Amine Question of the Day

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Here is an interesting question. What fraction of the organic nitrogen in your body is ultimately from the Haber-Bosch Process?  Any guesses?  This question arose during dinner discussion following a rousing seminar on frustrated Lewis pairs. There is no connection to frustrated Lewis pairs, but the speaker raised the question.

Oh, I don’t have an answer. This happens in science.  I’m guessing ~50 %, depending on the extent of protein containing corn products consumed. Any meat science people out there?

8th Grade Science as a Path to Madness

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So it happens that my kid is in 8th grade and is studying chemistry for the first time in earnest. As luck would have it, the kid’s teacher is of Haitian extraction and is on some kind of leave of absence either due to illness or possibly because 3 family members perished in the quake. I don’t know. This fellow seems to be a good teacher.

His replacement, however, is not very good. In fact, his replacement is … awful.

For the first time, I had a serious discussion with a principal about a teacher’s performance. The principal is apparently aware of the substitutes classroom foibles and sins of omission. The principal’s own son is a student in that class and so he has a personal interest in the matter.

So, after some time with the kid at the whiteboard in our basement last night, it dawned on me that I had completely forgotten how utterly strange atomic theory and the chemical phenomena that derive from it really are. It is all quite abstract and maybe even a little weird.

The curriculum gives some emphasis to understanding the concept of pH. Alright. But this requires some ideas about logarithms and exponents. Then there is the matter of chemical equilibrium. While kids are wrestling with the math, you are also trying to tell them that only a very small number of water molecules actually come apart into ions. But the kids need to be comfortable with the notion of ions and charge.

But, what makes hydrogen ion different from hydroxide ion, really?  And why does hydroxide ion have the negative charge? How is it that acids corrode iron to form H2, but hydroxide does not? What does it mean to be an acid? What does it mean to be a base?

You can try to use structural models of sulfuric acid rather than line formulae like H2SO4 to appeal to the idea that these are little things with attachments that do things. One could argue that it is a bit more concrete that way- little structures with parts that are detachable. But as soon as you start drawing structures, you run into a rats nest of intermeshed concepts relating to bonds and lone pairs. Then there is the bloody octet rule, covalency, and orbitals!!!

For crying out loud!! How does anybody learn this stuff?? The learner has to absorb 20 abstract concepts almost simultaneously to begin to “get” chemistry.  Even worse, if a chemist/parent teaches the kid about a concept, almost certainly it will not mesh with curriculum, leading to confusion and tears for the teacher and the student.

I taught orgo to college sophomores, but evidently 8th grade chemistry eludes me. I’m just too dense to grasp the level of abstraction they will accept. Oh!  To have an hour with Piaget!

Thorium

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A short drive from my office is the Fort St Vrain power plant. The present electrical generating facility is powered by natural gas. But a generation ago it was a nuclear plant powered by a high temperature gas cooled reactor (HTGR). What’s more, the reactor used fissile uranium with fertile thorium.  The output of the plant was ca 330 MW electric and it operated from 1976 to 1989.

The utility eventually decommissioned the helium cooled reactor and converted to natural gas. Today, as before, the plant looks like a planetary humidifier, billowing great clouds of steam condensate into the thin dessicated air of the high plains. The link above outlines the trials and tribulations the utility experienced with some of the auxillary hardware. They had to learn the principle of KISS the hard way.

A thorium-based nuclear reactor uses a fissile element like U-235 to provide a source of neutron flux from which to jumpstart in-situ breeding of U-233. The absorption of a neutron by Th-232 gives Th-233 which beta decays to Pa-233 which decays again to U-233.  Remember, beta decay causes the atomic number to increase by one, but the atomic weight stays the same.  The resulting U-233 is fissile and serves as a fuel.

Thorium as a fuel has pluses and minuses. On the plus side, thorium is more abundant than uranium. And Th-232, the predominant isotope, is the desired fertile material. This is in contrast to natural uranium which offers less than 1 % abundance of fissile isotope U-235. A large part of our nuclear infrastructure involves separation of this isotope to a more concentrated form. After isotopic separation the uranium must then be converted to a suitable chemical form.

