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Enroute to other things I ran across an old Gulf R&D patent, US 3294685, titled “Organic compositions containing a metallo cyclopentadienyl”. Sifting through the description my eye caught the interesting content below:

July 1941. A test spray was prepared by dissolving 2.5 grams (3.2 percent) of iron dicyclopentadienyl in ml. of a typical household insecticide base oil. The tests made with this solution employed a dosage of IO-second discharge. An equilibrium :period of 15 seconds followed by an exposure period of 70 seconds, during which the mist was permitted to settle on adult house flies confined in a screen-covered dish, was employed in the tests. The results of the tests showed that of the flies which had been contacted with the base oil containing 3.2 percent by weight of iron dicyclopentadienyl, 53.6 percent were dead after 24 hours. Of theflies which were contacted with the base oil alone, only 13.0 percent were dead after 24 hours. Check flies which were confined for 24 hours without having been contacted with either the base oil or the base oil containing iron dicyclopentadienyl had a death rate of only 0.4 percent. The better than fifty percent mortality of the flies treated with the base oil containing iron dicyclopentadienyl is indicative of the insecticidal properties of naphthas containing a small amount of iron dicyclopentadienyl. Naturally, the amount of metallo cyclopentadienyl used in insecticidal compositions-will vary with the particular compound employed and also depends upon the particular insects for which the spray is intended. The amount of iron dicyclopentadienyl employed in insecticidal compositions intended for use on flies is between about 1.0 and 10.0 percent by weight.

Ya know, a greater than 50 % kill rate seems to be getting a bit sporty for the flies. The ol’ boys at Gulf were studying the suitability of a variety of ferrocene analogs for fuel additive application. What lead them to go from octane enhancement and smoke control to killing flies is not revealed in the patent.

Notice the nomenclature in the patent language. The word ferrocene is not mentioned. Looking at the timeline we see that the Gulf ‘685 patent was filed April 21, 1952, not long after the publication of this curious iron cyclopentadienyl compound by two groups, Kealy and Pauson on 12/15/51, and Miller, Tebboth, and Tremaine on 1/1/52. Though Pauson and Keely published first, an examination of the papers show that Miller, Tebboth, and Tremaine were first to submit- July 11, 1951 vs August 4, 1951 for Pauson and Kealy.

The day before Gulf filed the patent application, April 20, 1952, a groundbreaking paper by Wilkinson, Rosenblum, Whiting, and Woodward was published on the proposed structure of iron bis-cyclopentadienyl. It is reported that the name ferrocene was invented by Mark Whiting, a student of R.B. Woodward and coauthor of the 1952 paper in JACS. The name derives from the ferrous ion and the aromatic (“benzene”) nature of the cyclopentadienyl ligands.

The curious structure was proposed largely on the strength of a single C-H IR band at 3.25 μ. Since all of the C-H bonds appeared to be equivalent, the only structure compatible with the formula, charges and symmetry was the famous η5 (eta five) sandwich structure. Later the word metallocene finds use for this class of substances.

There is disagreement as to some of the details outlined above. An excellent article by Pierre Lazlo and Roald Hoffmann navigates some of the narrower channels in the history of ferrocene. It is well worth the read. Lazlo and Hoffmann suggest that Woodward is thought to have conceived the sandwich structure.

Ferrocene and derivatives would soon prove useful in many areas. A more obscure application is found in the field of rocket propellant additives and function as burn rate stabilizers. In fact, certain ferrocene derivatives appear on the US Munitions List, 22 CFR 121.1, Category V, (f)(4) Ferrocene Derivatives. A good overview of ferrocene and other metallocenes can be found in Wikipedia.

 


Wilkinson, Rosenblum, Whiting, and Woodward J. Am. Chem. Soc., 1952, 74 (8), pp 2125–2126. DOI: 10.1021/ja01128a527

Kealy and Pauson, Nature, 168, 1039 (1951). Received Aug. 7, 1951.  DOI: 10.1038/1681039b0

Miller, Tebboth, and Tremaine J. Chem. Soc., 1952,0, 632-635. Received July 11, 1951. DOI: 10.1039/JR9520000632

Laszlo P., Hoffmann R. ACIEE, 2000 Jan; 39(1):123-124.  DOI: 10.1002/(SICI)1521-3773(20000103)39:1<123::AID-ANIE123>3.0.CO;2-Z

 

Some questions regarding the internet and the problem of hacking.

