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Amines and Sarin – Hexamine, Isopropylamine, and the Rest…

May 3, 2017

By Dan Kaszeta

Translations: Русский

(Revised edition, May 2017)

One subject that keeps coming up in ongoing debates about Sarin chemical attack in Syria from 2013 to date is the nature, role, and presence of possible additives to Sarin. A molecule of Sarin is pretty much the same molecule however and wherever it was made. However, even in the best laboratory settings you don’t ever get truly pure Sarin. Relatively pure Sarin, with some additives, is the best for long term storage and the engineering needed to get pure Sarin is usually a level of expense and difficulty greater than anyone wants to expend, or is even capable of doing. The “other stuff” that ends up in Sarin – byproducts, impurities, contaminants, residue, additives and whatnot is often what gives away the most useful information. The purpose of this article is to explain in general terms the roles amines can play in the manufacture or storage of nerve agents.

The issue of amines in Sarin has been a peripheral part of the Syria debate since shortly after the Aug 2013 attacks. First, there was the discovery of Hexamethylenetetramine, commonly known as hexamine, in a large number of the field samples taken at the August 21st impact sites examined by the UN/OPCW team. Second, there were various amines reported to be in the inventory of the Syrian government, including hexamine and isopropylamine. These chemicals are on the inventory lists in the OPCW’s released document because these amines were judged by somebody, somewhere, to be part of the Syrian government’s chemical weapons production program. Whether that was an assessment by the OPCW, an admission by the Syrian government, or both, remains to be seen. However, a thorough discussion of the history and role of amines in the production of nerve agents is necessary in order to understand the Syrian situation.

What is an amine?

Amines are a chemical family of compounds. In broad terms, amines are chemicals with a basic nitrogen atom with a “lone pair” – a valence electron pair which is not shared with another atom. Amine compounds contain one or more nitrogens attached to carbon or hydrogen. That leaves an unbonded electron pair on the nitrogen atom, one chemical definition of a base. Those electrons will attract and bond with compounds or atoms that are deficient in electrons, like H+ (hydrogen ion, proton), which is characteristic of common acids. H+ is missing a pair of electrons. These definitions of acid and base are those in general use in most elementary chemistry textbooks. There are many amines in widespread use in for scientific, medical, and industrial uses.

Why would you use amines in Sarin production?

While amines have a role to play in some other nerve agents, the nerve agent Sarin was involved in the a number of chemical weapons attack in Syria. For this reason, this article focuses on Sarin. However, amines have uses in other nerve agents as well, so where applicable, this will be noted.

The production of Sarin can be accomplished by a number of different production paths, about twenty of which are known to me. My own ethics and conscience, as well as various legal and regulatory issues, prevent me from providing an exhaustive listing of these various production paths. However, I can summarize by saying that all of the production paths end with either hydrogen chloride (HCl) or hydrogen fluoride (HF) as a by-product. The second to-last step of all of the production pathways is one of two reactions:

1 mol DF + 1 mol Isopropyl Alcohol = 1 mol Sarin + 1 mol HF

1 mol DF + 1 mol DC + 2 mols Isopropyl Alcohol = 2 mols Sarin + 2 Mols HCl

The resulting acid is bad for a number of reasons. HF is worse in general terms than HCl, but both are bad for the following reasons:

  • The production of acid in an exothermic (heat-creating) reaction, such as the reactions that produce Sarin, can rapidly cause an unsafe situation in the production lab or factory. A sudden arrival of a hot corrosive gas requires special chemical engineering measures to handle and can destroy equipment or kill people. Earlier in my career, I interviewed technicians who claimed that the production of HF in US binary shells (the M687 project) was enough to cause those shells to explode in flight on their way to the target, an obvious design flaw. These test reports remain secret, so I cannot confirm this.
  • The acid by-product can make the Sarin-acid mix unsafe to handle – for example, acids can easily destroy most of the standard types of protective clothing and equipment that a soldier or technician would wear. HF in vapour form will not be stopped by military chemical protective equipment, for example. There is anecdotal information from the Iran-Iraq war that Iraqi chemical soldiers suffered injury or even death from combining the binary components, as their Soviet-designed mask and suits, while adequate for protection from Sarin, did not resist the corrosive effects of HF.
  • The resulting Sarin-Acid cocktail will have a very short shelf-life. Sarin does not last very long in either high or low pH levels. The shelf-life of well-made Sarin can be very long under correct conditions. However, the shelf-life of Sarin with residual acid can be greatly reduced. Saddam Hussein’s Sarin had a shelf life of only a few months, in part or in whole due to residual acid.
  • The acid will corrode weapons and storage containers.  By weight, Sarin produced from the DF + Isopropyl method will have 140 g of HF for every kilogram of Sarin produced. This is a level of hydrofluoric acid that will be very corrosive to nearly any conceivable storage container or munition. Indeed, such a corrosive mix may, over time, interfere with fuzes or bursting charges, or leak out of the munition.  Saddam Hussein’s Sarin-filled rockets had serious corrosion problems, largely due to acids.
  • Mechanical and thermal methods of removing the residual acids are very difficult to achieve. The US and the USSR had to devote an extremely elaborate and expensive engineering effort to solving this problem, and it resulted in a very large infrastructure. The US and USSR had developed different methods for acid removal, but both are very expensive and require significant effort as well as specially designed apparatus.