The refractory nature of thorium oxide reportedly makes fuel element manufacture somewhat problematic. Interestingly, it is the refractory nature of thorium oxide that makes it valuable for use in thoria lantern mantles. The high melting point of thoria allows a gossamer web of glowing thoria (and ceria) to sit in place in the lantern burner and radiate bright white light.

On the minus side, there is no established fuel supply infrastructure to provide thorium oxide to industry. In fact, there is virtually no thorium trade in the United States today, with the latest annual US sales volume amounting to a paultry $350,000 according to the USGS. Some of the nuclear chemistry is of the thorium cycle is problematic as well.

The natural history of thorium mineral placement is rather different than that of uranium. Uranium migrates fairly readily, depending on its oxidation state and pH of mobilized hydrothermal fluids. As a result, uranium can be found in porous or fractured formations that have a history of water migration.  From what I can tell in the geological literature, thorium concentration results largely from magmatic differentiation in the distant past. There is considerable diversity in the details of each occurrence of thorium, so one should be careful of generalizations.

There is a notable monazite (a common thorium mineral) placer district across the central North and South Carolina border region. These monazite placer deposits sit in ancient stream channels and are the result of alluvial dispersion.

Colorado has two notable thorium mineral deposits. The Wet Mountains SW of Canon City and the Powderhorn district near Gunnison have substantial deposits of thorium as well as lanthanide elements. In fact, rare earths are commonly associated in monazite. Monazite is a phosphate mineral with a variety of thorium and lanthanide cations present. It is useful to recall that the rare earth elements include Sc, Y, the lanthanides, and the actinides. In Colorado, the significant uranium deposits are not coincident with thorium deposits. Uranium is found in sedimentary deposits of the Colorado Plateau, in the tuffaceous sediments of the Thirty-Nine Mile volcanic field, and in vein lodes along parts of the Colorado mineral belt.

There is considerable variability in the elemental associations found in rare earth deposits. Monazite seems to be fairly consistant in regard to the presence of Th and lanthanides. Scandium, however, is often absent or quite scarce in monazites from the assays I have seen in the literature. 

Perhaps the richest thorium district in the lower 48 states is in the Lemhi Pass district along the lower Idaho-Montana border. A company called Thorium Energy reportedly holds substantial claims of thorium rich deposits at Lemhi.

That’s Show Biz

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A few of us have formed a theatre company. It is a not-for-profit operation. It’s too sketchy to expect a profit in theatre anyway. May as well admit that up front. Among the founders is a playwright.

Our first performance as a theatre company is coming up soon and was written by our in-house writer. It is a play called Cow Dung Dust. The story takes place among hitchhikers in the back of a cattle trailer headed for California along Route 66 ca 1970. The same writer wrote the play Beets, which we performed in Loveland, Colorado, last spring. It was actually quite a hit.

The first public airing of Cow Dung Dust will be performed as readers theatre. This is much like radio mystery theatre with actors reading from a script and with a bit of lighting and sound effects.  Since we do not have a few kilobucks to throw into set pieces, costumes, and lighting, readers theatre is what we are able to do first thing. It is like a garage band having to do a bunch of lean and mean gigs in order to build up a following. I have a feeling that after the readers theatre we’ll be keen to do a stage performance of it. This approach gives the playwright a chance to tweak the script after he sees the audience react to it.

The next performance will be a well known stage play. This requires paying royalties for use of the script, which is typically copywritten tighter than a piano wire. Should be fun. It is so wonderfully different from chemistry, I can’t help but enjoy it.

The Passive Aggressive Opera. Act I. Reverse Delegation.

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Supervision of people is one of the things that a chemist can look forward to on the way up the ladder. The people who report to you may be called staff or report-to’s. The term “my employee” should be reserved for use by those who sign paychecks. What ever you call them, they’re your group.