I wonder to what extent hacking problems via the internet could be suppressed if we had a bit less connectivity or a bit less compatibility? Who decreed that critical systems like the power grid or banking or corporate enterprise systems be connected and compatible in a way that can be entered from outside? Why not trade in some convenience for greater security? Another approach would be to have intranet systems that are incompatible with internet protocols. Who is calling the shots here? Cisco? Microsoft? Fresh MBA’s wanting to implement the latest thinking from B-School?

A separate, air-gapped and incompatible system for intranet use in key infrastructure might be quite effective in blocking access to control systems from the outside. An electronically isolated conventional internet system would allow the public or vendor access to a store front site.

I’m sure there is ways a clever intruder who can cause some kind of trouble in this scenario, such as the intrusion of Stuxnet into the Iranian nuclear processing facility. So you epoxy the USB ports shut or remove the CD/DVD drives on as many computers as possible. Supervised data transfer could occur via numbered CD disc drives issued to employees temporarily for security. Again, cash in some flexibility for security.

But the basic question remains: Why should there be internet access to system wide locations. Who says it should be this way? Some IT/MBA enthusiast drunk on the idea of IoT?  C’mon. Why?

The local school board has recently voted to spend $482,000 to purchase iPads for a high school. “If we don’t do this now, and are already behind, we will get swamped. Instead of buying for a grade level or a school, it’s going to have to be for every kid in the district,” stated the board president. Chiming in was the superintendent who said “It’s not the wave of the future, it’s here now,” Mr. XYZ said. “It’s about the digital world we’re in more than it is about the device. We just have a device now that allows us to do that. The struggle now is getting everyone up to speed.”

There is utterly nothing novel or surprising about these sentiments among educators. The eternally open door to the brave new world beckons educators to outfit their classrooms with the latest and greatest. This is a healthy and vital impulse that I hope we all value.

From where I sit as a 59 year old industrial chemist, the image of new iPads holding a key to mending our educational woes seems like only the latest false prophet to pass our way.  Am I just grumpy or quietly jealous of the lucky young pups getting their iPads? Well, I am prone to grumpiness. Jealous of the students? No. I have declined the issuance of an iPad at work.

I think part of what we see is FOMO: Fear-Of-Missing-Out. To be sure, iPads or other brands are popular for a reason. They’re a wonderful tool for finding information about nearly anything and they are just plain fun to monkey with. So, as a resource to students, the iPad will obviously provide an ever widening portal to the world’s treasure of information. For this it has merit.

Two things can happen to those who frequent cyberspace. First, we find information through the use of search terms that lead us to a great many sources to choose from. But which are the most credible sources? Are they out dated?  Eventually, if civilization holds up long enough, we’ll relearn the importance of rigor in publishing. Secondly, and critically, when we find some information will we understand it? Searching and finding is not equivalent to substantive understanding.

A psych prof once related to me that true learning requires struggle. In my experience I have found this to be a fairly accurate truism. In my college teaching years I always conveyed to students that part of the secret to success in chemistry was to read the text several times and strive to understand the reasoning in the example problems.  Just as importantly, always do the assigned problems. Freshman chemistry is heavily weighted in quantitative concepts and math problems. In fact, freshman chemistry can often morph into a math class for many students.

Being an organikker I taught sophomore organic chemistry. Chemistry is highly vertical meaning that successive course work depends on content from previous classes. Organic chemistry is a bit different in that much of it is qualitative and heavily weighted with new vocabulary and the symbolic language of reaction mechanisms. I used to say that sophomore organic was the year of 10,000 structures. An important part of learning organic is the rote mechanical-tactile brain activity of drawing structures by hand. We chemists are just crazy about structures. Drawing pictures helps to seal the connection between vocabulary and structure. Being asked to draw structures correctly and adding functional groups forces one to associate symbols with composition and vocabulary, but also to acknowledge the 3-D aspects of molecules. Like freshman chemistry, organic requires a good bit of struggle.

