Lanthanide Contractions and a Dog’s Lunch

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The rare earths are a curious group of elements from the commercial point of view.  There are a variety of lanthanide products available from a handfull of vendors, most of whom cater to a small group of users. Some of the catalog houses have respectable collections of them.  My friends at GFS offer lanthanides- specializing somewhat in cerium products.  Aldrich, Gelest, and Strem, of course, offer a variety of rare earths (RE). Hard to say if they are big sellers-I’m guessing they are on the slow side of the 80/20 rule.  I’m aware of a single American company that actually refines Scandium Oxide and manufactures Scandium Triflate as well. They are one of the few, if not the only, companys in North America that refines any RE’s. Most everyone else imports from Estonia, Russia, or China.

From my perusal of the literature it seems that the field partitions roughly into reagents for chemical transformations and oxides for material science.  The material science side is way beyond my reach, so I’ll pass on that segment.

The least expensive and most basic RE products are the oxides. If you spend some time shopping around for various RE’s, what you’ll find is a sliding scale of purity specs, 99%, 99.9%, 99.99%, 99.999%, etc.  If you look even closer to the specs, what you’ll find is some sleight of hand in regard to what the number of nines actually represents.  Most vendors will offer a number of 9’s that are TREO, Total Rare Earth Oxides. So if you are keen on Scandium Oxide, 99.99 % (or 4N), chances are that the 4 nines really represents the total of all of the RE oxides present.  In reality, 99.99 % TREO Sc2O3 will be 99.9 % in Scandium and the balance of the 4 nines is a dogs lunch of Ln Oxides. 

As we all know, when you analyze for more and more 9’s, you eventually find most of the periodic table present in your material.  But if you really want 99.99% in Scandium, it can be relatively hard to sort from the TREO products.  You are forced to swim through spec sheets to find material that meets your need. BSC offers 4N in Scandium, and some others do as well.

One of the interesting applications of RE triflates is as a water tolerant acid catalyst.  Essentially all of the RE triflates have been reported, with the possible exception of Promethium. The lanthanides show a general decrease of ionic radius as one increases atomic number. This is the lanthanide contraction. It has been shown that the catalytic activity in certain acid catalyzed reactions (i.e., with a Ln(III) triflate) correlates with the charge-to-radius ratio in this group.  Not surprising, I suppose. 

So, for an ambitious person with designs of bringing rare earth reagents to the marrket, this is a classic “technology push” situation.  In order to convince people to buy RE triflates as acid catalysts, you first have to offer a value proposition.  They can use conc H2SO4 or they can use Yb(OTf)3 as an acid catalyst. Hmmm.  So which is cheaper in my application?  Given the sparse literature on Ytterbium Triflate chemistry, for instance, it could be hard to convince a customer to adopt your RE product beyond R&D use.

So, whaddaya hafta do to sell a boat load of this stuff? You probably have to come up with a killer application for the RE Triflate to convince people to buy it and try it. If you as the purveyor lack this application, they you have to rely on the customer to do it for you.  In the mean time, you could get very hungry.

30 Years of Star Wars

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It has been 30 years since the release of the movie Star Wars. Back then I had just started a job at the local movie house as a projectionist. We had two Phillips-Norelco 35 mm projectors with Xenon arc lamphouses and 6000 ft reels. We’d splice 3 x 2000′ shipping reels onto one reel so that there would be fewer changeovers. 

The theater owner put down a $10,000 non-refundable deposit on the print and paid 90 % of the ticket sales to the distribution company for the first 6 weeks. So for the first month and a half, we made our money on popcorn, cokes, and Junior Mints.

In 1977 Star Wars was THE blockbuster of all time. We had sell-out crowds every show for the first 2 weeks. The concession girls could barely keep up with the popcorn demand. Other theaters were popping corn for us in an attempt to keep up. We blew through 5 gallon syrup cylinders like spent cannon shells on a battleship in Guadalcanal.

I ended up running Star Wars 186 times. But it was far from routine.  The projector chewed up a bit of the end of reel three, the famous dumpster scene. Unfortunately, I was operating the night the print failed. The projector shredded about 20 feet of film (18 inches/sec) in several places and the resulting film break  caused the automation to switch on the houselights, close the curtain, and start a Neil Diamond 8-track tape playing for the audience. After 3 seconds of bewilderment, the crowd turned ugly and started shouting and storming to the lobby to complain. The film stopped at a very exciting point and the customers were none too happy.  I didn’t venture downstairs.

