Gaussling is a senior scientist in the chemical business. He occasionally breaks glassware, spreads confusion and has been known to generate new forms of hazardous waste. Gaussling also digs aerospace, geology, and community theatre.
According to the online news source “Upstream“, what is at the time of writing the Category 2 Hurricane Francine spinning northeastward in the Gulf of Mexico has resulted in the shutdown of approximately 23.5 % of gulf oil and 26.6 % of gas production. Approximately 35 % of the 371 manned platforms in the gulf have been evacuated according to the US Bureau of Safety and Environmental Enforcement (BSEE).
Francine is projected to make landfall along the Louisiana coast Wednesday on 9/11/24 and move up through Mississippi. That is, unless Trump gets out his Sharpie marker and wills it in another direction ...
The “Who Dat Field” and more
Naturally, when investigating the gulf shutdown I saw mention of the “Who Dat Field“, I had to look into it. It is located in the Mississippi Canyon (MC) blocks 503 / 504 / 547 in the Gulf of Mexico (GOM) in water depths of 945m.
The Who Dat Field is made up of ten stacked reservoirs of the Pliocene and Upper Miocene age. Its reservoirs are located at a depth of 10,000ft-17,000ft, with pressures ranging between 6,000 psi and 12,500 psi.
The three wells drilled at the field encountered more than 700ft of net pay in the reservoirs. The wells flowed at the rate of 10,000 barrels a day of oil and 60 million cubic feet a day of non-associated gas. Source: “Who Dat Field“.
The origin of the phrase “Who Dat” comes from the Acadiana region of Louisiana. There are numerous claims to the origin of the phrase and there have been legal spats concerning the trademark ownership of the phrase. The NFL in particular has thrown its ponderous weight around in the matter. The reader is encouraged dive into controversy.
[Note: This is an updated version of an earlier post.]
Recently I spent some time tracing the very early history of gunpowder or Huo Yao (China, ca 850 AD). It turns out that the earliest clear description of a gunpowder-like composition was described in a document produced during the Tang Dynasty. A document titled “Classified Essentials of the Mysterious Tao of the True Origins of Things” contained a list of particularly dangerous elixirs. A comprehensive history of Chinese science can be found in “Science and Civilisation in China, Volume 5: Chemistry and Chemical Technology, Part 4, Spagyrical Discovery and Invention: Apparatus, Theories and Gifts” by Joseph Needham. Within this list of hazardous compositions, a warning was offered citing the dangers of mixing and heating together realgar, salt peter, sulfur, and honey. The document tells of alchemists mixing this combination and heating it, resulting in a deflagration leading to burnt beards, faces, and hands as well as the loss of the structure to fire. This mixture has been translated as “fire-drug”.
There are earlier references to admixtures that could produce a violent effect, but the compositions are not disclosed. The information in the 850 AD document clearly describes the components of classic gunpowder- a nitrate oxidizer, sulfur or sulfide for low ignition temperature, and a carbohydrate reducing agent- honey. What is notable about gunpowder is that is a self-contained redox system containing two sides of the fire triangle– fuel and oxidizer in intimate contact. All that is needed for an exothermic reaction is initiation with some kind of energy stimulus.
A couple of thoughts on the realgar present in the mix. First, alchemists were commonly in the apothecary trade and made their living preparing medicaments, not so much searching for the philosopher’s stone. It is not unreasonable to suppose that the composition was intended for some medicinal effect. Realgar is red tetraarsenic tetrasulfide (As4S4), possibly with some amount of yellow Orpiment (As2S3), and may have been a common apothecary ingredient of the time. Crystalline realgar is a ruby-like, eye-catching substance and it is not surprising that it captured the fancy of alchemists.
Second, realgar and orpiment are found in hydrothermal deposits as are copper, gold, silver, and mercury sulfides (metal sulfides as a group were referred to then by the obsolete term sulphuret). Back when roasting ore was widely practiced (and legal), it was common for miners in American lode gold districts to heap sulphuretted ores onto a wood pile and set it alight directly or air oxidize it in a reverberatory furnace. This process would actually ignite the sulphureted ore and in the case of gold and mercury, release the native metal. The point is that sulphuretted arsenic would be expected to contribute to the combustion process as a reducer of nitrate or just as a spectator fuel.
My understanding of sulfur’s role in gunpowder is that of a low-melting, combustible substance which, when ignited, maintains intimate thermal contact with the solid nitrate and carbon elements, transferring heat to trigger and sustain the deflagration or explosive redox reaction.
In medieval times, before blasting with gunpowder was available, it was common in hard rock mining to fracture rock by creating a large fire adjacent to a rock face to get it hot, then water was splashed on it in an attempt to fracture the hot rock by thermal shock. [In my lonely voice squeaking out from under my rock along the riverbank, I would offer that this activity might have presented the opportunity to discover that some (sulphuretted) minerals were combustible. Alternatively, building a ring of sulfuretted rock around a campfire may have led to the same discovery.]
Just WOW!! A team from Nagoya University in Japan performing synchrotron X-ray diffraction experiments at SPring-8 were able to selectively extract an image of valence level electron density in the amino acid glycine. Did you get that? And guess what they found? The valence electrons were occupying a space the shape of a molecular orbital also derived from computation!! Amazing.
The aerial view of the facility is shown below. Despite the ring being situated on bedrock, the alignment of the magnets in the storage ring is so precise that the moon’s tidal forces can have a measurable impact on the ring’s performance.
Source: Spring-8. Schematic of the overall beamline.
Source: Spring-8. There are 62 beamlines coming from the synchrotron storage ring.
The experimental work in question is that of Takeshi Hara, Masatoshi Hasebe, Takao Tsuneda, Toshio Naito, Yuiga Nakamura, Naoyuki Katayama, Tetsuya Taketsugu, and Hiroshi Sawa*, “Unveiling the Nature of Chemical Bonds in Real Space”, Journal of the American Chemical Society, accepted July 10, 2024. https://doi.org/10.1021/jacs.4c05673. As of this writing the full journal citation was not available.
