD, stating "mustard gas thus purified still corrodes steel containers and the corrosion rate is fairly rapid at temperatures in the range of 110F. to 150F". Additionally, when considering that "pure" HD is actually only 96% pure, it makes sense that while it should degrade slower it might still need some stabilization.

Trying to settle this discrepancy I looked into the sources of the first publication and found the most significant one to be this research, which I could not find in full. However, according to its summary it is based on samples taken from US stockpiles held for 50 years. Obviously, these stocks were intended for long-term storage, which according to the other sources contain stabilizers. 

So apparently, the low degradation findings refer to the actual final product (containing Hexamine), and not the hypothetical chemical. 

While investigating this issue, I also found this interesting quote (here): 
"Regardless of the exact reasons for the instability of Levinstein mustard, the problem is fully recognized and is extremely serious during time of war and national emergency when it becomes necessary to build up a very great strategic reserve of this chemical warfare agent in contemplation of the fact that chemical warfare may, at any time, be resorted to."
This brings up another option: That the Hexamine in Syria's stockpile was intended for emergency production of large amounts of H. Since HD's advantage over H is in storage and not in battlefield use, this is a very plausible scenario.

Finally, Dan's response still fails to explain why Hexamine was found in the sarin-negative samples.

As a more general claim: Hexamine seems to have multiple uses in chemical warfare and multiple reasons to be found in the field samples (see many more here). Correlating the two is impossible before meticulously striking off all the alternative causes.

Conclusion: The Hexamine findings in the impact sites are not indicative of Syrian government culpability as they are not reliably linked to the Hexamine from Syria's chemical stockpiles.

Did I miss anything? Please share your evidence and analysis and help improve the conclusions.

48 comments:

  1. Hexamine could be used as a hydrochloric acid (HCl) scavenger in binary Sarin. Especially that of the precursor DF produced through the di-di process: fluorinating DC with HF.

    Residual DC in the precursor DF will react with the isopropyl alcohol liberating the respective halogen. You have HCl from residual DC and HF from the DF. I don't know if isopropylamine could also scavenge HCl or conversely if hexamine would scavenge HF adequately in binary sarin, but both seem reasonable.

    Hexamine is preferentially used as a scavenger and corrosion-inhibitor in Levinstein process mustard gas - presumably the process Syria was using. Mustard gas degrades quickly and becomes increasingly corrosive at temperatures above 100F. You can keep mustard agents in a relatively cool underground bunker for long-term storage. How hot would a missile warhead get on the back of a truck in the desert? Worse yet, an aerial bomb slung under a MIG while it was sitting on a runway baking in the sun?

    I would think a pretty substantial quantity of hexamine was intended for use in the mustard agent. Syria's stocks (OPCW report) were 80 tonnes of hexamine and 40 tonnes of monoisopropylamine.

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  2. Since hexamine is used to produce HDX, RDX and C4 - I imagine there's a lot of it available in Syria. It may be far easier to obtain than mono-IPA, so I could imagine that might be the *preferred* stabilizer in either government or opposition CWs.

    Quantities of hexamine in Syria would unlikely to draw any attention in the outside world, while mono-IPA would start raising red flags for CW use.

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    1. That was my attempt to explain why Assad would possibly declare *that much* hexamine as part of his CW stockpile. It's unusual to say the least. To Dan's point, *if* Assad was using hexamine in his di-di GB2 as stabilizer, then it *would* point the finger back at the SAA simply because it's usually not normally used in GB2. Trouble is we have no idea if he's actually using it in GB2, sulphur mustard or anything else as an acid scavenger. It simply sounds like it might work and be a good idea, especially if you're cooking up a mustard - GB brew.

      We also have no idea how the opposition has sourced or formulated their Sarin so far. It would probably make more sense for the opposition to use it like that (availability, keeping under the radar, etc.) providing it worked as a substitute. I wouldn't think it's something you would stumble upon by accident in a bare-bones lab. Not necessary now I guess since every homicidal salafist in Syria building their own little CW production labs will try it. That is, until they start diverting hexamine stocks to producing that blue methamphetamine they gobble down like candy.