In the past I was involved in public outreach with the science of astronomy. Having racked up many seasons of observing and studying the topic I was conversant enough to give star talks and usher visitors for a chance to peer through the 18 inch Cassegrain in the dome. I did this for some years but finally tired of it. What wore me out was that the public rarely had more than superficial interest in the topic. They were just happy to see the moon. It was infotainment and I had been an infotainer. What I finally realized was that to truly appreciate the wonder of astronomy and the mechanisms that grind the universe forward, a visitor would have to sit down and grapple with a lot of physics and new phenomena. A person has to be willing to commit to some struggle to gain the wonderful insights. My hard won knowledge offered to visitors just washed over them for the most part. It was a show and I was a performer.

So let me close the loop by connecting struggle with educational technology. It is my fervent hope that curriculum does not confuse learning to operate a device as evidence of subject knowledge. Most devices are designed to be easy to learn. What is crucial in K-12 education is that a groundwork of basic facts and knowledge of systems and processes are absorbed by students. A basic knowledge of geography facts, government facts, history facts, math facts, grammar and vocabulary facts, sciency facts, etc. are still necessary to have to build upon in the future. Any notion that facts can be left by the wayside in favor knowing where to look for them is a tragic mistake. Eventually people have to draw upon facts to properly search Google. After all, facts have names and to dig deeper into a topic, the user must supply the right search terms. The wrong synonym in a given search may not take the searcher to what they are looking for. Facts in your brain are still very necessary.

 

The short video above is of LLNL atmospheric test shot Turk in Operation Teapot in 1955 at the Nevada Test Site. The test was of the primary for the XW-27D thermonuclear weapon, giving a 43 kt yield.

What struck me about the footage was that it captured detail of the expanding fireball as it contacted the ground. Turk was a tower shot with the explosive sitting at 150 m above the ground. As the roughly spherical fireball expanded, jets of roiling material protrude radially from the growing incandescent ball. In particular a conical extension of incandescent material protrudes from and is overtaken by the expanding fireball.

A commenter below offered what seems to me a quite plausible explanation of the conical “jet” observed in the footage. It is a cable from the tower caught in the act of cooking off into plasma from the much faster radiant energy.

Addendum 6/28/17. Thanks to a link supplied by commenter K, we find there is a name for this phenomenon- it is called the “rope trick”. See this link for more information.

The recent news footage out of Syria showing victims of a chemical attack is haunting. When I first saw it I couldn’t quite comprehend what I was looking at. But after a minute of increasing discomfort I began to grasp the horror of the situation. Victims lying on the ground in puddles of water or in the midst of being flushed with a stream of water, gasping for air and limbs quivering in wide-eyed disbelief and fear of what they were experiencing. Others were unconscious or dead. Rescuers were moving around the victims not knowing what to do beyond rinsing off the bodies. Those handling the water, I’m sure, were grateful to be giving some kind of aid no matter how small.

It is interesting to see how people, myself included, react to this kind of news. I mean, this shouldn’t be happening. After all, the world has international conventions and treaties banning the use of chemical and biological agents in warfare. Humanity has gone to some length to bar the use of war shots designed to release toxic gas or aerosols over anyone anywhere.

When we shudder and express sincere horror at the barbarity of a chemical attack on civilians, along what track is our thinking guided? What kind of decision process might lead us to believe that a sarin attack is a higher level of depravity than a bomb blast? Could it be true that people who release chemical agents are actually guilty of a higher crime than those who send bombs in the direction of a civilian neighborhood or even just 50 caliber bullets?

Explosives are chemicals that unleash kinetic and thermal violence for a few seconds per explosion. Nerve agents move like the wind, breathing lethal aerosols or gas as they flow and leaving who knows how much contaminated … everything … and for how long. Bombs can be aimed, a gas cloud not so much. Bomb violence is much more common than death by acetylcholinesterase inhibition, yet our attention is always drawn to chemical violence.

We have an industry called show business that exploits bomb violence in its entertainment products. And we the viewing audience have become desensitized to the horrific effects of explosions by sheer repetition of highly staged portrayals. Perhaps it is the very novelty of a chemical attack that captures our attention. If you survive a bomb blast, there is a chance that you can be sewn back together again. If you receive an exposure to sarin, well, what do you do to stop the inhibition of an enzyme? Find a dose of atropine if possible from someone who knows it’s in stock somewhere.

The acceptance of explosives but not chemical agents as legitimate weapons of war is at best a false dichotomy. But, we are a world of men and women and weaponized conflict. If a ban on chemical and biological weapons can be negotiated faster than a ban on the use of explosives, then we take what we can get. But let us not get desensitized to high explosives and the horrific tragedies they produce.