Density Function Theory (DFT) calculations were performed with Gaussian 16, revision A.03.
Below is an illustration by a Riken artist comparing the theoretical valence level molecular orbital (MO) of glycine by DFT calculations and the experimental valence electron density distribution, or VED, collected by synchrotron x-ray diffraction at SPring-8.
Credit: Reiko Matsushita / RIKEN. Results from the XRD study of glycine.
If you’ve been through college chemistry, then no doubt you are familiar with atomic orbital theory beginning with Linear Combination of Atomic Orbitals, LCAO. Beyond LCAO is MO theory which goes on to help in the understanding of optical, electronic, magnetic and bonding properties of molecules. In the 1980’s and 90’s commercial software became available (and affordable)
Experimental details from the JACS paper-
Single Crystal XRD Experiments and Structure Analysis. Single crystal XRD experiments were conducted at BL02B1 beamline in SPring-8, using the quarter-circle diffractometer (Rigaku Co., Japan), with diffraction reflections detected by a two-dimensional semiconductor detector, PILATUS3 X CdTe (DECTRIS Ltd., Switzerland). X-ray energies of 40 and 37 keV were used for Glycine and Cytidine, respectively. Temperature variation was achieved using a helium-gas-blowing device (Japan Thermal Engineering Co., Ltd., Japan). The intensities of Bragg reflections were collected by CrysAlisPro program. Diffraction reflection averaging and crystal structure analysis were performed using SORTAV program and JANA2006 program, respectively. VESTA program was employed for drawing the crystal structure and electron density. The structural analyses of Glycine and Cytidine were performed at 45 and 35 K, respectively. In the present XRD experiments, the resolution limit of Glycine was dmin = 0.28 Å [(sin θ/λ)max = 1.786 Å−1] and that of Cytidine was dmin = 0.30 Å [(sin θ/λ)max = 1.6565 Å−1]. Accurate determination of structure factor Fcal(K) is crucial for the VED analysis using the CDFS method to obtain phase terms of crystal structure factors. To achieve this requirement, we refined the structure parameters using only high-angle data, a technique known as “high-angle refinement” (Section S1).
VED Analysis Using the CDFS Method. The CDFS method, a technique for directly observing a 3D VED in crystals, employs single crystal X-ray diffraction data obtained from synchrotron radiation. A detailed explanation can be found in previous papers. In this method, the experimental VED distribution is derived by subtracting the calculated core electron density from the experimental total electron density. In both cases, Glycine (C2H3NO3) and Cytidine (C5H9N2O3), the core electron density corresponds to 1s2 orbital density of C, N, and O atoms. Therefore, the phase relationship and distribution of the hybridized orbitals by 2s and 2p should be visible. DFT Calculation. Theoretical valence orbital calculations were performed using DFT with LC-BLYP functional (μ = 0.47)36 and ccpVTZ basis set by Gaussian 16 Revision A.03 program. The structure parameters determined in the present XRD experiments were used for the calculations (Tables S2 and S5). The structures, orbitals, and electron densities are illustrated using ChemCraft program, while the contour plots are drawn using the VESTA program.
Source: The Sawa paper cited above. The experiment was a single crystal X-ray Diffraction (XRD) study using the very narrow x-ray beam available from the synchrotron ring. The underlined text above reveals that the 1s2 orbital electron density was subtracted from the total experimental electron density. This would leave the partially filled 2s and 2p valence level MOs in isolation.
While structural determination by x-ray diffraction has been around for a very long time, what makes this work notable is the detection and imaging of electron density in valence level MOs and the close correlation to computational modeling.
For more information about the SPring-8 synchrotron storage ring, visit their website. The name stems from “Super Photon ring–8 GeV”.
Historically, scientific papers have been not where loud, confident proclamations are made about academic research results. The trend has been a sort of unpretentious modesty to avoid overconfidence and exaggerated claims. A sort of snobismus. Instead, conclusions from research results tend to be more guarded in the interpretation of data. An article in the Scienceinsider section of the AAAS journal Sciencepublished 28 July, 2023, has reported that of 2600 papers published in Science between 1997 and 2021, there was a drop of about 40 % in the use of hedging language. Researchers in the study scanned for about 50 terms including “might,” “probably,” “could,” “approximately,” “appear to” and “seem.” They found that these hedging words dropped from 115.8 per 10,0000 to 67.42 per 10,000.
Analyses of other scientific journals and a 2022 paper that examined nearly the same group of papers from Science have found growing use of a positive, promotional tone—expressed with superlatives such as “groundbreaking” and “unprecedented”—which may lead to exaggerated claims.
The authors suggested that researchers are increasingly unwilling to undersell their work and instead, are using more hyperbolic language such as “groundbreaking” and “unprecedented.”
In an earlier study by C.H. Vinkers et al., published in BMJ, 2015, finished his paper with the following paragraph-
“Currently, most research findings could be false or exaggerated, and research resources are often wasted. Overestimation of research findings directly impairs the ability of science to find true effects and leads to an unnecessary focus on research marketability. This is supported by a recent finding that superlatives are commonly used in news coverage of both approved and non-approved cancer drugs. The consequences of this exaggeration are worrisome since it makes research a survival of the fittest: the person who is best able to sell their results might be the most successful. It is time for a new academic culture that rewards quality over quantity and stimulates researchers to revere nuance and objectivity. Despite the steady increase of superlatives in science, this finding should not detract us from the fact we need bright, unique, innovative, creative, and excellent scientists.”
