Category Archives: Chemistry

The Quicksilver Monopoly

Hydrargyrum, also known as mercury (Hg) or more colloquially as quicksilver, was in the 19th century the object of monopolistic desire by a large banking concern. In 1835 the Rothschilds acquired the rights from the Spanish monarchy to manage the production of quicksilver in the village of Almaden, located approximately halfway between Seville and Madrid.

The Rothschilds, being ever more interested in controlling their bullion trade, understood that the key to the control of the silver market lay in the disposition of quicksilver. The liquid metal was crucial in the extraction and refining of silver. Silver was purified by amalgamation with quicksilver. Control over the distribution and price of quicksilver in America would put the market in their pocket. They were monopolists- it’s what they do.

Quicksilver has been known for more than 2000 years.  Since Roman times it has been known that everything but gold will float on a pool of quicksilver.  Artisans in Idria, an important old-world reserve of cinnabar in what is now Slovenia, observed quicksilver in its native form in1497.  Quicksilver was mined in earnest in Almaden, Spain, since perhaps the 4th century BC or earlier, according to Pliny. 

Alternating conquests transferred control of Almaden from the Romans to the Visigoths to the Moors and to the crown of Spain, among others.  Having been the seat of mercurial desire for two thousand years, the Almaden cinnabar mines have only recently shut down in the name of public health. Spain’s epic quest for silver and gold in the new world was made feasible through it’s own natural abundance of quicksilver.

Quicksilver was discovered in California in 1845. The New Almaden and subsequently the New Idria mines were quickly pressed into production. The smelting of cinnabar (HgS) into fluid quicksilver is simple in concept and relatively uncomplicated in practice.  A stream of hot flue gases are played over a bed of crushed cinnabar. Oxidation of the sulfide to oxide and subsequent thermal decomposition produces mercury vapor which flows to a condenser surface (brick) where it is knocked down into the liquid state and collected.  Simple technology to perform in undeveloped territory.  Quicksilver was sold in 76 pound lots called a flask. This is thought by some to represent what a laborer (or slave) could reasonably carry.

Within a short time the Californian supply of quicksilver robbed the Rothschilds of their monopoly, resulting in strong price pressure on the European suppliers.  For a few decades, the American quicksilver dominated the Pacific rim. Chinese demand for quicksilver or cinnabar for vermilion was strong.  Silver mining in Mexico and the Andean districts to the south was dependent on quicksilver, most of which was controlled by Spain and later Mexico after its independence. Eventually, the Rothschilds regained control of the market, but at a time when cyanidation and chlorination were playing a larger role in gold extraction. The Rothschilds relenquished their hold on Almaden in 1921.

It is interesting to note that quicksilver, so crucial to the isolation and refinement of gold and silver, was discovered a few years before the discovery of placer gold at Sutters Mill. This happy circumstance surely facilitated the prompt extraction of wealth from the gold and silver mining districts that opened up in the west.

Adiabatic Delta T

We ran our first experiments in the reaction calorimeter today. They were very elementary, involving only the metering one reactant into another at constant reaction temperature.  The results suggested strongly that the reactants were consumed promptly and that good control of temperature is obtained by adjustment of the feed rate. Halt the feed and Qr falls off promptly. This is a very desirable attribute in semi-batch processing. 

From the data workup we determined the adiabatic ΔT, or ΔTad, and were able to follow the heat evolution measured in several ways, but most interestingly in watts per liter. It is desirable to know how many watts of heat evolution your reactor is capable of removing. Engineers think in terms of heat evolution as watts per unit volume. Calibration of a reaction vessel can tell you how many watts of heat the reactor can remove at a defined level of fill and agitator speed.  RC1 data can tell engineering how many watts per liter the reaction mass is capable of. 

Next we ran the reactor in adiabatic mode where the jacket temperature is programmed to follow the reaction mass temperature. The idea is to exert dynamic temperature control via the jacket to make the vessel behave as a Dewar.  We predicted the maximum reaction temperature  by simply adding the ΔTad to the initial temperature. We allowed the reaction enthalpy to ramp the temperature.