Amines, in general, are useful as acid scavengers. Depending on the structure of the amine, the amine molecule will latch on to acid molecules, such as HCl or HF. In layman’s terms, the “lone pairs” in amines are, in effect, like parking spots for acid molecules. This means that if you add an amine in at the correct step of the manufacturing process for Sarin (or Soman) a lot of acid can be removed from the mix. Amines have a long history as acid reducers and anti-corrosion additives for basically the same reason.

Various Amines in Nerve Agents

Some commentators have recently claimed that only isopropylamine is used in Sarin production. This is patently untrue, as any basic research on the subject will indicate. None of the thousands of tons of US unitary Sarin produced at Rocky Mountain Arsenal use isopropylamine for acid scavenging. The assertion in various documents that this is the “standard US method” are misleading.

Numerous amines have been experimented with in nerve agent production, for various reasons. As the open literature on nerve agent production represents only a tiny fraction of the total body of knowledge on the subject, I cannot claim by any stretch that the following list of chemicals is comprehensive.

Tributylamine (CAS 102-82-9): Tributylamine was used as an anti-corrosion inhibitor in Sarin produced by the US Army at Rocky Mountain Arsenal in the 1950s. It was added after Sarin was produced and the vast majority of the acid removed by the US’s secret refining method. Pure Sarin has a slow corrosive effect on steel over time, and any residual acid exacerbates this problem. Tributylamine was needed as an additive to prevent corrosion in the bomblets for the Honest John missile and was added to much of the Sarin arsenal in order to prevent corrosion in steel containers or munitions. Unitary Sarin in the US inventory had an average tributylamine content of 1.95%.

It appears that tributylamine was used in quantity by the Libyan chemical weapons program, as quantities of it were destroyed as part of the chemical demilitarisation effort there.

Triethylamine (CAS 121-44-8): This substance is used in many commercial acid reduction processes. A declassified document from Porton Down in 1956, now available online through the US government, discusses that triethylamine was used in the United Kingdom as an acid-reducer in Sarin. This document indicates that triethylamine was considered the standard acid-reducing additive in UK Sarin. The same document also notes certain problems with triethylamine. UK-produced Sarin had shelf-life problems and, based on the production rate of the UK’s pilot plant at Nancekuke, Cornwall, which produced Sarin at a small rate to replace Sarin that had degraded, it seems that UK Sarin had perhaps a shelf life of a year or two. This is only an estimate, however.

Iraq is known (through revelations from UNSCOM) to have attempted to use triethylamine as an acide scavenger and additive. It is also known that the Aum Shinrikyo cult in Japan experimented with triethylamine as a Sarin additive, but without success. In Syria, 30 tons of triethylamine were declared in Syria’s OPCW declaration.

Isopropylamine: (CAS 75-31-0):  Isopropylamine is another useful acid scavenging amine, with a history of use in nerve agents. It’s primary documented use was in the US M687 binary chemical artillery shell.  (See my reference on binaries for greater discussion of binary Sarin.)  This substance is highly soluble in isopropyl alcohol, giving it utility in binary formulations wherein the materials are mixed inside the weapon system. The prime example of this is the US M687 155mm binary Sarin artillery shell.   One component of the M687 binary shell was a canister containing a cocktail of isopropyl alcohol and isopropylamine. It would appear that isopropylamine is actually less efficient at scavenging acid than many other amine compounds, and I can find no use for it outside of binary applications. The Syrian OPCW declaration includes 40 tons of this chemical.

N, N-diethylaniline: (CAS 91-66-7) The Aum Shinrikyo cult used N, N-diethylaniline in their Sarin formulation.  This was apparently done after their experiments with triethylamine failed.  The Aum cult acquired 50 tons of this chemical.  The overall effectiveness of this approach is not known, as we have very little idea about the overall shelf-life or corrosive properties of the Aum group’s Sarin.

Hexamine: (CAS 100-97-0) Up until the war in Syria, the chemical hexamine had not been noted in the manufacture of or post-manufacture storage and handling of nerve agents.  It was not considered a precursor or relevant chemical in any of the schedules of the Chemical Weapons Convention (CWC) nor was trade in hexamine of particular interest to people studying chemical proliferation.  However, hexamine appears to have been incorporated into the Sarin produced and used by the Syrian government in at least three different Sarin incidents: April 2013, August 2013, and April 2017. In all three incidents, hexamine was found in environmental samples.  In the case of the April 2013 attack, the French government obtained an intact grenade-type device which contained Sarin and hexamine.  The joint UN/OPCW report in late 2013 provides a high degree of detail about the various places in which hexamine was found in the environmental samples from the Aug 2013 Ghouta incident. It should be noted that the report uses hexamine’s alternative name hexamethylenetetramine.  French intelligence services report that hexamine was also found at the site of the April 2017 attack, in the same report referenced above.