I was a casualty of Star Wars and actually had to be taken to the hospital during the run.  In trying to investigate the source of some troublesome image chatter, I got my finger caught on a sprocket and ran it between the teeth and the guard post.  Ended up with a meaty gash that required stitches.  Of course, I never told George Lucas…

The print grew progressively worse over time. The dumpster scene would chatter through the film gate in defiance of our best adjustments.  But despite this, few complained when they walked out of the theater. It remains a great movie.  Eventually, as a college student I moved up to a 4-plex theater with platters and automated Simplex 35’s.  This night job paid for much of my BA in chemistry. I read much of Solomons Organic Chemistry in the projection booth.

Solar System Simulator

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NASA has a great website with a solar system simulator in it.  For instance, it will simulate the positions of the various satellites of the planets.  It also gives the user a choice of sites from which to take in the view.  So, if you are going to look at Jupiter some evening through your backyard telescope, you should be able to identify the 4 brighter moons.

The Murder Room

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I have attached a cast picture of our recent production of The Murder Room.

murder-room-cast.jpg

It turns out that there is a small number of people walking around who do several plays per year.  They have no real designs on Hollywood or Broadway.  They do dinner theatre or community theatre just for the pure joy of it.  Despite the fact that the work is gratis, local, and not run by Spielberg or some other big name, it is nontheless a sizeable ordeal to prepare for. 

I am grateful that not a single bit of rotten vegetation was thrown my way and that at least some of my lines drew a smattering of laughter.  I did it with a British accent somewhere between Terry Thomas and Rex Harrison. 

The sensation of this kind of performance was what I would imagine ballroom dancing might be like. A fluid and coordinated dance of repartee, movement, and subtext. To have performed with experienced actors was great experience and I am eager to do it again.

Halogenate with extreme prejudice

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Reacting one element with another to make a compound. How much more “elemental” can it get? No solvent and no waste, just element on element at Venusian temperatures. But, an organikker doing inorganic synthesis?  Is this a Coen brothers movie? What strange overlap of events lead to this redox redux?

Paracelsus would have been pleased at this transformation, though his interests with this compound might have diverged from mine. Whereas I as a modern chemyst would add a nucleophile to my blessed conjugation of elements, Philippus Theophrastus Aureolus Bombastus von Hohenheim (Paracelsus) would probably have more mundane applications like the treatment of consumption or perhaps an indelicate medicament for that tell-tale abscess.

After a career of conducting elaborate procedures for the preparation of strange organic compounds, it is refreshing to spend a month performing a non-incandescent combustion of elements.  There is joy in doing a thing well, taking the elements to their endpoint as fast as the equipment will allow. Squeezing maximum performance from the system and myself. It is a kind of poetry in motion. 

Frequently wrong, but never in doubt

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More and more I find myself afflicted with fellow travellers along the timeline who are never in doubt of their judgement, but they are frequently wrong nonetheless.  There has to be some archetype from literature or Greek mythology that symbolizes this. Maybe there is some character from a Greek tragedy who, as a leader, was destined for a fall as a result of such a trait. Perhaps someone out there has a nominee for this position.

One sees examples of this in business organizations not infrequently. Some openly discuss their views, but often with the presumption of making a disclosure of “what we’re going to do”.  Others sit quietly, rarely contributing to open discussions where ideas are put on the table for dissection.  These fellows might listen to others debate, but they prefer to sit quietly and observe while others reveal the content of their thinking. Rather than adopt or synthesize new concepts openly, they will tend to note commentary that aligns with their pre-existing view. This is where that most loathsome of characters, the yes-man, can gain a strong foothold in an organization. 

Howard be thy name

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A few posts ago I wrote about buying chemicals from Asia. I mentioned the weakness with shipping. But there are other snags in the system to contend with.  Recently I received a parcel of non-hazardous material that I bought from China. I have been trying to source this stuff for years and I finally found a candidate vendor. We already make the stuff, but we’re short on capacity.  The qual sample was a white granular product and was packed in thin plastic zip-lock sandwich baggies jammed into a used stereo speaker box (!!@#*!). Hell, the foam part for protecting the speaker was still in the box. OK, not smart. And it was mislabeled as some other product. That was the really dumb part.