The actual endpoint temperature was within two degrees of the predicted temperature and below the bp of THF. This is a measure of the potential for runaway.  If the Maximum Temperature of the Synthetic Reaction (MTSR) is below the solvent bp, then you are in a lesser hazard zone. This temperature would be achieved in an adiabatic system.

A few observations- the heat capacity, Cp, is not constant over the course of a reaction. A little reflection should suggest this.  But it does not automatically follow that the Cp increases in magnitude over the reaction progress, which would offer some thermal buffering capacity.

A Fine Caloric

I’m getting to know the RTCal software that animates my RC1.  Thinking about reactions in terms of their enthalpy profile continues to provide deeper insights for an organikker like me.  It is yet another indication that P-Chem is the central pillar of the central science.  

Our culture is driven foreward by exothermicity. We energize the machines of progress and of war by harnessing the exothermic drivers, be they nuclear or chemical.  

Our exothermic sun pumps a global weather machine that provides the motive force to spin the wind turbines to energize our iPads. The sun evaporates water for it’s eventual depostion at high gravitational potential for the release of hydroelectrically accelerated electrons.  Hydroelectric power is an expression of stellar nuclear exothermicity.

The thermal web of our world is an eternal equilibrium of latent and sensible heat flows.  Water’s latent heat of condensation helps to ramp up thunderstorm formation with the result of flowers and high fructose corn syrup and tornados.  The metabolic heat of formation of water and CO2 warms our bodies and provides animation for our desires and our many methods of locomotion.   Dancing and laughter and lust thrive because of exothermicity.

Our lives are spent in the semi-fluid atomic matrix of our bodies while a continual stream of energy flows through them, energizing  metabolism through the magic of ATP and then diffusing into the surroundings.  This energy has resulted in the universe becoming self-aware through the sentience of material beings.

Eventually, because of the disorder accumulated by the large number of exothermic transformations inherent to continuous metabolism, our legs will stiffen and our jaws will lock shut in death as the stream of energy ceases to issue from us. The transience of sentience is rooted in thermodynamics.  How this can be is still quite mysterious.

Ways to be a chemical entrepreneur

I had a discussion with some professor friends recently about the subject of entrepreneurialism among chemists.  I made my usual points about how people become captains of industry. Be more like an engineer. Preferably one with an MBA.  Naturally, my professorly friends were unmoved. Having spent their entire careers in academia, they just didn’t know about this. I didn’t expect them to.

After I made a gross generalization about the lack of entrepreneurialism among chemists, one prof pointed out that in her field of research, there were indeed people who were starting ventures.  I do not doubt this. But it made me think.  People, perhaps especially those in higher education or just advanced technology, naturally conclude that an entrepreneurial venture has to be based on new technology.  Yes, we need people to start businesses in nanotechnology or what ever you call the latest iteration of biochemistry. We need to have a constant churn of people trying to put new products and capabilities on the table.

But we also need businesses who are able to make polysubstituted phenols, anilines, pyridines, alcohols, ketones, aldehydes, halides, and all of the other “ordinary” raw materials and intermediates that are now largely made in Asia. We need companies who will make 100 kg or 1 MT of some obscure organic material.  Entrepreneurialism isn’t just about the bleeding edge. It is about having a dream and seizing opportunity.  It can be cookies or chemicals.

For the most part, intermediates have moved to Asia because of the economics of batch processing fine chemicals. And a moribund approach to chemical manufacturing in the USA. Chemical manufacturing in the USA is complicated. There are environmental permits, TSCA, high waste disposal costs, high labor costs, expensive processing equipment, and layers of business structure to manufacture safely and with high quality. A chemist faced with navigating the maze of regulations, engineering details, and business operations is a busy person indeed.  Few people can do all of it alone.

There are two fundamental approaches to starting a technology company- Market pull and technology push.  Market pull is an activity where one builds manufacturing capacity with the intent of filling it by making exsting items of commerce. Technology push is where one intends to construct a new kind of technology in the form of a service or widget. Market pull is an approach wherein customers buy known technology. Technology push is the activity where the customer is asked to buy into a new product or service. In this case, you’re necessarily asking customers to be first adopters or to find new forms of value.