I’m not going to write about how to manage people. After many years of doing it I’m not sure I really understand it yet. All I can say is that every day some people show up and expect you to keep them busy.

Okay, I’m just kidding. But I am serious about the mysteries of management of people. I think most would agree that the best way to lead people- the way most of us would prefer to be lead- is by setting a good example. It’s pulling instead of pushing. Inspired leadership by a charismatic and talented individual is preferable but, unfortunately, rather unusual. 

There are many theories of management and more management consultants than you can count out there urgently interested in telling you how to manage your staff.  All you have to do to sample the many management theories is to stroll through the business section of the local bokstore. Every one of the authors will trot out a set of polished anecdotes that outline the path to their own professional enlightenment.

Chemists on the  management track may move in many directions in a business organization. Most obvious is management of a technical activity like R&D. But there is also management opportunity in scale-up, pilot plant, production, QA/QC, and analytical services activity. Management of the production side is sure to include inventory and warehouse control, regulatory affairs, personnel issues, engineering, and maintenance. Itis not uncommon for engineers to head the production unit.

On the less technical side is sales, procurement management, and business development.  While perhaps less technical, the chemical industry needs (requires, really) chemically savvy people to handle purchasing and sales activity. It is not uncommon for sales oriented people to ascend into the upper reaches of management generally and the chemical industry is no different.

What is perhaps different in the chemical industry is that chemists are often disfavored in the track to the CEO’s office by their lack of economic training. The ability to deliver big projects on time and on budget is a key attribute and engineers are especially well positioned to do this very thing. The bigger the scale of operations the greater the likelihood that an engineer will be in charge. Or so my experience has been.

Among those I have observed, managers who have exemplary experience in controlling the big money are often the ones groomed for executive leadership. And the big money is in big projects with lots of sales volume. It is the source of life giving cash. That which makes the corporate world go ’round. The elusive spondulix.

But back to management. One of the most vexing aspects of managing people is that you have to manage people. People are complex and prone to nonlinear behavior. Everybody knows this. But the manager is tasked with using human resources to provide some kind of work product on time and on spec. How do you compel people to do this every day?

The threat of termination is a good though heavy handed tool to compel folks to do their job. But this is a tool that can also backfire. Frequent termination of people is stressful and puts the manager in the position of having to be in a more or less constant training mode. Best to hire hard working people who are self-starters.

I have not found a simple formula for management. All I can do is to support down and fight up. I fight for resources and reasonable expectations. I treat people in the most hospitable manner I can muster and in return I expect the same.

One of the most annoying behaviors is the phenomenon of “reverse delegation”. You ask your report-to to do a particular thing. In reply you are told that they can only do the thing if you first make some arrangements. You have to get this or that ready, or perhaps you have to write an SOP or work instruction, or maybe even they will need to fly to a hotel in Vegas or Orlando to take some training course. It is all push-back: a kind of passive aggressive behavior meant to deflect your attention.

What I have found is that these reverse delegators may be very concrete in their approach to the unfamiliar. They will assert that they must possess a good deal of skill to even begin some new task. Sometimes this is true. But often it is only a matter of time on task to make some good progress.  The hard part for some of us is dealing with the simple truth of the matter. Not everyone desires being collegial and operating on the give and take level of colleague. A lot of folks only respect the brusque barking of orders by a Captain Bly figure and the sight of a**holes and elbows hustling in the plant. I would have been Captain Kangaroo, not Bly. It’s just a fact.

Old Knowledge and New Problems in Chemistry

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I’ll admit to having a bit of a book fetish. I love everything about books except moving them. I collect new and old books. I have a professional chemistry library that is consuming quite a bit of wall space. And that doesn’t include the boxes of JOC, Organometallics, and JACS. It’s getting out of control.

My amateur geology library has gone from one book last summer to about 50 books and USGS circulars today, and more are enroute this very minute thanks to Amazon.com, Paleopublications, and many more booksellers.