If you sit through a week of presentation sessions at an American Chemical Society national meeting or walk through a poster session, you’ll see a mix of enthusiastic young chemists standing next to their posters and you’ll sit through talks by more established researchers anxious to emphasize the importance of their work. Giving a talk or a poster at a meeting is inherently a promotional activity. It is getting the word out about you and your work in a particular area in front the scientific community and possibly some influential people. It also is something to add to your resume.
Self-promotion by scientific publishing and participation in meetings, called “ballyhoo” in the movie business, is a great way to expose yourself to greater and more frequent opportunity. Make no mistake, the quality and frequency of publications is a very important metric of your accomplishments and potential. This is a sad reality for some and a fortunate reality for a few, but it is reality.
It is hard to draw much from the above research on the hedging frequency as a metric of … what, the unseemly disappearance of proper modesty? The competitive environment of “big academic science” for funds and exposure to impress colleagues and the rank and tenure committee is inevitable. It has been like that for a very long time, but perhaps hidden under the veil of snobbery.
You never know who you might meet at these venues for academic ballyhoo. I once loaned my laser pointer to Al Cotton (who kept it!) and I met Glenn Seaborg at a poster session at the Disney Hotel in Anaheim, CA. I had too many gin & tonics before I spoke with Seaborg and I’m sure that it showed. At a symposium at Purdue University in honor of H.C. Brown (in attendance), I got to see two prominent scientists get into a rather strong “discussion” during a question-and-answer period about who discovered what first. Professor Suzuki (Suzuki coupling) from Japan said something that got under the skin of prof Negishi (Negishi coupling) from Purdue, so they began with point-counter-point exchange (a type of coupling?) which soon accelerated into an argument. As it got more contentious, they switched to speaking Japanese and continued their argument. After a short time, they realized it was best to just sit down as they were providing a “Clash of the Titans” spectacle. This is not a criticism, just an amusing anecdote. Guys like this should battle it out in public more often.
Self-promotion using exuberant language isn’t inherently bad. It is likely that others have already judged you based on far smaller misperceptions. If someone wants to embarrass themselves, let ’em.
Note: Not residing in Russia, I cannot grasp the full extent of the events and mood unfolding there. All that remains is to perch on a power pole across the polar cap and try to discern fact from fiction.
>>> Let’s ask a very basic question about today’s Russia. Why can’t Russia Putin play nice? <<<
Like most, I have anxiously watched Putin’s invasion of Ukraine. The prevailing Russian narrative is trying to say that the sovereign nation known as Ukraine has historically been a part of Russia or some earlier Russian empire, a view promoted by Putin. Following the Bolshevik Revolution, Lenin directed the Bolsheviks to seize the territory now recognized as Ukraine. The goal was to claim territory for the Soviet Union, but also territory that was extremely fertile. Stalin ordered that Ukrainian industry and agriculture were to be collectivized. An independent Ukrainian government was briefly established but just as quickly collapsed. After several years of intense Ukrainian resistance and significant suffering, Lenin conceded and established Soviet Ukraine, enabling its incorporation into the Soviet Union as a constituent republic.
In the current action, with the support of an extensive security apparatus, Vladimir Putin has resolved that what is now Ukraine will be assimilated into a growing Russian empire. The process will methodically transform its Ukrainian identity through Russification, transforming it into southwestern Russia. Ukraine is expected to become an agricultural hub and potentially a strategic forward base for further military operations into Poland the Baltic states, and likely Moldova.
Why does Putin desire Ukraine when there is considerable open land to the east and north? Well, it’s the geography. The land beyond to the north and east of Moscow consists of vast stretches of challenging subarctic taiga and arctic permafrost, much of which is now thawing, making it unsuitable for roads, urban development, agriculture, and industry. In contrast, Ukraine boasts rich, productive farmland with significant annual grain exports. Additionally, along its southern coast, including Crimea, Ukraine possesses the only warm water ports available in the region, other than possibly the Neva River to the north which are vital for commerce and the military.
Historically, western European colonization was driven by the prospect of trade opportunity including raw materials, cheap labor as well as power projection. Like all countries, Russia would like room for its prosperity to grow. It is desirable that agricultural and industrial capacity also rise. However, Russia has learned the hard way the value of having a buffer zone between Moscow and Western Europe. The relative ease with which both Napolean and Hitler crossed the Eastern European territory enroute to Moscow, Leningrad and other cities through greater Russia did not go unnoticed by Stalin. By absorbing the Eastern European territories after WWII, Stalin built a picket fence protecting the Soviet state.
As the Nazi’s Operation Barbarossa was failing and Stalin’s Red Army began pushing the Germans into a westward retreat, the Soviets took advantage of the opportunity to install Soviet political structure in captured Nazi territory like the Baltic states, Eastern Europe and the eastern half of Germany. While Stalin did not share Hitler’s enthusiasm for exterminating Jews, he did act to eliminate preexisting local political structures which included substantial Jewish presence. This meant executions and large-scale banishment of politically unreliable people to the Russian gulag system. Poland was hit particularly hard by both Hitler and Stalin because it was directly between Russia and Germany and had a large Jewish population.
The above map shows the population density of Russia. A substantial fraction of Russians live in the southern and western regions of the country. If you assume that people are living there because it is at least somewhat livable, then the map shows the extent of land poorly suited for habitation.
Map of Russia showing areas that are 90 % populated by ethnic Russians.
Russia has a great deal of acreage but the livable turf is much smaller.
Putin views the world partially from the old cold war perspective. It’s Russia against the aggressive, corrupt and immoral west, but without the fever dream of a Soviet-style socialist world. Putin’s state-controlled media endlessly repeats that the west wants what the Russians have and stokes the fires of fear. For the Soviets, “aggressive, corrupt and immoral” included resistance to Soviet influence.