I’ve seen startups fail because their one-act pony didn’t work. Instead of trying to make a go of it with a one-act pony, a whole circus of acts should be going at once.  A batch reactor is capable of making many things. A plant built around one product is entirely dependent on that one product.  Batch reactors occupied with products from many market segments are batch reactors that will remain busy over a variety of market conditions.

Pharmaceutical intermediate manufacturing is a business weighed down with substantial overhead and structural immobility.  It is not automatically a great place to start. The GMP world is very complex and peppered with many operational land mines. Many early intermediates are not covered under GMP. That is a good place to start. 

ISO certification is another area where I take issue. While ISO certification brings good business practices, it also brings layers of administrative structure. It is possible to mimic this structure without formally adopting it. The ISO label on you advertising will impress some buyers, but a surprising niumber will be indifferent. If you want to be in pharma intermediates, this will be necessary.  What an ISO certification says is that you will do what you say you are going to do. That is a good idea regardless.

What has to change is the economics of manufacturing in the USA. One way to do this is automated synthesis.  A good example of a problem:  How would one automate the synthesis of an OLED chemical like 1 MT of 8-hydroxyquinoline? This is an existing item of commerce, so entry into the market means taking share from someone else. You’ll probably have to best the market price by 10 % at minimum to induce someone to switch vendors. 

The chemistry isn’t cutting edge, but the processing economics may be. This is an example of how entrepreneurialism can and should  tackle manufacturing problems and gain a competitive edge. Since labor cost is a huge driver, find a way to shave off labor. An entrepreneur’s competitive edge may be process cost savings alone. You don’t have to wait for a scientific paradigm shift.

Part of success is just showing up. Just having capacity and a knack for a particular transformation can attract buyers. If you are handy with borylation and are flexible, somebody will call and want a quote. And maybe a sample. Pretty soon you have a PO and a deadline.

It is good to consider that an advance may be in the form of processing economics, not just the science.

Thoughts on Process Development. Outsourcing.

I have not put pen to paper (Okay. Fingers to keys) on process development lately. I can’t discuss much in the way of specifics. But there are some generalizations that can be put on the table for discussion.

When should you outsource a raw material? Depends. Does the process for the raw material match your skill set? Namely, does it require, say, bromination of an olefin or an aromatic ring? This can be deceptively troublesome. It is easy to scribble down a reaction mechanism for a bromination. It can seem like a no-brainer to say “yeah, we can do that”. Same is true for a Sandmeyer or a Friedel-Crafts reaction or some oxidation reaction for instance.

You may not do much of a particular kind of transformation or handle certain reagents enough to have an institutional expertise to safely handle some materials. You may have safety kingpins who will nix some reagents because they don’t like the looks of the MSDS.  Or, your pots and pans may be booked well into the future and you have no opportunity to make the raw material.

The trouble with outsourcing a raw material is that the supplier’s price is your cost which must be passed along to your customer. You may or may not have the margin to play with to do much outsourcing.  If you suddenly need to outsource a raw material, you will have to find a shop that will make the stuff.  Preliminaries include doing a secrecy agreement, a disclosure of the desired material, and possibly disclosing a technology package.  After the disclosures it might transpire that the vendor isn’t interested, they can’t do the job in the desired time frame, or they want too high of a price. Lots of things can go wrong.  Meanwhile, you’re relentlessly screaming down the timeline towards you’re own delivery date. You should be planning your outsourcing 6 to 12 months in advance. Or even 18 months.  Outsourcing always involves the discovery of new failure modes.

Let’s say that they agree to work up a quote. There is the matter of specifications. They’ll need to know some specifications even before they quote a price.  What kind of purity are you needing? Be reasonable now. There is what you want and what you can get by with. OK, you can live with “97 % purity”. What does that mean? Does it include solvent residuals? What about color and haze or mesh size and appearance? If it comes in at 96.8 %, are you sure you want to reject it?  If it can be easily reworked, and you have the time to spare, rejecting the material might be the best choice. But if they are late and you are late, you may have to take the material on waiver.