In the UN/OPCW report, hexamine was found in a wide number of places in and around the Moadamiyah and Zamalka impact zones, wherein rockets containing Sarin were used to kill over 1000 people.  I have produced this table to summarise the locations where hexamine was found, and what it was found alongside of.

After the Aug 2013 attack, Syria signed he CWC and allowed the OPCW to dismantle and dispose of its declared inventory of hardware, weapons, and chemicals.  The declared inventory of precursor chemicals given to the OPCW show a substantial stockpile hexamine.  80 tons of hexamine were declared in the inventory, a quantity indicative of industrial-scale use.  As it was not a scheduled chemical, there would have been no reason nor any requirement to disclose this stockpile unless it was part of the Syrian chemical weapons programme.

The role of hexamine as an acid scavenger in the production of Sarin was alluded to by members of the UN/OPCW mission that went to Syria in 2013 in a briefing to the press in December 2013.  A number of references (see references 1, 2, and 3 below) point to the fact that a molecule of hexamine can bind with up to four molecules of HF.  A patent from the Soviet Union points to the use of hexamine to remove HF from gas.  Much comment has been made in various comments and documents about the solubility of hexamine in isopropyl alcohol.  This is basically a red herring.  Dissolving hexamine in isopropyl alcohol makes engineering sense if you are trying to make a binary weapon that mixes in flight (like the US M687). However, none of the weapon systems used in Sarin delivery to date in Syria are such a system.  Use of hexamine by some other means, such as a slurry of finely powdered hexamine, have already been alluded to in comments by at least one chemist in the comments section of other Bellingcat posts.  To date, no viable technical objection to the use of hexamine as an acid scavenger has survived scrutiny.  And we are left with the very appropriate question – if it cannot be done, how is it that hexamine is all over the environmental samples AND was in the declared inventory of the Syrian CW programme.  Several commentators have pointed to the lack of specific literature stating this particular use in Sarin. However, many aspects of manufacturing modern chemical warfare agents, particularly nerve agents, are not widely documented in open literature for understandable reasons.  This should not be taken as a reason that it couldn’t be done.

There are other uses for hexamine, and some of these uses have been posited as alternative explanations for its presence in the environmental samples.   It is used as a medicine for treating urinary tract infections,  in some types of medical laboratory procedures, as a food additive, as a heating fuel (tablets of hexamine have been used as a cooking fuel in many militaries), as an anti-corrosion agent (such as an additive to paint), and for the manufacture of various kinds of explosives.    Several of these bear additional comment.

Paint Additive: Theoretically, hexamine could have been added to paint as a corrosion preventer.  This might have been a viable hypothesis if the environmental evidence was one or two fragments of a device and nothing else.  Indeed, one cannot rule out (on the basis of evidence in the public domain) that hexamine may have been added to the paint on the ordnance used.   Hexamine was found in a lot of places that seem to not have any paint, but also have either Sarin or its distinctive hallmarks.  However, the quantities would be quite small, and certainly not enough to account for an 80 ton inventory.    Furthermore, Sarin mixed with hexamine appears to have been found in the intact grenade-type device recovered by the French.

Cooking Fuel: Use as cooking fuel could, theoretically, account for a small portion of the samples, particularly debris from inside buildings. However, cooking fuel does not account for its presence in a crater in the road, or soil samples from Ghouta, or on the residue of different devices from three separate incidents.

Explosive manufacture:  Hexamine is used to manufacture the explosive RDX, which is, in turn, incorporated into other types of high explosive, for example C-4.  Some commenters have latched onto this as an explanation for the prevalence of hexamine in environmental samples.  Discussing this with chemists as well as EOD technicians who do post-blast investigations, the easy way to say this is the Hexamine goes into the explosive as an ingredient, but it doesn’t come out as a byproduct. The chemistry does not appear to work that way, as explained in references 4 through 7 below.  I can find no reference to hexamine as a decomposition product or residue relevant to explosive incidents, having conferred with several experienced post-blast investigators.  (Indeed, the author would be happy to hear from one who has found it, in the cause of thoroughness. Please contact me.)   Hexamine left over from the production of RDX is another proposed theory, but established methods (example here) wash away the leftover hexamine for re-use, and it would appear terribly wasteful and inefficient for a modern manufacturer to leave excess hexamine in their RDX, reducing the purity of the RDX.   Furthermore, has it been established that RDX or RDX-based explosives were the disseminating explosives in these incidents?  This is certainly plausible but I do not see where this has  been clearly established.  Indeed, one of the environmental samples showed TNT, not an RDX-based explosive.  Finally, hexamine is flammable.  If explosively disseminated some of it would surely combust. Signs of this are not in evidence.   Finally, we get back to the 80 tons declared to the OPCW.  It was declared as a component of the chemical weapon programme, not as a component in explosives manufacture, which is beyond OPCW’s remit.