Oh, one pet peeve. They’re not ‘explosive devices”, they are bombs. The former may infer skillful and clinical dispassion. The latter suggests dumb, blunt force. The latter seems more to the point.

In the past I have written posts on the adventure of having two stage 4 cancers and the journey down the rabbit hole one takes as treatment goes forward. Three years ago I had surgery, radiation and cis-platin for throat cancer. Three years later my throat or oropharyngeal cancer is undetectable. Of course, this is good news.  What remains of the experience are the lasting effects of intense radiation exposure in and around the target volume. I developed the normal array of after effects: stunted salivary glands resulting in chronic dry-mouth; periodontal disease and the loss of a few teeth; a substantial loss and distortion of the sense of taste; inadequate thyroid function requiring medication; difficulty in swallowing dry foods; radiation scarring on the neck; and lymphedema where 33 lymph nodes were removed from my neck. I’ve adapted and manage quite nicely to plod down the timeline much as before.

My situation with the stage 4 prostate cancer (Gleason 8) is stable. One of the treatments for prostate cancer is chemical castration. Since testosterone has the effect of accelerating the growth and spread of prostate cancer cells, the commercial drug Lupron is used to down regulate the production of testosterone. Loss of body hair and muscle mass as well as the onset of hot flashes were some of the highlights of my experience. A substantial nulling out of the sex drive happens as well.  Effectively I spent about two years as a eunuch.

It’s been nearly a year since the Lupron injections have stopped. I’m getting a more strength and some body hair is returning. I’ll leave it at that. The radiation treatment was intense in the target zone, but largely without significant discomfort overall. The tricky part of external radiation treatment of the prostate is it’s proximity to the bladder and the bowel. Fortunately, modern IMRT equipment is capable of modulating the x-ray beam intensity as well as shaping the beam with a multileaf tungsten collimator as it rotates around the patient.

After 11 months since the last Lupron shot, my PSA has increased only slightly from being non-detectable.  The return of testosterone after having it shut down for 2 years is a weird experience for a fella. But weirdness is normal in the world of cancer treatment.

Now we’ll pivot to a different topic.

A delicate parting thought for friends and family of those with cancer. Invariably a well intentioned friend or family member will say that their thoughts and prayers are with you or that a prayer group is holding you in the light. Another expression of sympathy might be that there is a reason for everything and that God has a plan for all of us, and as the story goes, our lives have purpose after all. Such sincere well wishes are expressed with the best of intentions, but for myself and other non-theistic people it rings hollow and offers little consolation. A prolonged and agonizing illness is part of some plan? Seriously? If a person set forth such a plan we would rightly consider this foul individual a psychopath worthy of punishment.

People express these sentiments when presented with an existential conflict- it is when the need to connect their belief system with reality the observable world is confronted with the paradox of the divine sanctioning of pain, suffering and untimely death. The need is met by the supposition that there must be divine purpose rather than the unthinkable alternative of the illness happening in the stark emptiness of a godless universe. If such a universe existed, what possible purpose could there be in existence? Well, yada yada. I’ll take this topic up in a later post.

Here is an alternative for your non-believing friends and family. Consider renewing and expressing gratitude for their love and friendship. Confess what the person means to you and commiserate with their condition. Let your emotions flow. Hold their hand. A bit of listening goes a long way too. Mirth is always welcome- the regaling of past exploits, funny stories or people, jokes or the sharing of what experiences you have in common. A light heart and cheerful smile is always welcome in sickness and in health.

 

The US Chemical Safety Board has approved and released the final report on the Macondo /Deepwater Horizon  blowout and explosion of 4/20/10 in the Gulf of Mexico. The report is in two volumes and does include an animation of the sequence of events. I have found the CSB animations to be particularly helpful in understanding the key features revealed by their investigations.

The CSB recently released their final report on the ammonium nitrate fire and explosion in West, Texas on 4/17/13. A few months after the release of the final report the ATF announced a reward of up to $50,000 for information leading to the arrest of person or persons responsible for the industrial fire and explosion that killed 15 people.

If the forensic aspects of industrial accidents is of interest to you, I’d recommend having a look at the CSB website. Knowledge of various initiation and propagation modes in past industrial accidents is useful for those of us trying to prevent initiating events on our own sites.