Apart from the mere chemistry is the matter of TSCA regulations and/or import restrictions. Will your vendor have to file for an LVE (low volume exemption) or is the material already on TSCA?  An LVE will take time even if everything goes well. Need to put these regulatory filings into the timeline.  Want to import bulk Hazardous When Wet materials? Plan on a boat ride across the ocean.

Asking a company to develop a new product for you requires good communication, person to person relationships, and lots of patience.  Your custom vendor may be smaller than you are and may have considerable resources tied up in your order. They’re taking some risks as well. Shoot for win-win.

Retro NMR

We received our picoSpin 45 MHz NMR last week. It’s the size of a toaster and sits on the benchtop next to the computer. We brought in a bunch of chemists to see a demonstration. Most of them were fresh PhD’s on their first job out of grad school. I think they were non-plussed. What on God’s green earth would someone accustomed to using 300-500 MHz NMR want with a low field FT instrument like this?

Let me say that I am a fan of this thing and the company. Yes, it is retro in some ways. It lacks the sensitivity and features many of us are used to. However, it is an FT instrument and can be used to examine a great many substances. In a high field instrument, it seems like everything  is a doublet of doublets. Not in this instrument. For routine analysis of reaction completion, for instance, you may already know the spectrum of your product or starting materials. One or two reasonably isolated diagnostic peaks is all you need to gauge the state of your reaction. You almost never need coupling constants and fancy 2-D spectra at this point. Often, high resolution amounts to excess capacity. And you can have picoSpin in the lab with you. No need to trudge to the NMR room for a routine spectrum. Oh yes, it’s $20,000 for the unit.

We have a high field instrument, but not at my location. Between the GCMS and the picoSpin, I have a good bit of analytical capability.  What I like about this is that the picoSpin offers a lot of analysis per dollar. Of course a high field instrument offers superior capability. But the fact is that most instrumentation on the market today provides considerable excess capacity. For instance, how much of the capability of Microsoft Excel or Word do you actually use? Perhaps 10 %?  I’d offer that a large fraction of the total dollar amount spent on scientific instrumentation worldwide amounts to excess capacity.  People are easily dazzled by the possibilites in a list of features. Sales people know this and actually depend on it.

So, I’m exploring how this miniature marvel can be integrated into daily use in a chemical manufacturing plant. Chemists are a stubborn lot and it may be that I can’t crack this nut. We’ll see.

US Chemical Business Innovation. Policy or Culture?

The May 23rd, 2011, issue of C&EN, pp 30-31, printed an article titled “Innovation Policy Urged for U.S.”.  The article addresses more than a few considerations regarding the matter of innovation aspirations in the US. You can read the article for yourself. It details some silliness about government programs meant to stimulate startup’s. 

Startups are always in need of money. Like the salmon’s struggle to swim past the grizzlies to the upstream breeding waters, the struggle for resources is part of the Darwinistic screening process.  The struggle for operating funds is a way of screening out weak management. The trouble is, entrepreneurs are often awful managers so good products and services may die for the wrong reason.  Investor money is always loaded with conditions, as any startup operator knows.

The article quotes Richard Bendis, president and CEO of the consulting firm Innovation America. To quote Bendis, “Major research universities are the primary drivers of the future economy and job growth, mostly through science and technology. Global economic competitiveness requires the confluence of scientific discovery and the enabling resources of government and industry.” 

Well, Ok. It’s hard to take him to task here. But the last sentence is gobbledygook. What government cannot provide is the motivation or gumption on the part of chemists to start a company. Chemists need to be exposed to entrepreneuralism well before the day they set out to hatch a startup.  The current course of study in the bachelors program at virtually any US college or university is proctored by faculty who almost without exception come from a purely academic background. They know nothing about “industry” other than the salaries are probably better.