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  3. Hexamine is used as a corrosion inhibitor, including in paints and a coating on bolts.

    e.g. http://www.waynepigment.com/index.php?option=com_content&view=article&id=4&Itemid=7

    or

    http://kanoriachem.com/index.php?option=com_content&task=view&id=31&Itemid=71

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    1. Would this be the same bolt where the trace of sarin was found?

      Evidently corrosion and sarin prefer the same kind of environment. It is thus be no surprise to find sarin with corrosion inhibitors.

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    2. My understanding is that, when hydrolyzed, Sarin yields highly corrosive compounds. Not sure what you mean by Sarin preferring the same environment as corrosion. It does not - in the environmental conditions that make corrosive effects evident, Sarin ceases to exist.

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    3. Interesting. Added to the post.

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  4. It seems to me that those whom always wanted an intervention in Syria are now finding new excuses by creating theories of there own that dont have any evidence to back up there own claims.

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    1. Looks to be that way Bruno. It seems as the official narrative is crumbling those that were to the forefront of pushing this narrative are now set on trying to explain away why they were wrong.

      When people put forward a theory of their own and sell it as "a smoking gun" they in essence leave themselves and their credibility open to criticism.

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  5. Sellstrom a few days ago
    http://www.innercitypress.com/syria6khandelay121313.html

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    1. Sellstrom apparently accepts the range estimate of 2 km for the Zamalka rockets. This is also the figure quoted by Hersh from the unpublished study by Postol and Lloyd at MIT. So there's now a consensus that the rockets were fired from insurgent-held territory, though it might be a while before this finds its way into mainstream media.
      The UK government, or at least its UN ambassador Mark Lyall Grant, seems increasingly desperate to reassert that the regime did it.

      Mark Lyall Grant ‏@LyallGrant 23h
      #Syria CW in #UNSC: Russia uses Giant Squid Defence - squirt lots of ink in attempt to muddy waters on regime culpability. Doesn't work.
      Mark Lyall Grant ‏@LyallGrant 15 Dec
      #UNSG & Sellstrom will present final #Syria CW report to #UNSC Monday. Leaves no doubt that regime used CW against its own people.

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    2. Thanks. I added a new post on this press conference.

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  6. Sasa, not sure where I was put this so please move at your will.

    Russian UN envoy Vitaly Churkin talks tough on western claims of Assad culpability in Sarin attacks. Well worth the watching as it is only a few days old.

    http://www.youtube.com/watch?v=O5l8RP3opfE&feature=youtu.be

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    1. Thanks! I couldn't find any new evidence there. Did you?

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  7. Theory:

    Considering we know that Zamalka was hit by sarin on the 21/8, how likely or unlikely is it that the sarin was dispersed via some other method rather than from the rockets?

    I'm going to enter the conspiracy realms for a moment so bare with me. I am content that the launch position falls within rebel controlled area but I just want to pick your brains with this.

    Scenario:

    SAA attacked Zamalka using Volcanos on 21/8 with no chemical warheads. A rebel group in Zamalka is possession of the now accepted "small amounts of sarin" they have in their arsenal - unleashed the sarin around the impact sites. Such a plan had been in the pipeline for a while but on 21/8 amid a SAA onslaught this rebel group seized their chance.

    Some of the victims were then bussed into Moadamiyah to make the case for a sarin attack stronger by being able to suggest that several areas had been victim to CW attack. It is hard to explain away the fact that several areas came under government attack on the night but yet they chose only one area to hit with sarin. But if we could say several areas were hit it starts to look like a very well laid out, premeditated attack.

    Again I am sticking with my theory not all rebels knew about this plan or that some pot their people had CW in their possession. This would the work of an "elite" group if you will.