In my many years of trying to be as informed as possible in many areas in a free and open society, not once have I heard anyone suggest “Gosh, I wish the USA could occupy Russia (or the USSR) as an American territory and take all of their stuff.” Imagine the scope of the folly in stupidity of such an attempt. It is mindbogglingly absurd to believe that one could or would want to do such a thing. Russia is for the Russians. Maybe one day they will hit upon a way to craft a free and open society.
The Soviets were ardent promoters of global socialism. Although not overtly socialist, Putin appears more focused on preserving Russian culture and dominance from across a substantial territorial buffer with the West. He asserts his aim to shield Russia from Western cultural influences and what he perceives as a “belligerent” military stance.
The “belligerent military stance” of the West amounts to NATO responding to Soviet adventurism and their habit of hybrid warfare. They would say the same thing from their perspective, but which side was the more authoritarian?
Historically, Russia has endured invasions by King Charles XII of Sweden, Napoleon, and later Hitler. The history of the Kievan Rus from 830 to 1241 is jammed with bloody feuds, wars and invasions. From the Principality of Moscow in 1281 to the end of the Tsardom in 1917, and even beyond into the era of the Soviet Union and into Putin’s time, near continuous conflict has plagued the Russian people. Fortunately, Russia’s northern geography and harsh winters have often played to its advantage, compelling invaders into prolonged conflicts and misery with eventual withdrawal. But not always.
Most nations would like to have global hegemony. Putin is fond of saying that Russia has suffered greatly from American and Western hegemony since WWII and hopes to put an end to it. He has reestablished a Soviet-like security state apparatus with strict media control when he assumed power after the 8 years of Yeltsin’s chaos following the collapse of the Soviet Union. He is trying to resume for present day Russia the former Soviet Union’s international status but largely without the manpower and resources of the former adjacent Soviet states.
Source: The Fuller Project. Unexploded cluster bomb in Ukrainian wheatfield.
Like his Soviet predecessors, Putin both envies and worries about overreach of western hegemony and is moving to unseat the West. For that matter, so is China. This is only natural. I believe they resent western influence generally. The English language as the global lingua franca and the US dollar as the standard international currency are seen as an annoying affront to their own cultures, sovereignty and political significance. Again, this is only natural. And so is the temptation to use power projection or coercive propaganda to achieve their own hegemony. Casualties would be considered the West’s fault for being in the way.
Both Russia and China have long been critical of the West for internal propaganda purposes but to be fair there has been some valid criticism as well. In truth, the US has done some bone-headed things that we should not be proud of and that hardly serve to highlight our presumed “special” nature. But in fairness, most all cultures can look back at regrettable conduct in their history. Neither Chairman Mao’s China or Stalin’s USSR have sparkling clean histories either. Often the benefit of hindsight doesn’t come into focus until far down the timeline.
The Soviet Union in the person of Joseph Stalin, had brutalized Ukraine previously in an attempt to halt its independence. The Holodomor, meaning death by starvation, of 1932-33 is estimated by scholars to have killed 3.5 to 5 million people. This period of time is marked by forced collectivization of agriculture and industry in the USSR and Ukraine. Collectivization meant taking control of farmland owned by the peasants (especially the Kulaks), many times banishing them to the gulags never to be seen again. Already by 1931, Moscow had taken 42 % of the Ukrainian grain harvest, forcing some locations even to turn over seed for the following harvest. By early 1932 some districts in Ukraine were already experiencing famine. The governing committees in Ukraine in 1932 believed that the 6 million tons of grain demanded by Moscow was unachievable, yet they ratified the plan anyway.
The current brutal murder and devastation of Ukrainian citizens and their infrastructure and agriculture will take a generation or more to repair even if Russia prevails. Russia has done great damage to the Ukrainian environment in addition to the many casualties. Much of the country is cratered, littered with destroyed vehicles and war debris, denuded of vegetation, and rendered deadly by the landmines.
The great equalizer among the leading nations is Mutual Assured Destruction, or MAD, by virtue of the threat of the use of nuclear weapons for mutual annihilation. Sometimes just called “the bomb”, it was indeed invented by an international cast of scientists and engineers using American uranium and Plutonium and first used in successive releases by the US on Japan near the end of WWII in the Pacific theater. This will darken a stretch of American history indefinitely. Some continue to argue that the bombing was not necessary because Japan was soon to surrender, but it happened, and nothing can change that. However, to our credit, the US has never used it since and has actively sought with other nations to suppress the proliferation of nuclear weapons and remove the hair triggers for their use. That said, the US remains a no-first-use country but will participate in the principle of Mutual Assured Destruction as needed.
A Nuclear Sidebar
Very soon after the discovery of nuclear fission in December, 1938, in Nazi Germany by German-born chemists Hahn and Strassmann, and Austrian-born physicists Meitner and Frisch, the theoretical potential of using the vast energy output of nuclear fission for a bomb was quickly realized. On May 4, 1939, Frédéric Joliot-Curie, H. Von Halban and L. Kowarski in Paris filed for three patents using a fission chain reaction. Two involved power generation and the third was for an atomic bomb, patent No. 445686. Fission was experimentally discovered in Dec. 1938, theoretically explained in January 1939, and a patent for the atomic bomb was filed on May 4, 1939.
The point of this atomic interlude is to highlight the short time interval between the discovery of nuclear fission, conceiving the idea of the atomic bomb and filing for a patent by scientists. On August 2, 1939, a letter written by Leo Szilard and signed by Albert Einstein was sent to President Franklin D. Roosevelt warning that Germany may be developing an atomic bomb. This led to the Manhattan Project and America’s entry into nuclear weaponry.
During and after the Manhattan Project, Stalin’s spies detected and infiltrated the American bomb project and presumably used important stolen information for their own nuclear program. This was an important shortcut benefitting the Soviets greatly. The first Soviet atomic bomb burst so soon after the war shocked the world.