As Bendis rightly states, “Major research universities are the primary drivers of the future economy and job growth, mostly through science and technology.”  But major research universities, with a few exceptions, are poorly equipped to find and train chemists to be the future captains of of industry. It is a culture problem. The structure of the university chemistry department is not constructed to groom anything but scholarship. The American Chemical Society certification is part of the problem. The ACS recognizes and endorses a particular kind of curriculum. Most all chemistry departments have secured this endorsement long ago.  While the curriculum defines the minimum standards for a degree in chemistry, it also has the effect of freezing out much real innovation or adaptability in the field.

Faculty with business or industrial backgrounds are largely deselected from joining the club, if for no other reason than publication rates. Industrial chemists rarely have the opportunity to publish their work in the normal spread of journals owing to IP restrictions.  I’ve been a part of  a few search committees and I know how it can go.

The main exception to my generalization is MIT. Whatever it is that MIT is doing to stimulate startups, it’s does it very well. They are practically a force of nature by themselves. I would argue that the Mojo that MIT plainly possesses has more to do with culture than policy.

And it’s not just chemistry faculty that have to adapt to a new endgame in the program. The matter of turning a program to applied science must necessarily involve deans and university presidents.  They will all want to have their say. In the end, to most presidents, getting in the top 25 of whatever group of schools they aspire to be in is what matters. And that involves keeping the enrollment numbers and the endowment figures up. That is how they are measured and that is what they will look after.

Putting out applied science oriented majors will involve considerable cultural change in the academy. I’ve seen nothing to indicate that the academy is ready to embrace a real step towards the kind of entrepreneurial spirit in the aspirations expressed in the article in C&EN.  It is very difficult to be heard over the clucking in the academic henhouse.

Memorial Day and Inventors Conscience

Here is an interesting post called When Chemists go to War.  It is a good reminder of how our work can be taken to places where we ourselves wouldn’t go.  Ever develop chemistry that has killed someone? What would you do if you developed a substance that was used for destructive purposes? Would it bother you?  Some scientists from the Manhattan Project were troubled by their work on the bomb, but others slept quite well.

I suppose it could be considered similar to the situation with the inventor of the baseball bat. Could this inventor have forseen the use of the bat in committing violence? Probably didn’t cross his mind.  But if you’re inventing new military explosives, how do you cope with the knowledge that your invention’s use is specifically for more precise application of killing power?  The fact is that there are many scientists who have no difficulty with this at all. I’ve met a few of them and they are very sober folks. They know exactly what their invention does and they are eager to do even better.

I think it is this ability to stand behind the abstract technical details, sheltered from the blood and guts reality, that allows scientists to rationalize their work on killing technology. Scientists will never have to carry with them the olfactory battlefield  memories of bomb smoke and shredded bowel.  Weapons labs are relatively safe places to work.  The weapons scientists biggest hazard, realistically, is the commute to and from the lab. Perhaps weapons designers and munitions manufacturers should have to clean up after a car bomb or carry bodies from the scene so as to emphasize the exact consequences of this work.

Maybe the most important thing we can do to honor soldiers lost and wounded in battle is to resolve that we will produce fewer dead and wounded soldiers. One approach embraced by many is to make war more effiicient and more automated. Send machines into battle rather than people. The other approach is to be a bit less warlike. Throttle back on weapons spending. Take the view that war isn’t really glorious, but rather that it is an uncivilized duty we are called upon to do on occasion. 

Amassing huge armed forces presents the temptation to use them.  The goal for our national leaders should be … lead us not into temptation.

Cyanide-Based Legislative Voting Machine

The US patent literature is full of wondrous inventions and its easy access by computer-machine over the internets is a real boon to historians and hacks like myself.  In the course of my studies into 19th century gold metallurgy, I stumbled across US 7,521, issued July 22, 1850. This patent was issued to Albert N. Henderson of Buffalo, NY.  Mr. Henderson’s invention is entitled IMPROVEMENT IN THE APPLICATION OF ELECTRO-CHEMICAL PRINTING IN COLORS FOR TAKING AYES AND NOES. 