After a weekend in the Alma, CO, mining district, I have come around a bit on the merits of gold mining. Oh sure, I have always known that it was a dirty business, what with the mercury, the cyanide, the acidic tailings piles, and the blighted landscapes. But for God sakes man, it’s GOLD!

Last weekend was different. It wasn’t a dispassionate examination of mining history. I could see miles of blighted landscape heaped with spent alluvium along the road from Fairplay to Alma. To the north, over Hoosier Pass, are the McMansions of Breckenridge where new and old wealth mingle.  To the south of Fairplay is a sizeable expanse of gravel and cobble heaps from past placer mining.

Placer mining north of Fairplay 6-14-14

The photo shows just a short stretch of the creek bed undergoing placer mining on the north end of Fairplay. Granted, the mining company is using gravity separation by way of the sluice to recover the gold. The stones are all rounded and well weathered, so one might expect the tailings to release little in the way of toxic leachate. But what a colossal mess they have made of the landscape. Perhaps they have put up a bond assuring that restoration of the landscape will happen when the mining ceases. I don’t know. That does not seem to be the way of past mining in the district.

My point is this. Isn’t there some madness in gold mining? At best a handful of people get wealthy from putting more gold on the market. I would argue that gold does not have the utility of iron, aluminum, or copper for instance. It does not go into items that advance civilization and economics like tractors, bridges, ships or wires. Gold does not go on to enable the growth of industry in the manner a base metal. Some of it adorns our fingers but most falls into the hands of anonymous individuals and governments who hoard vast caches of the metal. Granted, a bit of the annual production goes into electronics and a few other applications.

The madness in gold mining is that people are willing to go to any length or bankrupt themselves to obtain a metal that in the end benefits approximately no one. Most of the metal will quietly sit in a vault somewhere producing nothing. It won’t support a building or a roadway over a river. It won’t produce goods or services, nor will it bring a silent heart back to life. It can only support abstractions like the notion of value. We’re willing to put up with scarred landscapes, mercury pollution and acidic runoff produced by other people for an abstraction. That is pretty funny.

 

I just have to say that in regard to the deteriorating situation with the Soviet Union Russian Federation, it does not appear that either the EU or the US have their best thinkers working on it. I think US leaders have misunderstood Putin from the beginning and I see very little to convince me that Obama’s people, the Congress, or any other high level functionaries known to me have a clue how to get their arms around Russian behavior or a workable diplomacy.

Certainly recent (post-Ford) US incursions into foreign lands with troops or drones have taken us off the moral high ground in this regard. How can the US lecture Russia on the invasion of Crimea when we invaded Iraq based on lies, subterfuge, and outright errors?

Bush 43 and Clinton had historical opportunities to gain better alliance with Russia. But we supported Yeltsin in the Clinton years and ignored Putin’s offers of assistance after 9/11. The Russian people were mystified when the US supported Yeltsin, widely regarded as a drunken buffoon. Gorbachev’s memoirs paint a lackluster and untrustworthy picture of Yeltsin.  And the US has done nothing but confirm Putin’s paranoia about US intentions by adding membership to NATO, ABM’s in Poland, petroleum wars in the middle east, and the general appearance of weakness by in-house political fratricide.

We have no use for milquetoast administrations like Obama’s, nor do we need rabid swingin’ dicks like John McCain or his hawkish brethren. We do need Russian and Slavic scholars who speak the language and understand the history of Russia at least back to Peter the Great. They can be immigrants from former Soviet territories of the ilk of Zbigniew Brzezinski, Madeleine Albright, or even a world savvy guy like Henry Kissinger. Who are the current brain trust for eastern European politics and is the CIA giving them good intelligence? Did the CIA predict the takeover of Crimea?

Being a devotee of the HBO series True Detective I became intrigued with the purported allusions to the 1895 book of short stories The King in Yellow by Richard W. Chambers. I received my copy from Amazon yesterday and read the first three stories.

I have never ventured into the horror genre so this is refreshing. Chambers was reportedly influenced by Ambrose Bierce. His prose is considerably less dense than Bierce’s- closer to a 20th century cadence and vocabulary. H.P. Lovecraft took notice of Chambers as well. Lovecraft and Bierce are next on my reading list.

As with the story line of True Detective, The King in Yellow (or Yellow King) is not really centered on the fictional play of the same name. Rather, it is a kind of story telling device that motivates and launches characters along the arc of another story. It’s an interesting device.

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