Humans have a gift for the invention and use of weapons. I’m sure it has always been that way for humans. The inclination for war and conquest is also an ancient instinct. It is hard to see how aggression will ever change. In view of this distressing thought, how are we to proceed?
Looking forward
In the short term we in the west must continue to discourage Putin’s expansionist push. A win for Ukraine will set a precedent that might even unseat Putin. It is up to the many good people in Russia to be rid of him. However, Russian citizens will have to struggle against the vast authoritarian political machine in place just like the Poles, East Germans and the other Soviet states had to do in the late 1980’s. The intimidation and resources of the Putin authoritarian state are a huge obstacle.
My guess is that in general, doing the “right thing” in a culture of normalized authoritarianism, bribery and corruption is more difficult to accomplish than doing the “right thing” in a free and open culture where doing the right thing is occasionally practiced and always admired.
To a westerner like me, Russian withdrawal from Ukraine seems like the optimal solution to Russia’s present economic and military race to the bottom. Even in winning, Russia will inherit a devastated region that will require vast resources and a decade to repair, as well as a population of angry and vengeful citizens looking to kill a Russian or two. Then there are all of the land mines to contend with. There is amputation or death by landmines in the future for many unsuspecting people regardless of who wins.
A cessation of hostilities led by Putin is likely to end his career. Thus far, Putin’s invasion has led to over 500,000 Russian casualties, of which there have been over 80,000 Russian fatalities. In a way, this pales in comparison to Stalin’s murderous handiwork, but the comparison is really more like “terrible versus really, really terrible.”
Whether or not Putin is a reanimated Soviet leader or “just” another Tsar isn’t a question to dwell on. He is a creature of his time who happens to be a former Soviet KGB officer but has rejected Marxist/Leninism and rules by a roughly mafia-style kleptocracy behind closed doors in the Moscow Kremlin. For Russian citizens, the rule of thumb is if you stay out of political business, the government will stay out of your business.
The Environmental Protection Agency announced on August 6th, 2024 there would be an emergency suspension on all registrations of the preemergent herbicide chlorthal-dimethyl, or dimethyl tetrachloroterephthalate (DCPA or Dacthal). It has been 40 years since the US EPA has issued such an emergency suspension of registrations. This order has immediate effect.
US patent US2923634A was granted to Diamond Shamrock 1960-02-02 with a single claim-
1. THE METHOD OF CONTROLLING UNDESIRABLE PLANT GROWTH WHICH COMPRISES CONTACTING SAID PLANT GROWTH WITH AN ACTIVE AMOUNT OF DIMETHYL 2,3,5,6-TETRAHALOTEREPHTHALATE.
An early patent claiming the use of DCPA, but not the composition.
Graphic and physicochemical data. PubChem. DCPA structure tilted just a bit for clarity. Octanol/water partition coefficient: log KOW = 4.40 @ 25 °C, water solubility = 0.5 mg/l @ 25 °C, Vapor pressure: 2.5 x 10-6 mm Hg at 25 °C
The octanol/water partition coefficient, log KOW, sometimes called Log P, is a measure of how a substance will partition itself between 2 phases, a hydrophilic phase and lipophilic phase. This logarithm is used to give some insight into the type of living tissues a substance will tend to accumulate in on exposure or dosing. A log KOH of 4.40 represents a ratio (antilog) of 25,119 to 1 favoring the octanol. This indicates considerable lipophilicity.
The industrial manufacture of DCPA is neither complicated nor difficult. The terephthaloyl chloride (pronounced: terra THAL oh illchloride, soft TH as in “thing”) raw material is used in the manufacture of Kevlar and is readily made in several ways. Whether or not the DCPA manufacturer makes their own or outsources it is not available information. In either case, the terephthaloyl chloride is chlorinated to exhaustion (fully chlorinated) and then the methyl ester is prepared by contacting the chloride with methanol to form the diester (pronounced: DYE ester).
Why does DCPA have 4 chlorine atoms on it? Hard to say exactly what the thinking was, but from the process chemistry perspective forcing 4 chlorine atoms on the ring rather than just 1, 2, or 3 solves the problem of ending up with a dog’s lunch of mono-, di-, tri- and tetrachlorinated compounds in the product mix. Individually, each may have differing potency, selectivity, biochemical mechanisms, and human or environmental toxicological properties. Subsequent environmental and tox studies would be complicated by the potential of 4 analogs each possibly requiring individual testing at some point. Another thing to consider is that single component solids are much more easily purified by crystallization than a solution of solid components. A solution of mixed components can be quickly precipitated by cooling or concentrating, but pulling out one pure solid among many solid close analogs can be difficult and low yielding. Single component products are almost always better for ease of processing.
Graphics by John Jacob Jungleheimer Schmidt. The “oyl” fragment of the name indicates the presence of the acid chloride group.
DCPA is a selective non-systemic, or contact, herbicide used for pre-emergence control of annual grasses and some annual broad-leaved weeds. Coverage rates of 6-14 kg/hectare are common.
From PubChem: “/IT IS/ PRESENTLY APPROVED FOR USE ON TURF, ORNAMENTALS, STRAWBERRIES, AND AGRONOMIC CROPS INCLUDING COTTON, SOYBEANS, AND FIELD BEANS. /IT IS/ EFFECTIVE AGAINST SMOOTH & HAIRY CRABGRASS, WITCHGRASS, GREEN & YELLOW FOXTAILS, FALL PANICUM & OTHER ANNUAL GRASSES. /IT IS/ ALSO USEFUL AGAINST CERTAIN BROAD-LEAVED WEEDS SUCH AS CARPET WEED…PURSLANE & COMMON CHICKWEED. /IT IS/ TOLERATED BY MANY CROP PLANTS.”