Other Relevant Appearance of Amines in Nerve Agents:

Thickening agents:  At least one declassified study refers to the use of various amine compounds in order to thicken G- and V- series nerve agents.

Decontamination: Not every amine is useful in the presence of a chemical warfare agent. Some can be quite destructive to some chemical warfare agent substances, some on their own, others in solution, e.g. dissolved in water or another solvent. The use of amines for decontamination of chemical warfare agents, has been well established in available literature for some time.  For many years, the US military used a substance known as DS-2, which contained 70% diethylenetriamine.   Monomethylamine, mixed with water, is a very good decontamination agent for G-series nerve agents. The older versions of the US Army’s decontamination manual FM 3-5 refers to dichloramine and hexachloramelamine as possible decontaminants for Sulfur Mustard.  Isopropanolamine was investigated as a possible decontaminant. Numerous other amines may have utility in this regard.

Byproducts:  Diisopropylamine is a commonly found impurity in VX. It is a possible decomposition product after decontamination of VX by decontamination involving hypochlorites. See ref 9.

Pyridostigmine:  The drug pyridostigmine is a quaternary amine. It has some applications as a pre-treatment before human exposure to nerve agents, to improve the efficacy of oxime-based antidotes.  It is of great value in protection against the nerve agent Soman, but of dubious value for protection against other nerve agents.

 

The author would like to thank the commentator “DDTea” for the references, which are previously published in comments sections for other Bellingcat posts.

References

  1. Ennan, A. A.; Brazovskaya, O. M.; Chopotarev, A. N. Products of the reaction between hydrogen fluoride and hexamethylenetetramine. Zhurnal Obshchei Khimii, 1975, Vol. 45, Issue 3, p. 706.
  2. Ennan, A. A.; Chobotarev, A. N.; Brazovskaya, O. M. “Hydrofluoric acid-​hexamethylenetetramine-​water system,” Zhurnal Neorganicheskoi Khimii, 1975, Vol 20, Issue 3, pp. 786-790
  3. Ennan, A. A.; Lapshin, V. A.; Brazovskaya, O. M.; Grishuk, N. S.; Mikhailovina, S. K. “Corrosion of steels in aqueous solutions of hydrogen fluoride containing urotropine,” Izvestiya Vysshikh Uchebnykh Zavedenii, Khimiya i Khimicheskaya Tekhnologiya, 1975, Vol.18, Issue 5, p. 840.
  4. J. D. Cosgrove and A. J. Owen. “The Thermal Decomposition of 1,3,5 Trinitro Hexahydro 1,3,5 Triazine (RDX)-Part 1: The Products and Physical Parameters” Combustion and Flame, Vol 22, Issue 1, Feb 1974, pp. 13-18
  5.  A.C. T. van Duin, J. Oxgaard, and W.A. Goddard III. “Thermal decomposition of RDX from reactive molecular dynamics” J. Chem. Phys. 122, 054502 (2005).
  6. T.R. Botcher and C. A. Wight. “Explosive Thermal Decomposition Mechanism of RDX.” J. Phys. Chem. 1994,98, 5441-5444 .
  7.  R. Behrens. “Thermal Decomposition of HMX and RDX: Decomposition Processes and Mechanisms Based on STMBMS and TOF of Velocity-Spectra Measurements” Chemistry and Physics of Energetic Materials
    Volume 309 of the series NATO ASI Series pp 347-368
  8. Munro NB, Talmage SS, Griffin GD, et al. The sources, fate, and toxicity of chemical warfare agent degradation products. Environmental Health Perspectives. 1999;107(12):933-974.

 

Dan Kaszeta

Dan is the managing director of Strongpoint Security Ltd, and lives and works in London, UK. He has 27 years experience in CBRN response, security, and antiterrorism.

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121 Comments

  1. Sean

    It seems like sarin is the star of the ACE-inhibitor but Perform the reaction on the chemical in roundup * esterify….

    Reply
    • DDTea

      *AChE (acetylcholinesterase) inhibitor. ACE (angiotensin-converting-enzyme) inhibitors are heart drugs.

      Reply
  2. Andrea

    This article doesn’t show up in the homepage…
    i had to go back to the link on Twitter to read it..
    And it has to be put in the home due to its importance; thanks to the author.

    Reply
    • Dan Kaszeta

      It was an old article and it has been revised, so I think it still has it’s old publication date. I’ll see if we can get it re-dated.