What I’m beginning to see is that university libraries across the country are withdrawing older chemistry books from their shelves. I do not refer to textbooks. I am referring to the valuable secondary literature that has accumulated descriptive chemistry knowledge.  These books are snatched up by specialty book sellers and are placed on the internets for sale where odd characters such as myself will gratefully buy them.

Recently my fetish for old books is helping me solve a thorny contemporary inorganic analysis/synthesis problem. You see, the older texts are rich in wet chemical methods. While a book like Chemistry of the Elements by Greenwood and Earnshaw is fantastically broad in its scope, it is not meant to transfer the pargmatics of procedure. The older chemistry and ore refining texts are full of practical information that seems to be fading away. While the primary literature may be available on SciFinder, books that cover accumulated descriptive chemistries are becoming scarce.

I can’t reveal the details of my revelation. But I can say that a process development person can learn quite a bit about materials processing from the late 19th and early 20th century literature. Our predecessors couldn’t depend on ICP or GDMS or XRD to help them follow the process. The wet chemical methods they developed also give us insights into the transformations necessary to produce purified products.

The unit operations of calcining, comminution, reduction, oxidation, flotation, dissolution, drying, etc., have not changed much in a fundamental way since the days of Agricola. But they are better quantified by virtue of a century of research.

Our collective drift from wet chemical methods to instrumental and computational approaches to analysis are also taking many of us away from the pragmatics of chemistry. The hyphenated instruments of today are leading large numbers of chemists away from the art of chemical transformation and isolation in favor of chemist-as-software-expert. Certainly this computational intensive investigation is not lost in our university curricula. Our hypnotic embrace of technological triumphalism meshes with the perceived need to minimize hazardous material inventories in the chemistry department stockroom. And with the perceived need to minimize chemistry students to exposure to chemicals.

Chemical industry is centered on the art of making things. In the end, somebody has to figure out how to make chemical substances and somebody else has to do the actual work. We chemists have to make sure that university curricula meets the needs of society and that the librarians of the world understand the importance of older chemistry books.

On the pitfalls of process intensification

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As any process development chemist knows, there is motivation to optimize a chemical process to produce maximum output in the minimum of reaction space. In the context of this essay, I’m referring to batch or semi-batch processes. Most multipurpose fine chemical production batch reactors have a capacity somewhere between 25 and 5000 gallons. These reactors are connected to utilities that supply heat transfer fluids for heating and cooling. These vessels are connected to inerting gases- nitrogen is typical- and to vacuum systems as well.

Maximum reactor pressure can be set as a matter of policy or by the vessel rating. Organizations can, as a matter of policy, set the maximum vessel pressure by the selection of the appropriate rupture disk rating. Vessel pressure rating and emergency venting considerations are a specialist art best left to chemical engineers.

Reactor temperatures are determined by the limits of the vessel materials and by the heat/chiller source. Batch reactors are typically heated or chilled with a heat transfer fluid. On heating, pressurized steam may be applied to the vessel jacket to provide even and controlled heating.  Or a heat transfer fluid like Dowtherm may be used in a heating or chilling circuit.

Process intensification is about getting the maximum space yield (kg product per liter of reaction volume) and involves several parameters in process design. Concentration, temperature, and pressure are three of the handles the process chemist can pull to increase the reaction velocity generally, but concentration is the important variable in high space yield processes.  Increasing reaction temperatures or pressures might increase the number of batches per week, but if more product per batch is desired and reactor choices are limited, then eventually the matter of higher concentration must be addressed.

The principle of the economy of scale says that on scale-up of a process, not all costs scale continuously or at the same rate. That is, if you double the scale, you double the raw material costs but not necessarily the labor costs. While there may be some beneficial economy of scale in the raw materials, most of the economy will be had in the labor component of the process cost. The labor and overhead costs in operating a full reactor are only slightly greater than a quarter full reactor. So, the labor component is diluted over a greater number of kg of product in a full reactor.

The same effect operates in higher space yield processes. The labor cost dilution effect can be considerable. This is especially important for the profitable production of commoditized products where there are many competitors and the customer makes the decision solely on price and delivery. Low margin products where raw material costs are large and relatively fixed and labor is the only cost that can be shaved are good candiates for larger scale and higher space yield.