DCPA is a relatively simple small molecule that is made from cheap and abundant early feedstocks like para-Xylene, Chlorine and Methanol. It has good potency and desirable selectivity in its ability to kill crabgrass in the presence of turf grass. The chemical process steps are well understood, each with a long history of successful use. It can be sold in solid form or in liquid form and may be applied by a large variety of methods. It can be applied for pre-emergence or folial use.
According to EPA “DCPA is a chlorinated benzoic acid herbicide which inhibits cell division of root tips in target plants. It controls many annual grasses and broadleaf weeds in a variety of agricultural crops and ornamental varieties (e.g., broccoli, onions, tomatoes, cabbage, cauliflower, dogwood, azalea). Annual agricultural use from 1998 through 2008 averaged approximately 500,000 pounds over 100,000 acres with broccoli and onions accounting for 79 percent of that use (Ratnayake, 2011). Information also suggests that on average 50 percent of broccoli is treated and 15 percent of onions (SLUA).“
As useful of an herbicide as it may be, it has a dark side that spooked the US EPA into issuing an unusual emergency suspension on August 6, 2024. In particular is the potential toxicity to the unborn and the risk to “post-application workers involved in tasks such as transplanting, weeding and harvesting.” Female farmworkers are at high risk since DCPA has been shown to be toxic to the fetus producing lifelong health problems. The reader is invited to read the link for details in the toxicology. The successive degradation of DCPA is shown below. In addition to hydrolysis, it is also subject to photodegradation in sunlight.
Graphics by John Jacob Jingleheimer Schmidt.
Why wasn’t this discovered earlier? I’m not an EPA pesticide guy, but discovering the specific toxicity of herbicides registered many years previously requires some kind of trigger to get an investigation started. Today, other than an overt incidence of toxic effects making the news, that trigger can be the Registration Review Overview conducted by EPA every 15 years for each registered pesticide.
Having interacted with a certain division of the USEPA for the last 3 years, I can say that there are many intelligent and knowledgeable scientists, engineers and other professionals who try to get things done in a very constricted space bounded by layers upon layers of federal laws converted into regulations. They are about as loved as the Internal Revenue Service and, like IRS, are forced to work wildly understaffed and with an IT system that is decades out of date. A doff of the hat to EPA.
Wow. The evolving kerfuffle around Robert F. Kennedy, Jr. (RFK Jr.) leaving a dead bear cub in NYC’s Central Park is another odd chapter in this guy’s bio. He had posted a video on X where he recounted a story to Rosanne Barr about the bear cub incident.
Harvesting roadkill for food is not something people often do in the big city, but up the holler it is occasionally indulged in. I lived for a time outside of Durango, Colorado, where an elk herd would winter-over north of town along the Animas River. My experience was that elk were a little different from skittish deer in that a bull elk would just stand in the road and stare at you as you closed in on it. Not only would the damage to your vehicle and the elk be serious, but the height of an adult elk assures that it would slide over the hood and through the windshield and into your face. An unpleasant scenario to be sure.
One morning while commuting into Durango I passed the carcass of a large bull elk lying alongside the road, dead as a door nail. On my return commute that evening the elk carcass had been replaced by a large pile of glistening pink entrails. It was a bonanza for some lucky sod. I learned later that this was fairly common and was told that the forest service (or some other lucky group) even had a special disposal facility for roadkill.
It is worth noting that RFK Jr. mentioned that he is a falconer. It stands to reason that a falconer might be inclined to collect roadkill to feed the falcon. Our natural instinct to avoid handling roadkill might be overridden by a falconer.
He did say that he was going to take the bear cub home, skin it and put the meat in his refrigerator. He didn’t mention eating it. Maybe he was going to use the meat to feed his falcon. From personal experience I can say that bear meat is less than choice eating. As a starving undergrad living off campus, I was gifted some bear sausage which I made into chili. It was awful- the sausage spices were meant to cover up the taste, but it just didn’t work. I fried the bear sausage first before adding to the chili and it stunk up the whole apartment.
The stashing of the bear cub carcass in Central Park by RFK Jr. and his drunken friends was meant to be a prank, he claims, relating to recent published accounts of bicycling fatalities there. He said the intention was to make it look like a bicyclist hit the bear. I don’t know, if I were with drunk buddies late at night, it might well seem funny to me too, especially since the carcass was in the trunk anyway.
Nonetheless, a story like this going public for a politician can only detract from their campaign and should have been left unrevealed and deep in the murky depths of time. The revulsion to an animal carcass can only translate into revulsion to the candidate.
Though not at all a fan of RFK Jr., I can sympathize with him just a tiny bit on this fiasco, anti-vax flake though he is.
The news service Reuters recently published an article on the ease with which the raw materials for the production of the opioid Fentanyl. From their $3600 expenditure on raw materials they estimate they could have produced $3 million worth of Fentanyl.
For an estimated 74,702 Americans in 2023, Fentanyl provided them with a narcotic experience prior to death. The lethal dose is reported to be 2 milligrams for an adult. It is 20 to 40 times more potent than heroin.
Outside of medical use Fentanyl should be described as a highly (neuro)toxic substance rather than just an opioid. Yes, it is an illegal narcotic, but it is also a potent deadly poison. Hidden with other illegal drugs in pill form, it is just a highly toxic contaminant.
On January 5, 2024, I posted a piece titled “A Bit of Fentanyl Chemistry” which is reproduced below. It turns out that the Janssen synthetic chemistry I wrote about then is quite close to what the investigators at Reuters had in mind for their story. In the world of chemical commerce, a process using easily available raw materials is highly favored.
My take-home message from the Reuters story is that unless China seriously clamps down on those who export the raw materials, all that is left to do is to suppress demand. The import of Fentanyl raw materials is aided by deceptive packaging and small quantities needed. Worse, Fentanyl raw materials have other uses in pharmaceutical chemistry and are too useful to completely shut down. The death and incarceration that Fentanyl can bring in the US does not appear to be sufficiently convincing to the at-risk American population. Nothing new here.