    On my Moadamiyah conspiracy I supply a paragraph from al-Ahkbar which sums my theory up well:

    "A third explanation, mentioned by Bretton-Gordon, is that patients might have been “brought in from other areas.” All the patients were pre-selected by Ghouta doctors and opposition groups for presentation to the UN teams. And if this is the only plausible explanation for the discrepancy between environmental and human test results, then it suggests that “patients” were “inserted” into Moadamiyah, possibly to create a narrative of a chemical weapons attack that never took place."

    Thoughts?

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    1. It's obvious that much of the crime scene and casualty images and figures have been manipulated. That's pretty much SOP for Syria.

      The question is how much and what exactly.

      Regarding whether the rocket attack was faked, it seems almost certain the rockets were fired at the target area and probably at the time suggested - though earlier times are possible and could account for the lack of eyewitnesses to the launch on the night.

      Either they carried Sarin or they didn't. If they didn't, the only possible explanations are that it was either too dangerous/unreliable to fire them loaded with Sarin or that they carried a different payload. This also implies that the Sarin or traces of Sarin were introduced by other means.

      NB the same missile type were fired at Adra (a few km away) and Douma earlier in the month and also in July. Of interest is the sooted ground and walls in the immediate vicinity of one - not burned grass or vegetation - indicating a fuel type payload rather than a chemical payload.

      "Adra: one chemical rockets, which targeted the city and the events of black smoke on the walls and roads on 05/08/2013"

      https://www.youtube.com/watch?v=3-cAyWnnLcI

      Also of interest is the Adra and Douma incidents didn't result in any fatalities, nor any serious interest from overseas.

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    2. Thanks for the feedback Charles.

      I agree that rockets were fired on Zamalka but for my theory, as you pointed out above, "Either they carried Sarin or they didn't".

      I don't usually take to conspiracy theories in trying to find answers but I'm just allowing this theory of mine to surface to see where it goes. What strikes me is that the "victims" in Moadamiyah tested highest for Sarin exposure yet the UN has concluded that there was no Sarin attack there. So the only logical conclusion is that the "victims' were bussed in there from Zamalka. Is that a logical explanation or is there a better one?

      If the victims were, as I say, bussed in then this opens up a plethora of questions in itself.

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    3. I guess it's possible that water-filled Volcanoes were fired and then sarin distributed, but it seems like a more complex and weird operation. I think it's more likely that these were repurposed to carry sarin and then the group just decided by themselves "let's win this war".

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  8. Charles, I agree with you that even only for the sake of being able to reject the scenario, it would be a good idea to think your alternative through.
    Comments to your theory:
    - Are we sure the Sarin needed to be ´sprayed´around the impact sites of the rockets? The UN report found Sarin or/and its signatures. The UN lists the methods they use but don´t say for the specific cases what chemical they found detected with what method. For the impact sites it might have been only the Sarin signature, which is then IMPA I presume? That chemical could easily been added to the site just before inspectors came, without health risks. Finding the real Sarin would be unlikely seen the degrading time.
    - The ´small quantity´ Sarin could have been used by other means to explain the victims in the video´s.
    - For the biological samples on victims:Again we don´t know what UN inspectors found and in what concentrations. The unsuspecting victims could of had a drink with Dimp in it before the inspectors came, that would give an IMPA metabolite.
    - An "elite group" being in the plot would be sufficient.
    - Concerning Adra video. I don´t see a clear indication of sooted ground, sooted walls yes but that seems to be caused by a previous incident. Or in any case it might have been. If so much soot is produced, why are rocket remnants not sooted?

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  9. Does todays Wall Street Journal article

    http://online.wsj.com/news/articles/SB10001424052702303330204579248333326432514?mod=WSJEurope_hpp_LEFTTopStories

    change anything? Doctor in story was there on August 21st. He reports 200 dead in his underground clinic. He also smuggled out samples.

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    1. Thanks. I think this somewhat increases the likelihood of the higher death toll estimates.