Torqued about this, I fired off a grim and terse torpedo-gram expressing my shock and dismay at their poor judgement in these matters.  The vendor rapidly replied, exclaiming in much poorer English this time, that since it was a colorless solid product, they believed there would be “problems” shipping it to the USA.  Well, let’s see … hmmm.  It is TSCA listed, it is non-hazardous, no conceivable abuse issues, it is a salt so it won’t burn, but if you dropped a 200 kg drum of it on a cockroach, the cockroach might die.  Yeah, they thought it would be suspected as an illegal substance so they would be clever and ship it under another name. But it is ACS grade material completely innocent of any conceivable abuse potential.  So by being “clever” about it, they revealed their facility with underhandedness.  How can I go forward with a vendor willing to do this crap?

So, you might be tempted to think “Golly, they’re some pretty dishonest chaps”. Well, I’m not sure yet. They may be redeemable. Thank Howard, I myself have been given many second chances. It’s a karma thing. So we’ll inch along and see how they do on the next round. I suspect they’re just naieve in these matters.  Never attribute to malice what you can first explain by ignorance.

Moral of the story- just be honest and above board in all of your business dealings. Ya can’t fall off the floor.

Update:  It was suggested that this is actually a ploy by the exporter to get around import duties.  Well, I’ll happily pay the duties rather than monkey with this sort of thing. Crimony.

Chemical Logistics

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Any chemical company manager will have to admit that order fulfillment isn’t over until the product is in the hands of the customer.  Chemical manufacturing isn’t just about running reactions in big pots.  It’s about attracting a skilled, reliable, and safe work force. It is about building a supply chain for the timely delivery of raw materials. It is about executing the manufacture of products in spec the first time through. It is about warehousing raw mats and products and keeping the stream of wastes moving through the system.

Chemical manufacturing requires the careful management of cash flow by minimizing costs and maximizing profits. The business office must attend to receivables and collect payments in the most expeditious way that customers will tolerate. This is no different that any other manufacturing arena- sprockets, fur caps, or rocket motors.

One of the key jobs required of any chemical company is the matter of managing logistics.  That is, managing the timely transport of raw materials onto the site and the transport of products off the site. So how does this affect the chemist??

The tender shoot studying chemistry in their junior year of college may not know it yet, but if their path is in the fabulous world of business, then some aspect of logistics may be in their future.  What kind of chemist would need some knowledge of shipping? Well, project managers, sales managers, business development managers, plant managers, procurement managers, etc.  All these positions are often filled with chemists and all have to have some knowledge of this topic.  And how does one get this knowledge? Why, on-the-job training, of course.

If you have read many of my posts, you know that I tend to prattle on about this. There is a reason. It is not uncommon for a sales person or a business development manager to spend no small amount of time with a customer trying to work out how the product will be delivered.  The transport of materials is complicated in proportion to the hazard and the chemical sensitivity to decomposition. 

Let’s say that you are in the chemical business and you are just starting the custom mfg of a trialkylphosphine.  The customer will state that they want say, 100 kg, of their R3P with a list of specifications (e.g., 99% in R3P, oxides < 0.1 %, etc, Karl Fisher water 200 ppm) for their new product. The customer has accepted the quoted price and the delivery date. Hmmm. Price, delivery, and specs. Sounds like everything is in place.

So, the question then arises: How are you going to ship it? Glass bottles? Drums? Polyethylene totes? Whoops, the material is excruciatingly air sensitive, so charging and discharging the product will have to be done airlessly. Sounds like a cylinder is just the thing. But what are the materials of construction? I seem to recall that phosphines are ligands, so can we really use a steel cylinder? Soft steel? Stainless steel?

But there is yet another question.  Do we offer the phosphine neat or as a solution? If the neat R3P is a liquid, we can move it around airlessly and charge a cylinder with it. If it is a solid, then it could be a serious problem to transfer it from a filter to a shipping container. How will you or the customer actually handle it? This is the kind of detail that chemists might find themselves groping with. If it is a solid, the customer might have to consider receiving it as a solution in a non-interfering solvent.