      Reply
  3. Marko

    There must be many other OPCW reports on suspected chemical attacks not involving sarin that include chemical analysis of environmental and munition samples. And I trust that hexamine is nowhere to be found in these reports ,
    correct ?
    If hexamine was present in these cases , would it have been detected and
    reported ?

    These non-sarin event investigations could go a long way toward proving that hexamine is a marker for sarin , at least in some cases. It still wouldn’t prove that it’s only a marker for Assad’s sarin.

    Reply
  4. Ghostship

    This is all irrelevant, because it’s quite clear that the local sources are lying about this incident. The current claim is that there were four devices dropped by the aircraft over Khan Shaykhun and there is video evidence that four dust clouds from explosions appear over Khan Shaykun. The three in this video which most people have seen:
    https://www.youtube.com/watch?v=MYOMEDK_uVs
    There is another video which features two dust clouds. One which is almost certainly the right-most dust cloud in the above video and another which appears between 0:05 and 0:06 in this video:
    https://www.youtube.com/watch?v=yTx0kmQnZLw
    Such an obvious oversight as missing an entire bomb explosion and trying to hide that fact suggests very strongly that the local sources are lying and if they’re lying about such a fundamental fact as the number of bombs dropped on Khan Shaykhun then that suggests that their narrative cannot be trusted at all.

    Reply
    • DDTea

      Can people who lie about the presence of a warehouse full o’ sarin be trusted when they invent new stories?

      Reply
      • Ghostship

        Is that the best you can manage? Suggesting that I’m a Putinbot?
        The trouble with the narrative that you’re pushing is that it was too complete from the beginning – any new evidence surfaces that disagrees with your narrative and you have no wriggle room to explain it away as in this instance. There were four bombs dropped by an aircraft according to all the witnesses and bomb explosions are quite difficult to ignore or pretend didn’t happen. Evidence of a fourth conventional bomb explosion turns up and that’s your narrative in shreds.

        Reply
        • Marko

          After looking at the NYT explanation of how they did their study , I’ve got similar questions , but I see the video evidence a bit differently from your interpretation.
          First , the main video shows four clouds not three – you don’t need the second video to come up with the fourth. Both videos show one bomb cloud that is much smaller than the others , but still an obvious strike. So , these four bomb strikes could correspond to the reports , since these would have been the ones associated with loud explosions. That means the sarin strike has to be the fifth strike , but it’s the one not so easily noticed because of limited noise or concussion on impact , which could explain the reports of four , rather than five strikes.

          What I’d like to see is a single geolocation map showing all FIVE strike sites , as well as the two camera locations. And the area where the CW casualties came from – show that , please.

          Then I need to know why the NYT is so set on insisting that the Syrian/Russian story doesn’t hold up , because no warehouses in east KS were hit , just homes and the street crater. This makes no sense. They’re not admitting to dropping ANY of those near-sunrise bombs. The bombing run they admit to was near noon , one of which the White Helmets claim dropped on their clinic , and at about the time the Syrians admit to executing air strikes.
          Were there other strikes around noon , and if so , where are they on the map ?

          And why all the attention on the long-ago bombed silos , which have nothing to do with anything , yet keep arising as a topic we should take note of , and which were the subject of extensive video tours in the days just after the
          attack ? Does someone want us to look over there so we don’t look somewhere else ? Was the dead goat a teaser for the interminable silo tours ? If so , it didn’t work.

          Malachy Browne acts like he’s put together a nice , neatly-wrapped package , when in reality he’s got flaps and loose ends sprouting everywhere.

          Reply
    • Ian W.

      Could not agree more. I have no love for Assad, but Nusra and the White Helmets are worse. They lie for a living. Assad lies less than they do, and he lies a lot.
      We’re supposed to believe that these fancy PhDs from SSRC made dirty, chlorine-tainted kitchen Sarin and dropped it on a bunch of kids on purpose? It does not feel right. With all due respect, I think bellingcat are all wet on this attack, bolstering a case for Israel, France, the UK and America who want Assad’s scalp so badly they can’t think of anything else..

      Reply
  5. Mark

    I’m curious if you updated anything besides adding the recent French report information.

    What is the best case made against your hexamine conclusion?

    Reply
    • DDTea

      Dan (and I) are arguing that hexamine was used to scrub nascent Sarin of hydrogen fluoride and/or as a long-term stabilizer inside shells. The best argument against this, as far as I can tell, is that it is from conventional high explosives. Ake Sellstrom mentioned this possibility in an e-mail to a certain professor. That same professor, in his recent report from April 30, mentions the same possibility.

      This argument has not been supported by any data. Moreover, available peer reviewed data (and there is a lot) contradicts this claim. So it appears to be a myth that nobody’s been willing to squash until now.