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  10. Of note is that the stocks of Hexamine and Isopropylamine slated for destruction are the 'left-overs' or are for use in totally different applications - such as explosives.

    Operational stocks of Hexamine are already in the HD Mustard doing their job. In the GB case the isopropylamine (doubtfully Hexamine) are already dissolved in one of the two precursor components ready for delivery.

    Finally, the quantity of GB for the strategic application must be able to be delivered in the 500kg gravity bombs and scud missiles. Operationally the SyAF couldn't possibly deliver more than three hundred tonnes of GB (ignoring the VX entirely). Say 100 scud missiles @1000kg (very generous) and 150 sorties at @1000kg - incredibly generous considering most aircraft would be on a one-way mission.

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    1. A few technical points you (or maybe I) have missed, Charles:

      Re left-overs: CW programs are always tossing out 'old' stuff. I would expect they would always have to brew new poison or reprocess their existing stocks. CW program development may end, but not their maintenance. They always need some stock of raw materials because they always make more for replacement.

      Syria listed old-school sulphur mustard precursors in their declaration: chlorethanol to make thiodiglycol, and either phosphorus trichloride or hydrochloric acid to chlorinate the thiodiglycol.

      Syria's CW arsenal is designed to kill Israeli soldiers (and vice versa). You don't launch Gx or Vx at troops that have CW protection and hope that they won't notice. I was taught (courtesy U.S. Army) that when the T-72s came pouring through the Fulda Gap, the Soviet Union would always use a combination of three things: 1) something to make us unmask (sulphur mustard instead of nitrogen mustard for some reason), 2) VR, Vx or the newest insecticide they brewed up, and 3) some kind of respiratory or CNS depressant (like Fentanyl).

      The point was Soviets would be trying to kill us. 1) would make 2) more effective at killing us, and 3) would finish the job (or at least incapacitate us) when everyone used their atropine/PAM antidote injectors because of 2). Cold war field medics were suppose to assume all three were present all the time. The brass downplayed this because there really isn't much of an effective defense against all three, especially not in the quantity either side was expected to use.

      I don't think Syria got to the point of 3), but they are not so stupid as to simply lob Gx or Vx at Israeli troops. They supposedly had a large amount of mustard and I presume that was for 1). They sure didn't stock mustard for the vesicant effects.

      Regarding the GB: I think you mean GB2, since you're speaking of the binary components. GB generally means unitary Sarin - it's already purified, stabilized, etc. You just use it straight away from bulk if it's not already in a sealed warhead.

      GB2's usual binary components. In simplest terms, the DF part and the OPA part.
      - OPA is a mixture of isopropyl alcohol and isopropyl amine. Hexamine is also an amine that could potentially serve isopropyl amine's halogen-scavenging function. It would be in the OPA component *if* it was used.
      - The DF part is not pure DF, but a mixture of DC and DF (di-chlorine and di-fluorine, hence 'di-di' process). In a less-than-perfect binary reaction, some DC reacts with the alcohol yielding chlorine as hydrochloric acid. The amines would scavenge either the HCl or HF acid. Hexamine is interesting *here* because is was previously used as the amine scavenging HCl in sulphur mustard processes. As others pointed out though, the OPCW may have been detecting it from the paint.

      Can't speak to how Assad actually planned to get all that to a mounted Israeli Army streaming across the Golan. Psychopaths usually don't think that far out. Pressure washers and 'volunteers', maybe?

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    2. My understanding is that the Syrian GB (2 - I stand corrected) was part of a strategic reserve for use post an Israeli nuclear strike. A poor-man's version of MAD.

      The equipment was set up to deliver the chemicals using large gravity bombs and scud missiles. Of particular interest is the lack of conventional 122mm chemical ordnance - which would be the preferred delivery mechanism for enemy troop concentrations.