Henderson describes an apparatus for taking the ayes and noes by galvanic electricity and specifically proposed it for use in legislative assemblies. The concept was that at each desk in the assembly would be two keys (switches, as we now call them) for voting either Aye of No. The member would press one of the keys when called to vote, with the result of an electric current passing to a central apparatus with specially treated paper pressed between electrodes. The action of the current in the damp treated paper would be that a vote would be registered as a mark on the paper, recording the vote of the member.  In the end, the only gold connection in the patent related to gold electrodes as a preferred embodiment.

Claim 1.  This patent claims a mode of imprinting words, letters, & figures, etc, upon paper or other fibrous substances between two surfaces of a metal which is not acted upon by the substances employed, on one of which the letters or figures are raised by passing a current of galvanic electricity through the prepared material, substantially as above described.

Claim 2. Passing the electric current between metallic surfaces, as above described, through damp paper otherwise unprepared, and afterward applying a chemical solution, by which the effect of the electricity becomes visible whenever it has passed through the paper, for the purposes above described- telegraphing, etc.

Substances which may be used as part of the solution for the preparation of the paper- Copper sulfate (gives black impression), Potassium cyanide which may be acidified with H2SO4 or HNO3 (!!) to impart a green color with the galvanic current.  A strong solution of KCN with Ag chloride gives a green impression. All above leave white paper until acted upon by electricity.  A weak soln of potassium ferrocyanide (prussiate of potassia) colors the paper slightly and leaves a deep blue impression by the electricity. Henderson prefers to use electrodes of gold or platinum.

This invention has a kind of steampunk aspect that I find very appealing. On the other hand, it is hard to know what knowledge the inventor had with regard to the hazards of KCN or acidified solutions thereof. The patent is silent with regard to the chemical safety questions arising from the use of KCN treated paper.

Albemarle enters lithium market

Here is one I didn’t see coming.  Albemarle has announced that it will be entering the lithium carbonate market.  In case you didn’t know, Albemarle has been a leader in bromine and brominated flame retardants for some time.  Economically speaking, if you want to be a bromine specialist or brominator at the commodity scale you should probably be basic in bromine. That is, you get your bromine feedstocks from underground or the Dead Sea.

Everybody likes the benefits of flame retardants but nobody likes to pay much for it, so manufacturing has to be large scale to keep the retardant prices down. The way you do that is to pull bromide from the ground, often as a brine, and oxidize the bromide to bromine and isolate it from your process stream. Albemarle has recent US patent applications for the nth iteration of their technology: see US 2010/0047155 A1.

A quick perusal of Albemarle patents failed to turn up any US patents or published applications indicating that they had been working on this. This press release must have been given special consideration in view of anticipated demand for their lithium. 

Since Albemarle is already tooled up for brine work it is not such a stretch to see that they are piloting lithium extraction from their process streams. According to Specialty Chemicals, a chemical trade publication, the Albemarle brines contain 100-300 ppm of Li and sources say that they are using an exchange resin for the isolation. While the brines at it’s Magnolia, Arkansas, facility are a little on the lean side in lithium, the fact is that they are already set up for brine processing. A large chunk of capital costs for recovery have already been put in place for the bromine operation. So, it’s a matter of setting up a Li extraction train to intercept the brine stream somewhere in the Br process.

Setting up ancillary process trains like this to recover other values is not at all uncommon. According to the Specialty Chemicals article, Albemarle expects to be producing lithium carbonate in 2013.

The USGS publishes annual reviews on the global stockpile situation with economically important minerals, lithium included.  A prominent source of lithium in the US is the Tin-Spodumene belt at King’s Mountain District, NC. Spodumene, LiAlSi2O6, is the principal mineral variety at Kings MountainChemetall Foote, a subsidiary of Rockwood Holdings, now operates at Kings Mountain, NC, in Nevada, and  Salar de Atacama in Chile.

According to Virginia Heffernan at the website Mining Markets, the cost of spodumene processing to afford lithium carbonate is quite high, $5500 per tonne of Li2CO3. Acid roasting is used to process the ore to liberate the lithium.

According to the article at Mining Markets the three major players in global lithium are Chile’s Sociedad Quimica y Minera de Chile (30 %), Chemetall (28 %), and FMC (19%).