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A recent raid on a clandestine drug lab in the Hatzic Valley east of Vancouver, BC, netted 25 kg of “pure” fentanyl and 3 kg which had already been cut for street use. Precursor chemicals used to manufacture the fentanyl were also seized. Along with the drug, the raid also seized 2,000 liters of chemicals and 6,000 liters (about 30 drums) of hazardous chemical waste, according to an RCMP news release 2 November, 2023.
The police said that the seizure represented 2,500,000 street doses.
In August of 2023 the police in Hamilton, Ontario, announced the results of Project Odeon. This was a large-scale sweep of illicit drug production in the Hamilton and Toronto area. From January 1, to July 30, 2023 there were 606 incidents related to suspected opioid overdoses and 89 suspected drug related deaths in the Hamilton area. Twelve people were charged for a total of 48 criminal charges. The police disclosed the following items that they seized-
An operational fentanyl drug lab at 6800 Sixteen Road, Smithville.
A dismantled fentanyl drug lab at 4057 Bethesda Road, Stouffville.
Approximately 3.5 tons of chemical byproduct from fentanyl production.
800 gallons of chemicals commonly used in the production of fentanyl
Lab equipment commonly used in the production of fentanyl
64.1 kg of illicit drugs, including 25.6 kg of fentanyl, 18 kg methamphetamine, 6 kg of ketamine
A loaded, Glock firearm and ammunition and four extended magazines
Over $350,000 of seized proceeds, including cars, jewelry, furniture and cash
Fentanyl is a synthetic drug first prepared in 1959 in Belgium by Paul Janssen (1926-2003). Janssen was the founder of Janssen Pharmaceuticals, now a subsidiary of Johnson & Johnson. In addition to fentanyl, the Jenssen team developed haloperidol, the ultrapotent carfentanil, and other piperidine based congeners. Piperidine itself is a DEA List 1 substance in the US.
Carfentanil is just modified fentanyl. Graphics: Will O. de Wisp
The elephant in the room with fentanyl is its extraordinary potency as an opioid. In pharmacology, potency is a quantitative measure of the amount of dose needed to elicit a specific effect on an animal or human in terms of dose weight per kilogram of body mass. Potency is subject to variability across a population and rises to an asymptote which can be difficult to pin down. For these reasons potency is reported at 50 %. For highly potent drugs like fentanyl, the measure is expressed as milligrams or micrograms of dose per kilogram body weight (mg/kg or mcg/kg body weight). One milligram per kilogram is one part per million (ppm).
When matters of toxicity arise, it is important to remember the maxim that “the dose makes the poison”. This observation traces back to Paracelsus in the mid-sixteenth century.
“All things are poison, and nothing is without poison; the dosage alone makes it so a thing is not a poison.”
Fentanyl acts much like morphine in regard to its affinity for one particular opioid receptor. Morphine is commonly the “standard” with which other opioids are compared. For instance, fentanyl is said to be 50-100 times more potent than morphine. Only 2 mg of fentanyl is equivalent to 10 mg of morphine. Carfentanil is more potent still at 10,000 times the potency of morphine.
Morphine is an agonist which activates the μ-opioid receptor. Activation of this receptor with morphine produces analgesia, sedation, euphoria, decreased respiration and decreased bowel motility leading to the earthly delights of constipation. Fentanyl is thought to interact with this receptor as well.
Original fentanyl synthesis by Janssen. Graphics: Will O. de Wisp
So, how is fentanyl synthesized? See the synthetic scheme above. I’ll just comment on the Janssen synthesis and some issues. I have no idea of how it is made out in there by the Mexican cartels and in ramshackle American trailer parks. The synthesis above has some steps that may be undesirable for backwoods or jungle operations like hydrogenation. In the first step, aniline will be needed to make the phenyl imine. It’s pretty toxic and stinks to high heaven. Next, lithium aluminum hydride is needed to reduce the imine double bond to an amine. This innocent looking grey powder is very hazardous and should only be used by an experienced chemist. It is also available as a solution in tetrahydrofuran. The next step is the formation of the amide with propionic anhydride. While the reaction entails a simple reflux, you still have to isolate the product. Once you have recovered the amide, the benzyl protecting group on the piperidine nitrogen must be removed. It allowed amide formation exclusively on the upper aniline nitrogen and has served its purpose. Finally, the piperidine nitrogen must be festooned with a phenylethyl group and phenylethyl chloride was used to afford the fentanyl product.
In chemical synthesis generally, substances are prepared in a stepwise manner and with as few steps as possible to give high isolated yields. To begin, one must devise a synthesis beginning with commercially available raw materials as close to the target as possible. If the product has many fragments hanging off the core structure, it’s best to solve that problem early. Synthetic chemistry is almost always performed in a non-interfering solvent that will dissolve the reactants and allow the necessary reaction to occur. A low boiling point is preferable for ease of distillation. An important side benefit from a solvent is that it will absorb much of the heat of reaction which can be considerable. Left on its own, a reaction might take its solvent to the boiling point by self-heating, generating pressure and vapor. The benefit from evaporation or reflux boiling is that as a solvent transitions from liquid to vapor there is a strong cooling effect which helps to control the temperature. An overhead condenser will return cooled solvent to prevent solvent loss.
You can do any chemical synthesis in one step with the right starting materials. Unfortunately, this option is rarely available. The next best option is to take commercially available starting materials through a known synthetic scheme. People who run illicit drug labs are never interested in R&D. They want (and need) simple chemistry that can be done by non-chemists in buckets or coke bottles at remote locations. Chemical glassware can be purchased but sometimes the authorities will be notified of a suspicious order. This is especially true with 12 liter round bottom flasks.