      I've not seen any declaration by Syria on the use of Hexamine as a precursor. Do you have a solid reference? Even if it was a precursor I've not seen any declaration that it was also used as an HF scavenger post mixing. The isopropylamine they have would do an excellent job.

      Reiterating my original point, the strategic GB2 reserve will be based on binary components ready for immediate loading. That means the scavenger will already be mixed in either the isopropanol or methylphosphonyl difluoride components.

      Incidentally, the scavenging of HF by Hexamine has an efficiency range of between 1 and 4 HF molecules trapped by one molecule of Hexamine ( etheses.dur.ac.uk/6562/1/6562_3865.PDF ). This means that to guarantee scavenging of HF you need an equal weight of Hexamine to Sarin (both have a molar mass of 140 grams). At the optimistic end you need 1/4 the weight of Hexamine to Sarin.

      This means worst-case the delivery system will land Sarin at under 50% of the payload ( 140g/300g = 47% ). At very best case (and pretty unlikely) it will be 70% (140g/195g) . How does this compare to the isopropylamine path?

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    3. I don't remember seeing any references to the warheads type or caliber, so I guess I didn't notice the absence of Grad warheads. Didn't they just give a total number of warheads destroyed without specifying? I'll have to check again. But yes, I would think they would have. Grads would have played a part in repelling Israeli's next invasion/land grab. If the Sarin was only meant as a threat to counter the Israeli nuclear threat, then I wouldn't imagine they had anything besides larger missile warheads for use. Again, all speculation. Not enough information.

      I wouldn't normally think SAA used hexamine in any CW - *they're* the ones that declared it as part of their CW stockpile, not me. They listed a pretty significant amount without any distinction to use like precursor or stabilizer. It's simply on their list with no obvious reason. I was attempting to explain the possible relation it could have to their CW program *if* it was in the Sarin that was delivered with a UMLACA. I don't think it was at all - my comments were for the benefit of anyone who does.

      I'm not much on the chemistry. I've seen references to the produced HF content of GB2 to be around 10-15% by weight. Since nothing much appears about quantities in GB2, I just guessed an equal amount of isopropylamine, giving something around Sarin 70% best case. I'm just winging it here though - the example was just to suggest GB2 is never going to rival the 98% purity they can get with 'regular' GB through other processes.

      I'm kind of confused by your statements about why you would need as much hexamine as Sarin. Sarin degrades (hydrolyzes) after release yielding HF, but that's not the HF you're trying to bind. You're only trying to bind the HF resulting from the initial DC + DF + OPA ==> Sarin + HF reaction, not the subsequent HF produced by the Sarin as it degrades in the environment.

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    4. My analysis was based on chemistry inside the delivery vehicle, not any subsequent hydrolysis.

      Pure DF+Isopropanol generates 87.5% purity GB (diluted with HF). Add in the Hexamine HF scavengers and you get between 70% GB and 47%GB. Or 38.5kg to 26kg GB on target assuming a 55kg initial payload.

      For August 21, working on 8 to 12 missiles @ 55kg we have a total GB weight delivered to target between 208kg and 462kg.

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    5. Di-di GB2 uses a 50/50 mixture of DC and DF. The HF produced by the DF-alcohol reaction is consumed like this: DC + HF ==> DF. So you ideally end up with half of the HF at the end of the reaction than you would expect from a DF-only precursor.

      They can't bind the HF too aggressively because some of it is needed for the DC + HF conversion. I would expect they would only use a fraction of the amine as a scavenger in a fill-and-fire munition, so the purity is probably more like 80-90%. Again, just a guess. They could certainly tolerate a lot more HF and eliminate much of the amine if a warhead was used within tens-of-minutes of being filled.

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    6. Thanks,

      I didn't appreciate the use of DC/DF mix.

      I assume the 50:50 ratio is an arbitrary one? It would be possible for instance to have say 90% DC 10% DF and still get it to work, just slower - sort of an auto-catalysed chain reaction.