But the chemist must be wary of certain effects when attempting process intensification. In general, process intensification involves increasing some kind of energy in the vessel. Process intensification through increased concentration will have the effect of increasing the amount of energy evolution per kilogram of reaction mixture.

Energy accumulation in a reactor is one of the most important things to consider when attempting to increase space yield. It is crucial to assure that process changes do not result in the accumulation of hazardous energy.

Energy accumulation in a reactor occurs in several ways. The accumulation of unreacted reagents is a form of stored energy. The danger here is in the potential for a runaway reaction. Accumulated reagents can react to evolve heat leading to an accelerated rates and eventually may open further exothermic pathways of decomposition. As the event ensues, the temperature rises, overwhelming the cooling capacity of the reactor. The reactor pressure rises, accelerating the event further. At some point the rupture disk bursts venting some of the reactor contents. Hopefully the pressure venting will result in cooling of the vessel contents and depressurizing the vessel. But it may not. If the pressure acceleration is greater than the deceleration afforded by the vent system, then the reactor pressure will continue to a pressure spike. This is where the weak components may fail. Hopefully, nobody is standing nearby. Survivors will report a bang followed by a rushing sound followed by a bigger bang and BLEVE-type flare if the system suffers a structural failure.

Energy accumulation can manifest in less obvious ways. Here is an example. Assume a spherical reaction volume. As the radius of the sphere increases, the surface area of the sphere increases as the square of the radius. The volume increases as the cube of the radius. So, on scale-up the volume of reaction mixture (and heat generation potential) will increase faster than the heat transfer surface area. The ratios are different for cylindrical volumes, but the principle is the same. Generally the adjustment of feed rates will take care of this matter in semi-batch reactions. Batch reactions where all of the reagents are added at once are where the unwary and unlucky can get into big trouble.

Process intensification via increased concentration may have deleterious effects on viscosity and mixing. This is especially true if slurries are produced and is even worse if a low boiling solvent is used. Slurries result in poor mixing and poor heat transfer. Low boiling solvents may be prone to cavitation with strong agitation, exacerbating the heat transfer problem. Slurry solids provide nucleation sites for the initiation of cavitation.  Cavitation is difficult to detect as well. The instinct to increase agitator speed to “help” the mixing may only make matters worse by increasing the shear and thus the onset of cavitation.

Denser slurries resulting from process intensification are more problematic to transfer and filter as well. Ground gained from higher concentrations may be lost in subsequent materials handling problems. Filtration is where the whole thing can hang up. It is important for the process development chemist to pay attention to materials handling issues before commiting to increased slurry densities. Crow is best eaten while it is still warm.

Alien Fasteners. Wingnuts from space.

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Imagine that you and a companion are out for an evening stroll after a big dinner, say in a park somewhere. You hear a curious whining sound and look up to see an alien spaceship on a landing approach to the park. The craft lands and the crew scuttles off to perform some tedious abduction or organ harvest in the neighborhood.

Your companion exclaims “Golly! There is something you don’t see every day!”. But you’re unmoved by your companions incisive commentary. Because you see this as a long sought opportunity to examine an alien craft up close.

What would you look at? The propulsion system? Or perhaps the weapons array or guidance system? Pffft.

I would look at something much more mundane. I think it would be very enlightening to see what kind of fasteners they use. That’s right. Fasteners. Nuts, bolts, latches, bungees, straps, nails, hinges, hooks & loops, and rivets. How do these confounded exo-buggers hold things together? What’s the deal?

Fasteners are mechanical contrivances used to restrain objects into a desired configuration, often by the application and fixing of tension or compression through some structural element.  Think of all of the fasteners we encounter before we set foot out the door every morning.

Elastic articles of clothing perform a fastening function through the application of tension about numerous body parts through the miracle of Spandex/Lycra.  Shoe laces are fastening devices that apply and hold tension on opposing shoe upper elements wrapped over the arch of the foot.