      Reply
      • Mr White

        I thought the best argument against it is that it’s non soluble in the chemicals used to make Sarin whereas other amines are soluble

        Reply
        • DDTea

          As Dan mentioned in this article and as I’ve commented in other posts here, this is a red herring. It doesn’t have to dissolve in order to scrub hydrogen fluoride. For many organic reactions, having an insoluble component is advantageous in that it allows convenient separation and purification of the desired product. But if it *does* dissolve, then there should be no problem for it serving in role of an HF scrubber. So either way, it’s not an issue.

          The solubility of hexamine in DF/IPA is something that’s difficult to predict a priori. And given the safey and legal considerations around it, it’s not something that can be verified in any old lab. The researchers that are authorized to do such chemistry likely would not present the results in the open literature. So it’s an “unknowable,” but in no way does it alter the conclusion.

          Reply
          • Mr White

            Even I know a base dissolved in one of the fluids is far more effective and convenient than one that doesn’t dissolve.

            And we already know hexamine doesnt dissolve. You did that experiment yourself didnt you?

          • DDTea

            We know hexamine doesn’t dissolve in IPA. That doesn’t say anything about its solubility in DF or in the mixture of IPA and DF.

            We can’t possibly know anything about relative effectiveness in the absence of published data or our own experiments.

            As for convenient, I disagree. Imagine trying to stockpile a CW program in the Syria. Would you choose the volatile isopropylamine, which may build pressure in its storage containers or evaporate; or the solid hexamine? Also remember that any soluble components will be loaded into the shell, taking up space that could be occupied by sarin. Thus there would be an interest in using the purest sarin that’s practical. Settling insoluble solids and filtering is a very convenient, low-energy, purification method on large scale.

  6. RobTN

    Do we get some comments on Postol’s latest foray into the world of chemistry?

    Reply
    • Dan Kaszeta

      Postal makes reference to an “indigenous Sarin attack in Denver” – and it is quite unclear exactly what point he is trying to make by referring to a non-existent event.

      Reply
      • RobTN

        Well I’m quite intrigued by his showing an acid scrubber being responsible for the formation of DIMP.

        And what looks like labeling isopropyl alcohol (less one H) as an oxygen methyl fragment of sarin decay.

        Reply
      • RobTN

        I THINK he’s trying to make the argument that – based on the French criteria (hexamine, DIMP) – material from the USA stocks of old would be classified as “Syrian’.

        Reply
  7. Mr White

    And if we’re talking about using something that is not soluble in the Sarin precursors to neutralise HF, we dont need hexamine at all.

    Why not just use universally available and cheap calcium carbonate?

    just filter out your sarin when youre done, not exactly difficult.

    Reply
    • DDTea

      Calcium carbonate releases CO2 on contact with acids and may build enough pressure to burst vessels. In process chemistry, reactions that evolve copious amounts of gas are not desirable.

      The insoluble CaF2 would be readily removed though.

      Reply
      • Mr White

        so you have a pressure release valve, again that’s hardly pioneering science.

        Reply
        • DDTea

          Think through what you’ve just said. Design a pressure relief valve for a reactor that’s producing sarin? Not to mention that it would be impossible to load shells with sarin that’s effervescing CO2. It may destroy the shell before it reaches its target. And should have mentioned earlier that calcium carbonate may very well destroy sarin without solving the corrosion issue:

          2 DF + CaCO3 + 2 IPA —> Sarin + CaF2 + CO2 + H2O
          H2O + sarin —> IMPA + HF

          One other point: in these sorts of “nucleophilic acyl substitution” reactions, the amine also plays the role of catalyst.

          Reply
          • Mr White

            sure, why not? you’ve already made your Sarin by the time you add your CaCO3.

            vent the pressure release valve to the outside. no biggie.

          • Mr White

            by the way if water destroys Sarin, as you are now saying, Sarin is pretty useless as a weapon isnt it?

          • Dan Kaszeta

            The interaction of all of the nerve agents with water is extremely well documented. But it happens in a time-scale of hours and even days, depending on various factors. The ability of a Sarin molecule to react with water has little or no bearing on its use as a rapidly acting non-persistent chemical warfare agent for production of casualties.

          • RobTN

            Water’s effect on Sarin is actually pretty well known. Heck it even features on the Wikipedia page.

            Evidence suggests it’s not useless as a weapon either.

          • DDTea

            Mr White, you can go through those chemical engineering gymnastics…or you can just design a better reaction that uses hexamine and arrive at a superior, simpler process.

          • Woody

            As we “learn” about chemistry here all day long I wonder following:
            – Why the alleged bombing was carried out by one CW warhead only if there were three or four other projectiles used. What benefit does it bring to use a mixture of projectiles in a mission with one target only?
            – Why the international scientific community has been quiet on shooting down Postol if his analysis is so wrong that you state?
            – Why we still miss the remains of the crater debris – no international, independent operator has their hands on them?