      Separately, the conversion of DC to DF produces free HCL

      DC + HF <=> DF + HCL

      Hexamine reacts with HCl to produce a hydrochloride salt - which will probably inhibit its ability to absorb HF. I'd guess for complete neutralisation they'd need quite a lot of Amine.

      Without knowing any of the side reactions or knowing the equilibrium states, I could hypothesise a scenario of 99% DC, 1% DF, no amine, and plenty of time to produce a mix of GB and HCl (and a tiny bit of HF)

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    7. Reference to 50:50 di-di mixture used at Rocky Mountain Arsenal:

      http://goo.gl/5K5aYr

      (URLs shortened with Google have goo.gl/ so the link above is legit.)

      You fluoridate half the DC, mix back in with the un-fluoridated DC and then add the alcohol. No idea if other proportions would work - it's way over my head.

      Dan Kaszeta's Strongpoint paper gives 140g of HF for every kg of Sarin produced, but that wasn't for the di-di process.

      http://strongpointsecurity.co.uk/site/wp-content/uploads/2013/11/Sarin-Quality-and-Quantity.pdf

      I noticed I've been mixing up HF and HCl as an end-product when describing that process. The di-di process produces HCl that needs to be neutralized, not HF. You would think about using an acid scavenger in either case if you were going to mix and store. Mix, fill and fire would presumably require far less.

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  11. Incidentally with the Volcano delivery system and assuming Hexamine scavenging there would be between 29kg of Hexamine/HF(1) complex deposited in the immediate area assuming 1:1 scavenging, or at the other extreme 15 kg of Hexamine/HF(4) complex assuming 4:1 scavenging. Either way an awful lot of Hexamine to find. (all assumed 55kg total payload).

    The question then arises why the labs did not consistently find Hexamine in every location.

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    1. Considering the fact that there is no need to neutralize every last drop of HCl (if di-di Sarin) or HF (if other Sarin), there wouldn't be a need to add nearly as much as you would need for total binding. Depending on how fresh the mix was, you may not find any at all - it could very well all be consumed before dispersal.

      This would lead to a few other interesting effects:

      Excess HCl would form and be released, and victims would notice a chlorine smell.

      Any hexamine used is hydrolyzed by the HCl into formaldehyde and ammonium chloride. Ammonium chloride degrades giving ammonia and more hydrogen chloride.

      I would expect disbursing di-di process GB2 Sarin using a hexamine scavenger could potentially produce odors of any of: alcohol, chlorine, ammonia or formaldehyde even with the purest of precursors (in addition to whatever other odors might result).

      Not sure what odors non-di-di process Sarin would have from the corresponding amine HF scavenging. Have to dig around.

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    2. The short answer to "why not hexamine at all locations" would be because they wouldn't have any reason to use more than a minimal amount of hexamine in a mix-fill-fire munition. It could be completely used up in the warhead between mixing, filling and the moment the warhead explodes.

      Or it may have been consumed in Elvis' pressure washer between release sites. Which site didn't have the hexamine?

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    3. Di:Di process generates equal parts of HF and HCl as byproducts - not pure HCl

      Hexamine is not 'consumed' in the neutralisation process. With HF it generates a Hexamine HF(1-4) complex, or in the case of HCL it generates the monohydrochloride or dihydrochloride salt. In these cases the Hexamine molecule remains intact. Do you have any reference for the HCL hydrolysis path? And in particular any time-scale for the reaction?

      Pure Hexamine is considerably less volatile than sarin. e.g. those camping tablets take years to evaporate while sarin evaporates faster than water in a hot desert. It seems pretty certain that Hexamine will be found far more often than the same order of magnitude Sarin.

      On reflection, the use of Hexamine in a DiDi munition is problematic. It competes for HF, reducing the amount of HF available to convert the DC to DF. Perhaps it's energetically favourable towards the DC->DF path and Hexamine(n) complex can donate HF to DC? If so, the complexed Hexamine will also be able to corrode other material.

