Category Archives: Chemistry

Martian Swamp Gas

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According to recent reports, space scientists using infrared spectrometers at observatories in Hawaii and Chile have detected low levels of methane in the Martian atmosphere. This finding is consistent with results from as far back as 2003 when several studies reported methane at approximately 45 ppb.  Observers performing the latest work conclude that the observed methane must be of recent origin, given the short half-life of atmospheric methane due to photodegradation. 

The connection of these findings with the possibility of past or present life on Mars has proven irresistable. I’m sure there are group leaders beavering away at mission proposals this very moment based upon these findings.

An explanation that is much less exciting and much more challenging in regard to grant proposals is the abiotic explanation. Here on earth there we have a lesser known and widely overlooked abiotic theory of hydrocarbon origin. Abiotic hydrocarbons are often referred to as primordial and are known to exist in planetary atmospheres elsewhere.

According to John S. Lewis, Physics and Chemistry of the Solar System, 2nd edition, 2004, Elsevier, Inc.,  p. 159, the mole fraction of methane in the atmosphere of Jupiter is 0.001 and for Saturn it is 0.002.  The mole fractions of water are 0.001 and 0.002 respectively. Among heavy atom species, only ammonia, hydrogen sulfide, neon, and argon approach these levels within a factor of 0.5 to 0.1.

Oxygen and carbon are two of the most highly abundant heavy atoms and to see them richly represented as their respective hydrogen compounds isn’t so surprising.

At some point in the formation of the solar system, atomic carbon and atomic hydrogen were cool enough to collide and form molecular methane.  Hydrogen with its larger mole fraction would be expected to dominate bond forming interactions with carbon atoms, forming H-saturated methane.

Given the abundance of methane in the gas giants (and don’t forget the methane atmosphere of Titan)  it is hard to discount that Mars has trapped methane in the vast interstitial spaces of the interior of the planet. Methane is known to form clathrate structures with water, so perhaps the proposed underground reservoir of Martian water is comingled with methane.

I believe we should be exploring Mars. But I am increasingly uncomfortable with this stream of “Entertainment Tonight” titillation coming from NASA in regard to the possibility of life on Mars.  Perhaps our culture isn’t as advanced as we assume. Space exploration has always had a large political prestige component to it. Contractors need new contracts and politicians are always keen to bring funding to their districts.  If it takes our lesser angels to make it work, then so be it.

Chemist Alert! NFPA 400 to be posted in May 2009.

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The National Fire Protection Association (NFPA) is an international nonprofit organization dedicated to the prevention of fire related incidents. The have recently pitched a set of regulations as NFPA 400 pertaining to the storage of hazardous materials. The comment period is long over and soon the rules will be issued as a published document.  While the NFPA is not a regulating body, their rules are widely adopted by government organizations and promulgated.

If you have not taken the chance to review some of these documents, it is well worth your time as a chemical professional to do so. Why? Because the practice of chemistry is being dramatically necked-down in terms of the kinds of chemistry that can be practiced and the manner in which materials are stored. Not only is your local fire marshal packing a stack of NFPA based fire codes, but a whole host of federal regulators are armed with regulations from Homeland Security, EPA (i.e., TSCA), DOT, REACH, and an alphabet soup of regulatory coverage aimed at every conceivable substance.

Organizations that oversee chemical operations include the chemical industry, hospitals, agriculture, mining, and academia. All organizations are under the obligation to provide a safe workplace for the employees. It makes sense to minimize employee exposure to risk. But the web of applicable regulations for any given chemical operation is expanding by the day.

Not only is an organization obliged to conduct business in compliance, but quite often there is the requirement of self-reporting of noncompliance. An organization finding itself out of compliance is an organization in need of legal representation. The nuances relating to most any kind of regulation are such that your average company president will generally be unwilling to settle the malfeasance with the regulatory agency without the help of an attorney. This is the point where a jet of cash starts flying out of the company coffers.

So, the question of the effect on academic chemistry arises.  Academic chemistry departments are seeing increased coverage under the regulatory umbrella as well. Should academic research labs have some sort of dispensation given the nature of the activity? Given that OSHA regulations may not be applicable to students, academic labs are already under somewhat less scrutiny. More to the point, how much government intrusion should researchers accept in relation to the kinds of chemicals they work with and store and the kinds of risks that are taken during research?

This is important for a very good reason. The issuance of proposed rules by organizations like NFPA results in regulatory pressures that eventually find their way to individual researchers. But the researchers don’t hear about it directly from NFPA. The University Health and Safety department hears about the regulations (or guidelines) and they apply requirements on chemistry departments. Faculty being faculty, they’ll perform a gritching ritual and eventually comply.