Then the matter of transporting it arises. In the present epoch of security theatre, air transport of any quantity might be banned. So, surface shipment will be needed. The matter of heated shipment may arise if freezing or precipitation is an issue. The last thing anybody needs is a cylinder full of precipitated solids in it.  Remember, if you are shipping product in a heated trailer in the winter, you may have stiff competition from other customers who need to ship their lettuce or strawberrys. In some locations, reefer trucks as they are sometimes called may be in short supply.

OK. So you’ve specified a reefer trailer for heated transport of the goods. Let’s say that the product solution will crash out precipitate at 15 C. In the trailer everything is just fine. Fine that is until the shipper reaches a transfer point and moves the product out onto the loading dock where it sits in the freezing weather for a few hours waiting to be put into another trailer. Or it sits in unheated warehouse space for a while.

Eventually, the cylinder of R3P solution arrives and, sadly, has precipitated and won’t come out of the cylinder. So there you are. The customer is unhappy and you now face having to haul it back and recover the product. These are the kinds of problems that chemists on the business side (the plow horses) can find themselves dealing with. Of course, the R&D chemists (the show horses) are rarely bothered with such things.

In low gear

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Th’ Gaussling is in low gear this week due to extra-curricular activities. I’ve been in rehearsal since October for a play that opened last night- The Murder Room by Jack Sharkey. It’s community theatre, which is the only way a hack like myself would have had a chance. This is my first time on stage and it has been quite an experience. Acting is a lot like flying an airplane- it is exhilirating and terrifying all at the same time.  And like flying, you can fall from such a height that it takes a long time to smack into the ground.

Acting requires a type of learning that is rather different from learning chemistry. First, there is rote memorization. There is no escape from knowing your lines. With experience the actor can develop the character around the structure of the dialog. 

It is nowhere near as easy as it looks, and it does require a large investment in time and effort. But in the end, performing with other actors and pulling off a complicated show is quite satisying. 

Keystone Cops in Boston

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The mind still boggles at the recent cartoonish response of Boston authorities to the “viral” marketing campaign by Turner Broadcasting.  Turner Broadcasting’s Cartoon Network evidently sponsored a targeted marketing campaign for its “Aqua Teen Hunger Force” program.  In doing so, their 20-something hirelings violated local sign ordinances by hanging electronic signs on bridges and that is where it stood until police were called and one of the displays was “disarmed” by a controlled bomb squad explosion.

The tipping point came when someone looked at the sign and saw a circuit board, wires and something that turned out to be a battery.  Evidently trained in the school of television drama bomb squadding, the officer on the scene triggered the terror response protocol.  God help us if this local constable ever looks in his computer and sees wires, capacitors, and other mechanisms.

I have witnessed much smaller versions of this first hand.  What appears to be an emergency leads to the arrival of the police and the fire department. This is the part where civil liberties fly out the window, and often enough, sensibility as well. The police establish a perimeter and secure the “scene”.  If the incident involves materials unknown to the police, then they will notify the fire department and then pull the trigger on the hazmat team.  If there is an object that seems suspicious, then they may trigger the bomb squad people. 

Obviously, the fine people who serve the public in the capacity of emergency response or law enforcement are trained and dedicated to their jobs. But what happens is that these people are given precious little latitude in their range of responses to “situations”.  What happens then is that they tend to do what is called erring on the side of safety, which means that when in doubt, call the bomb squad or the hazmat people. 

But when a situation leads to the arrival of the bomb squad, then the natural conclusion of the authorities is that whatever caused this response looks like a crime and should be so investigated. So, irrespective of the merits of the officer-on-the-scenes judgement, there might arise a presumption of foul play and the whole law enforcement apparatus is activated to supply evidence to the district attorney for the filing of charges on the alleged wrongdoer.  In fact one might cynically argue that, especially in these dubious circumstances, it is in the best interest of your career to be able to rationalize the release of these resources as a response to criminal activity. 

So, these two hapless fools who hung the signs in Boston are now at the pointy end of the law enforcement stick and the authorities seem to be bent on saving face through the exercise of grim and officious talk of terrorism. What a mess.