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    4. Are you sure HCl smells like Cl? It's not described online as such. I was wondering about the Cl smell in Khan Al Assal.

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    5. HCl's odor is bit different from regular chlorine, but it has a chlorine-like odor. The two are quite distinct when carefully sniffed in, say, a lab. When released in the air a hundred meters away and fairly dilute - close enough. We can smell chlorine at very low concentrations.

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    6. I didn't think about the complexes or salts remaining as detectable hexamine, but that makes perfect sense. My layman's reckoning is that acids eat things, so they are consumed (I blame the U.S. education system). So we're still stuck wondering why it's missing at sites where we would have expected the OPCW guys to find it.

      Sorry - I have nothing on the hexamine hydrolysis path or reaction times in Sarin and inferred its use from my recollection about its use in sulphur mustard. Again, just a guess based on why Syria would even have so much to declare.

      Does isopropyl amine bind HF and HCL in the same way, Charles? I ask because that brings up the question of why no isopropyl amine complexes or salts were detected. Or were they?

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    7. My earlier query about why 50:50 is now explained.

      DC + 2HF <=> DF + 2HCl (each DF has 2 atoms of fluorine)
      DF + Isopropanol <=> GB + HF

      Therefore Two DF + Isopropanol are required to convert one DC which eventually returns one HF molecule after conversion to GB.

      50:50 mix will supply just enough HF but only after many generations - 1/2 + 1/4 + 1/8 + 1/16...

      I've also found a reference that pure DF + Isopropanol takes 7 seconds to fully convert to GB + HF. Fast enough for an artillery shell but possibly not enough for a DC->DF->GB reaction with multiple generations. That would more likely be in a missile or a pre-mix.

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    8. I'm not sure if we're saying the same things here, Charles. The Slovakian wikipedia page has a much better diagram of the two better-known distinct binary processes:

      https://sk.wikipedia.org/wiki/Sar%C3%ADn

      or the diagram I'm specifically referring to in the wikipedia article:

      https://sk.wikipedia.org/wiki/S%C3%BAbor:SarinDiDi.png

      Both are single-step GB2 binary sarin production methods.

      The top one is the plain (for lack of a better word) DF-only binary method. You start out with 100% DF and add alcohol. Sarin and hydrogen fluoride are produced. AFIK, isopropyl amine is used to scavenge the residual HF.

      The second one is the di-di process. You must start out with equal parts of DC and DF. That mixture is made before hand and stored as a precursor. The 50% DF is not part of the binary process, but is a separate step to produce the precursor. One assumes the HCl would be distilled out of that DC/DF mixture prior to storage and is not a factor at the time you're ready for the final Sarin-producing step. Then (on the diagram) it looks pretty simple - a mole of DC, a mole of DF and two moles of alcohol yield two moles of Sarin and two moles of hydrogen chloride.

      The U.S. 155mm Sarin shell uses the di-di process, and that completes in about the same time you mention for the pure DF process - 7 seconds. Considering the extra weight and the pointlessness of neutralizing the HCl in an in-flight artillery shell, I doubt they use any stabilizer except for a little in the DC-DF precursor. I even wonder about that, since any scavenger could interfere with the normal binary process.

      For the Syrian mix-fill-fire procedure, they may be a little more concerned with binding the resulting acids. At some point, they have to mix the precursors and end up (in what sounds like seconds) the Sarin + acid mixture. They could add the scavengers at that point, or else just dump the Sarin and produced acid into a warhead and use it.

      It would be interesting to find out if the UN had a clue as to which method (DF only or di-di) was used. There must be something they found that indicates one or the other. It could be significant if, for instance, the SAA sarin used one binary method and the opposition's sarin was found to be made using the other binary process (or maybe even a unitary process). Could point to the ultimate source of opposition Sarin as well: stolen from SAA stores, home-brewed, Libyan Qatari-Turkey smuggling, Iraqi Saudi-Turkey smuggling, even U.S. or Israeli sourced.