          • DDTea

            “What benefit does it bring to use a mixture of projectiles in a mission with one target only?”

            Good question. Ask Mohammad Hasouri a.k.a. “Quds 1.” Otherwise it’s unknowable.

            “Why the international scientific community has been quiet on shooting down Postol if his analysis is so wrong that you state?”

            The scientific community doesn’t stop to listen when he releases another error-filled, non-peer reviewed “report.” I doubt anyone in my department (besides me) has even heard of him. His words don’t command much awe from anyone other than audiences of RT, globalresearch, Infowars, or Holocaust-denying outlets. He’s still struggling to articulate a viable alternative hypothesis for what happened in Khan Sheikhoun.

            Anecdotally: among my colleagues, nobody cares about the residues of the Sarin used in Syria. I’m an oddball: a chemist with a bookish interest in chemical weapons who isn’t restricted by a security clearance/non-disclosure agreements.

            “Why we still miss the remains of the crater debris – no international, independent operator has their hands on them?”

            I’m curious whom you consider “independent” enough to trust. The Venn Diagram of these “independent operators” and labs that can perform forensic investigations of a chemical weapon probably has zero overlap.

          • Woody

            Goooooddd morning Washington,

            we’ve got a great day ahead of us, comin’ on your way is the “Coup or Loop” competition with our homies throwing out the best they get. Audience disclaimer: Coup or loop is a format created by CIA and its been running continuosly as the audience no 1 since August 1953, first broadcasted from Iran – APPLAUSE!

            So you say that Quds 1 – or is it God’s 1 – just by taking a morning shit before departure came up with an idea that “Lets bring in some of that funny gas”!
            It makes no sense and you gain nothing by such action.
            And then he went on picking from the stock the namely projectile that has the latest tech around manufactured by the Invisible man’s Invisible materials Inc?
            We still hold our breath for you to show how the flight path brought that bomb to that particular spot – one thing to start with before moving to the second reasoning.

            By now you keep up saying and repeating that Postol hardly is a factor to be dealt with and that he possesses no authority whatsoever? Yet you have made here the assumptions previosly of the composition of Sarin – on its hexamine etc saying that yes – you make assumptions that have not been proven wrong. How does the academic world position you and Postol?

            On this planet that apparently we both inhale there is no single scientist that could explain the debris residue with the tube to be a projectile that carried the alleged Sarin to the point of impact. So the answer to your question of a trusted third party is that there are many – I take even a US scientist for that case – you just name him/her. To underline the trouble here – for the sake of repetition – is that we still have people arguing if it was an aerial bomb, rocket or missile – let a lone to tell how the mechanism could have worked so that the blast left no tailfins, no real crater etc behind.

            Of course the media will say that Russia has not proven there was no warehouse. But nor has US proven that Russia had something to do with it. So why should Russia or Assad for that matter guess right what there was?

            For me – if I could – it would be the day of my life to shoot down an academic arguement made by a Yale, Princeton, MIT so on professor. Not gonna happen, though. In the academic world you build the merits for beating up the others’ research, how would that not be the case in the Postol’s? Know why? The puzzle they are holding does not fit into the picture.

    • RobTN

      Wouldn’t the solubility argument also rule out – say – activated carbon – or ion exchange resin as a means of removing impurities?

      However they both seem to work rather well.

      Reply
  8. Marko

    “…..the shelf-life of Sarin with residual acid can be greatly reduced. Saddam Hussein’s Sarin had a shelf life of only a few months, in part or in whole due to residual acid.”

    I believe the notion of the rapid decay of lower-quality sarin has been vastly overstated. Let’s say “shelf-life” equals half-life. If the half-life is 4 months , in 2 years you would expect to have 1/64 of the starting concentration ( technically , you’d probably expect it to be even lower , as it’s been said that the decay accelerates as breakdown products accumulate ).

    Iraq was making sarin at a purity of ~60% up to around 1990 or so. Thus you’d expect that any sarin in weapons found by the U.S. in the 2000s would be effectively entirely degraded , since they would have undergone a minimum of 30 4-month half-lives. Not the case , however :

    “The extraordinary arms purchase plan, known as Operation Avarice, began in 2005 and continued into 2006, ……It led to the United States’ acquiring and destroying at least 400 Borak rockets, one of the internationally condemned chemical weapons that Saddam Hussein’s Baathist government manufactured in the 1980s…..Many rockets were in poor condition and some were empty or held a nonlethal liquid, the officials said. But others contained the nerve agent sarin, which analysis showed to be purer than the intelligence community had expected given the age of the stock. ”

    ” The analysis of sarin samples from 2005 found that the purity level reached 13 percent — higher than expected given the relatively low quality and instability of Iraq’s sarin production in the 1980s, officials said. Samples from Boraks recovered in 2004 had contained concentrations no higher than 4 percent.