The most difficult and risky trick to illicit drug synthesis is obtaining starting materials like piperidine compounds in the case of fentanyl and its congeners. In the case of heroin, acetic anhydride shipments have been investigated for a long time because it is used to convert morphine to heroin- an unusually simple one-step conversion. Solvent diethyl ether is similarly difficult to get outside of established companies or universities. Many other common drug starting materials are difficult to obtain legally in the US or EU by the criminal element. However, China is thought to be a major supplier of starting materials outside the US and EU. Countries with remote coastlines, loose borders, lackadaisical or corrupt law enforcement reduce the barriers for entry of drug precursors.
China in particular has a large number of chemical plants that make diverse precursors for legitimate drugs. Unfortunately, some of these precursors can also be used for illicit drugs or existing technology adapted for this use. Precursors can be sold to resellers who can do as they please with them. Agents may represent many manufacturers and can mask the manufacturer’s identity and take charge of the distribution abroad. Shady transactions become difficult for authorities to detect and trace. The identity of illicit precursor chemicals are easily altered in the paperwork to grease the skids through customs. Resellers can repackage chemicals to suitable scale, change the paperwork and jack up the price for export. It has been my experience that many if not most Chinese or Japanese chemical manufacturers conduct business through independent export agents. However, behind the curtains there often a byzantine web of connections between companies and agents, so you may never know who will manufacture your chemical. As an aside, this complicates getting technical information from the manufacturer since the agent will not disclose a contact at that manufacturer.
Highly potent drugs like fentanyl must be taken in very small dosages which means that kilo-scale batch quantities of drug result in many individual sales per kilo. Small quantities of highly potent drugs are more easily smuggled than bulky drugs like weed with its strong odor.
There is a down-side to the illicit manufacture of drugs like fentanyl. It is quite toxic at very low dosages and must be handled with the greatest of care lest the “cook” and other handlers get inadvertently and mortally poisoned. Good housekeeping helps, but I have yet to see a photo of a tidy drug lab.
Fentanyl can be sold as a single drug but perhaps is cut with a solid diluent that some random yayhoo decided was Ok to use. Other drugs of abuse like heroin may be surreptitiously spiked with fentanyl to kick up the potency. In either case, a given dosage may or may not be safe even for a single use. There is no way for a user to know. Also, the concentration or homogeneity of mixed solids may be subject to wide variation. For more than a few people, their first fentanyl dose will be their last.
Numerous YouTube videos depict the widespread destruction of Russian tanks in the invasion of Ukraine, giving the impression that these tanks are more lethal to Russian soldiers than their opponents. Despite being equipped with Explosive Reactive Armor (ERA), their ability to withstand artillery, mines, and drone attacks seems minimal. Moreover, when the armor is breached, the cannon gun propellant tends to ignite violently, causing the warheads to explode and instantly killing the crew. Occasionally, the force of ammunition blasts is so strong that it hurls the turret with gun barrel into the air, a stark illustration of the power of such explosions. Consequently, videos frequently capture Russian tank crews abandoning their crippled vehicles and fleeing for safety. Instead of offering protection, tanks have become conspicuous and cumbersome targets, prone to devastating attacks.
One might question the practical value of reactive armor. The landscapes of eastern Ukraine are strewn with thousands of destroyed Russian tanks, their ERA blocks still intact. Perhaps its practical value lies in bolstering the confidence of tank crews to engage in battle, trusting in the ERA’s protective capabilities. However, it is now challenging to believe that ERA instills a sense of safety in tank crew members. The effectiveness of reactive armor seems negated by potent penetrator warhead countermeasures capable of breaching the ERA. The pertinent question remains: does the ERA diminish the impact of an incoming shell sufficiently to be considered effective?
The conflict between Putin and Ukraine will eventually conclude, and the victors will promptly seek to repurpose the battlefields for peacetime activities. However, they must first contend with numerous challenges, including the presence of unexploded ordnance. Thousands of mines may remain hidden, posing a threat for decades unless they are securely disposed of or neutralized.
The landscape of the battle zones is marred by bomb craters, charred vehicles—many with unexploded ammunition—minefields, unexploded ordnance scattered about, live explosive reactive armor on destroyed armored vehicles, and soil polluted with shrapnel and residues from countless detonated artillery shells.
Numerous cities and villages, particularly those near the Russian border, have been completely obliterated by Putin’s military, resulting in tens of thousands of civilian casualties and leaving most without homes. The remnants of homes, businesses, and infrastructure stand as a testament to the survivors. For them, social and economic frameworks are now just distant memories. Civilization has been set back by at least a generation due to Putin’s distorted ambitions for an imperial legacy. The man is not insane or unintelligent; he is quite astute and fully aware of his actions—he is simply a terrible person. Currently, the US is facing its own challenge with a figure of ill repute seeking control of the government, backed by a significant number of misguided followers.
In the conflict in Ukraine, it’s conceivable that one precisely aimed bullet could have altered the course of events, a notion that has been a sad reality in many wars. This was a concern even during Stalin’s time. Since 2000, Putin and his associates have been systematically constructing the framework for an authoritarian state and military power, positioning him at the apex of power. His ambition is to supplant the hegemony of the US and NATO with the hegemony of Russia.
The conflict has been a catastrophic event for the region’s flora and fauna, significantly hindering the biosphere in numerous areas. Ukraine, until recently, was a significant grain producer and exporter, essential for the sustenance of millions. In the early stages of the conflict, Russia targeted and destroyed much of Ukraine’s grain distribution infrastructure, aiming to debilitate the economy and hasten a surrender. The bombings of civilian residences, hospitals, and other infrastructures will tarnish Putin’s reputation, marking him as a tyrant and a fundamentally flawed individual. Additionally, the reported abduction of thousands of Ukrainian children by Russia for forced assimilation and adoption raises serious legal and humanitarian questions. These actions are meticulously recorded for potential future war crimes proceedings and historical record.
Lamentations on Chemistry 