Moving upwards, the zipper is a fastener that works in concert with a trouser/skirt button or snap fastener.  The belt and buckle are a fastener ensemble that together apply and hold tension about the circumference of the waist to keep ones trousers from succumbing to the pull of gravity.

Other fasteners include shirt buttons, brassiere connectors (damn those things!), earring wires, eyeglass frames (they connect to your face), cell phone belt attachments, the deadbolt on the front door, all manner of electrical connectors, and the list goes on and on. Electrical connectors are  especially interesting because they combine the functions of electrical continuity and fastener. All are a compromise between the competing interests of biomechanics, convenience, safety, regulatory standards, and custom.

So, back to the space ship. How would space faring beings approach the problem of fastening materials and components. Would they use individual components fastened together or would they use integrated component assemblies that support multiple functions? Perhaps the mechanical fastener question is moot because components would be cast, glued, or welded.

Integrated components have a certain appeal, but, by their integrated  nature could serve as a node from which to initiate failure propagation to multiple systems. For instance, if a battery was built to serve as a structural element for the craft, could a battery failure of some sort serve to initiate a structural failure mode? At what point is it foolish to integrate systems rather than leave them distributed? As always, it depends.

I think an alien spacecraft would have at least a few kinds of obvious fasteners. Surely alien technologies are subject to component failures and would require occasional repair.  Of interest would be the concessions to alien biomechanics.

Humans occasionally use wingnuts to fasten objects that need not be permanently affixed. The wingnut is simply a style of threaded nut that has two modest protuberances that allow for torsion and compression to be applied by the fingers and wrist. The wingnut is not functional for beings who lack the sort of articulated digits that we have. Perhaps an alien being would have a latch or other contrivance to accommodate its appendages.

Of course, all of this alien talk is just a device with which to cast the matter of fasteners into a more interesting light. Fasteners are part of our collective technological heritage and are rather under-appreciated. But, if you are unfortunate enough to be abducted by aliens, I suspect that the matter of alien fasteners might be of immediate interest.

Schneier on Security

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Over at CNN.com there is an excellent post by the security expert Bruce Schneier. Finally, somebody has spoken what must be said. Schneier, by the way, was the one who invented the Blowfish encryption algorithm.

“Security theater” refers to security measures that make people feel more secure without doing anything to actually improve their security. An example: the photo ID checks that have sprung up in office buildings. No one has ever explained why verifying that someone has a photo ID provides any actual security, but it looks like security to have a uniformed guard-for-hire looking at ID cards …

Despite fearful rhetoric to the contrary, terrorism is not a transcendent threat. A terrorist attack cannot possibly destroy a country’s way of life; it’s only our reaction to that attack that can do that kind of damage. The more we undermine our own laws, the more we convert our buildings into fortresses, the more we reduce the freedoms and liberties at the foundation of our societies, the more we’re doing the terrorists’ job for them. –Bruce Schneier

My take on Schneier’s thesis is that the public, i.e., the teeming masses, must not allow the many arms of government to further tighten its grip on our liberties. Liberties once taken are hard to recover. The combination of media sensationalism, advanced information gathering, and authoritarian reflex is driving the USA into a permanent security state. A mature and thinking public must buffer the exaggerations and sensationalism that is broadcast into our homes every minute of every day.

Counterterrorism is also hard, especially when we’re psychologically prone to muck it up. Since 9/11, we’ve embarked on strategies of defending specific targets against specific tactics, overreacting to every terrorist video, stoking fear, demonizing ethnic groups, and treating the terrorists as if they were legitimate military opponents who could actually destroy a country or a way of life — all of this plays into the hands of terrorists. –Bruce Schneier

By closely following the exploits of a handful of radicals as though they could bring down our civilization, we legitimize their efforts as being worthy of our sustained attention. These are low frequency high visibility events.  Unfortunately, lingering and repeated gawking at sensational events against a constant buzz of soaring narrative is what television does best.