    The new data became grounds for concern. “Borak rockets will be more hazardous than previously assessed,” one internal report noted. It added a warning: the use of a Borak in an improvised bomb “could effectively disperse the sarin nerve agent.”

    An internal record from 2006 referred to “agent purity of up to 25 percent for recovered unitary sarin weapons.” ( The 2004 Duelfer Report mentioned a binary shell with sarin at ~40% purity )

    The reason for downplaying the risk may have been due to financial considerations:

    “A New York Times investigation published in October found that the military had recovered thousands of old chemical warheads and shells in Iraq and that Americans and Iraqis had been wounded by them, but the government kept much of this information secret, from the public and troops alike….”

    “…Not long after Operation Avarice had secured its 400th rocket, in 2006, American troops were exposed several times to other chemical weapons. Many of these veterans said that they had not been warned by their units about the risks posed by the chemical weapons and that their medical care and follow-up were substandard, in part because military doctors seemed unaware that chemical munitions remained in Iraq. In some cases, victims of exposure said, officers forbade them to discuss what had occurred……”

    https://www.nytimes.com/2015/02/16/world/cia-is-said-to-have-bought-and-destroyed-iraqi-chemical-weapons.html?_r=0

    Reply
  9. RobTN

    “Let’s say “shelf-life” equals half-life.”

    OK, why make that assumption?

    Reply
    • Marko

      You need some definition. I picked one. You can too.

      It won’t change my conclusion. Shelf life (half life) is claimed to be months , I say field data says it’s years.

      Reply
      • RobTN

        I suppose it depends on the mechanism of decay.

        OK some impurities will decay the sarin, but if they are used up in the process then presumably they can only decay it to a point.

        Half life would suggest it happens spontaneously without a second chemical being involved.

        Reply
      • RobTN

        To clarify – I think that you assumption that shelf life and half life are synonymous isn’t sound.

        Reply
        • Marko

          The terminology tends to obscure the reality for our purposes , I think. “Shelf life” for Assad, Gaddafi, or Hussein would have referred to the time it takes to decay to a point where the sarin was no longer useful militarily , i.e. as a WMD threat to counter the nuclear threat from enemies like Israel. If they produced new sarin at 60% purity , they might decide that stocks needed to be replaced when it fell to , say , 40%.

          For purposes of small terror events as we see in the Syria false-flags , the useful potencies are much lower. You don’t need efficient mass killing to get the result you’re looking for , you just need to do enough damage to make it obvious that a poison gas attack has occurred. And the fact that the Iraqi unitary weapons still had considerable amounts of active sarin – after a decade or more under haphazard storage conditions – shows that the idea that the rebels would need an active production facility , or that any sarin they come across is a short-term “use it or lose it” opportunity , is a myth. They can continue to do what they’ve been doing by drawing from sarin stocks that may be many years old , especially so if those stocks are in binary form.

          Reply
  10. RobTN

    Except for the teensy problem of Sellstrom reporting HIGH purities.

    But hey, why let that interfere in your false flag conclusion?

    Reply
    • Marko

      How does that logic work ?

      I argue that sarin is more stable in the field after production than has been typically portrayed and you say that high purities in the field disproves that. ???

      I don’t presume to know where the rebel sarin came from , whether they have access to more than a single batch , or what the current potency(s) might be. I’m just saying whatever they’re using , it’s likely to be relatively stable over the time frame of the attacks that we’re dealing with.

      Reply
      • RobTN

        It works like this

        “For purposes of small terror events as we see in the Syria false-flags , the useful potencies are much lower. You don’t need efficient mass killing to get the result you’re looking for , *you just need to do enough damage to make it obvious that a poison gas attack has occurred*”

        But the actual potencies are higher. According to Sellstrom.

        So pick one, lower potencies are all that’s needed for ‘false flags’ or higher?

        Also

        “I don’t presume to know where the rebel sarin came from ”

        That seems to presuppose that the rebels HAVE sarin.

        Though there’s not a lot of actual proof they have it. (Also you’d have to distinguish which rebels too).

        And

        “They can continue to do what they’ve been doing by drawing from sarin stocks that may be many years old”

        Which takes us back to Sellstrom saying it’s high purity – which seems to rule out ‘many years old’.

        Reply
        • Marko

          ” So pick one, lower potencies are all that’s needed for ‘false flags’ or higher? ”

          If the rebels have access to high-potency sarin , I’m sure they’d use it. If they only had access to lower-potency sarin , I’m sure they’d use that as well.

          ” Which takes us back to Sellstrom saying it’s high purity – which seems to rule out ‘many years old’. ”

          I said I don’t presume to know the provenance of the rebels’ sarin – it could be new , it could be old. And I think it’s clear that relatively high purity or potency sarin can remain that way for years , rather than months.

          Carry on being purposefully thick , if you choose , but I won’t further encourage you. It’s a real waste of bandwidth.

          Reply

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