      I'll bet the Russians have some idea from their Aleppo analysis. That would be the perfect reason for the U.S. - U.K. - French stonewalling U.N. inspections there for so long. Odd that Russia doesn't just go public with details if that's the case. Not that I would necessarily trust them, but there's something else going on in the background we're not being told.

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    9. We are talking about the same thing. It's just the Slovak version is an extremely simplified black box analysis of what goes in and what comes out ignoring the multiple intermediate reactions. I'm fairly confident my sequential and iterative description is closer to the truth.

      Regarding Isopropylamine I'm not sure of the scavenging efficiency compared to Hexamine. For some reason that information is very hard to track down.

      Dan Kaszeta says that the M687 Binary Shell has an OPA mix of 72% Isopropanol and 28% Isopropylamine. Getting out my trusty slide-ruler that works out at 0.233 Moles of Isopropylamine per mole of Isopropanol (and per mole of DF). So assuming high scavenging efficiency it's around 1:4 or 1:5 molecules.

      That translates in the Ghouta case and using a nominal 60kg payload as 4.75kg of Isopropylamine - Add in 6.9kg of HF and you get Isopropylamine-HF(n) compound + free HF = 11.6kg. That leaves around 48kg of GB.

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  12. You assume the rocket was the delivery system

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    1. Sasa has backed up the conclusion based on rocket use throughout his blog. If there was any evidence clearly disproving that or proving the opposite, then I (and others, I'm sure) would have been jabbering about it by now, Anon.

      Elvis in a pickup truck disbursing Sarin with a pressure washer somewhere near the two UN-inspected sites produces a reasonably well-fitting plume model, but it's hardly solid evidence.

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    2. As Sasa says himself, his site is not about trust, it´s about evidence for everyone to see. So Paveway, if doubt is somewhere lingering in the back of your mind, I think it would be interesting to discuss...

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    3. Nothing much to say that hasn't been said, Veritas.

      You don't need a rocket to disburse Sarin. You don't even need a pickup truck or a sprayer - those would just make your job easier. If one of the groups in the opposition *or anyone else* was setting up a false-flag in Ghouta, then the only thing the need is 1) SAA artillery to blame, and 2) a good idea of the wind direction when you plan on releasing the Sarin.

      If you control access to the claimed impact sites, then you can be sure there's plenty of something to find when the OPCW shows up. Make sure the sites chosen are downwind of the real release points - you may not even have to spike the 'suspect' munitions. Each inspector will have a half-dozen camera men shadowing them and they'll only have time enough to take the most superficial samples anyway.

      They only have 30 minutes - it's not like they're going to rip apart a mattress, pace out soil sampling grids or take sub-surface soil samples. [Would they given the time? Sure. Not sure what to make of Scott Cairns - he could be an alien - but his team knows exactly what they are doing.]

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  14. What about this comment Sasa: http://www.the-trench.org/not-so-dead-lines-‒-some-updates-and-corrections/

    It states that hexamine was used as precursor to Sarin.

    Is this in line with what ifriqiyah states on twitter: ifriqiyah ‏@ifriqiyah eg ´ Feb 6
    @liberalfish @hesbol the way Syria declared its stockpile, was the clue re: Hexamine, but for Methylphosphonyl difluoride´etc...

    Have you covered this information? Just curious that you have insight.

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    1. He doesn't provide a source for that, and I've never seen any indication that this is the case, so it seems like a mistake. He doesn't allow comments, so if you feel like contacting him and asking for the source, that would be very helpful.

      Note that in another report he classified isoropylamine as a mustard precursor, when it is obviously a GB2 precursor, so it doesn't seem like he's practicing due care in his analyses
      http://www.the-trench.org/syrias-declared-precursor-chemicals/

      Having said that, I no longer believe Hexamine was used solely as a Mustard stabilizer - will write a post on it in a day or two.

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    2. Did you contact ifri also, seems to have some inside information.

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