Generally, the arrival of new regulations results in new constraints. The end result is that the department has to spend more to operate the labs and students receive less experience with interesting chemistry. This whole unfortunate trend of increasing government oversight of all things chemical will eventually neuter US chemical education and industry leaving a bland and uncompetitive culture averse to risk.

I hate to be critical of fire safety people. But I also hate to see chemical education and research hamstrung by well intended parties who have devised highly detailed and extensive rules that will seep into every aspect of the chemical sciences. I am aware of absolutely no pushback of any kind when it comes to this matter.

Flux-O-Links

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The US Nuclear Regulatory Commission website offers a downloadable set of documents pertaining to Fire Dynamics along with a few spreadsheets and loads of worked problems. The set of documents is quite well done in my estimation and is entirely suitable for we industrial chemists. My operating principle is that it never hurts to keep learning about fire phenomena when you work around flammable materials.

Gotten a little rusty in your welding theory?

An affordable spectrum analyzer is just what a fellow needs for the radio observatory.

Need pure Astatine, see p 19.  Light up the accelerator and dial up the proton current.

Spoolhenge

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Unlike many of my colleagues in the Chemical Industry, say in New Jersey for instance, Th’ Gaussling is able to enjoy a pleasant country drive to and from work every day. Among the many sights to enjoy is Spoolhenge. This curious archeological artifact is thought to have been constructed by ancient electricians in the early Cupracene Age of the Sparkezoic Era.

Who were these people? What strange rituals did they perform in this maze of paleospools? Only a few crude wirenuts fashioned out of elk antler remain in the soil surrounding these ruins.

Writer and amateur paleophrenologist Anders van der Klopp suggests the ruins may have been part of a temple built by ancient astronauts who crash landed on earth in the distant past. Van der Klopp’s panspermia theory is not taken seriously by mainstream paleophrenologists who balk at the idea of electricians in space. Perhaps one day we will solve the mystery.

Spoolhenge

Spoolhenge

Chemical Art in the Public Domain

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For the last few years I have been attempting to work with a full professor of chemistry who holds a named chair. He is fast approaching emeritus status and in addition to the other maladies of aging, he tends toward spontaneously bureaucratic demands and is rather hard of listening. His secretary types his correspondence which is written in the officious, pseudo-legalese tone remniscent of a 19th century divorce decree.

Recently, while discussing chemistry with the “judge” by email, I suggested that he look at the patent literature for clues to synthetic procedure. Procedures found in patents may have a general utility and are not automatically claimed. Minimally, a dip in the patent literature broadens ones knowledge of the prior art. Certainly, art found in expired patents has a high likelihood of being up for grabs.

My clumsy and sophomoric attempt at helpfulness sparked a multiparagraph recitation in reply on the anticipatory nature of content in patents and how “such material” is unacceptable for “we in academe”.

Suit yourself, says I. But like any prospector knows, gold is where you find it. And this brings me to a point.

Every week some number of US patents expire or lapse. This continuous stream of expiration represents a situation much like the periodic deposit of placer gold after the spring runoff.  Gold veins in the walls of the canyon spall and fracture allowing gold nuggets and dust to tumble into the creek.  Prospectors who know what to look for can pick up the occasional nugget of art that has fallen into the public domain.

Granted, expired art may be 17 years out of date, but many kinds of compositions and transformations in chemistry are not subject to the expiration of utility. Many kinds of oxidations, reductions, alkylations, halogenations, functional group transformations, etc., remain quite useful over time. What changes over time are the economic and regulatory compliance issues. It is possible to make C-C bonds without a platinum group metal, triflate, and boron.

The value of expired patent art is well known by the pharmaceutical industry. Pharma companies will fight like wounded bears to get extra days added to their patents or otherwise attempt to extend claimed art as far into the future as possible with formulation or other schemes. They know that the day after a cash cow drug goes off patent, there will be generic versions on sale by opportunistic producers.

Prior to June 8, 1995, utility and plant patents were allowed for a period of 17 years with the 17 year clock starting from the application date and the period of enforceability beginning on the issuance date. From June 8, 1995 onward, utility and plant patents are valid for 20 years.

It is in the nature of scientifically minded folk to be forward looking and lavish extra attention on the latest techniques.  In our enthusiasm for the new and exciting, we may forget the vast storehouse of knowledge accumulated over the last 100 years of chemical research.

There is an ever increasing store of public domain art at the patent office waiting to be extracted by those who have the interest to do so. If you do decide to adopt some expired art, it is worth paying attorneys fees to make sure your judgement is sound and to look for related patents that may be problematic. Due diligence is money well spent.

It is true that patents are written by lawyers with little interest in providing too much enablement to the public. But these lawyers also know that playing games with enablement is contrary to the intent of the sworn statements in the application and may ultimately weaken a patent during litigation. A patent isn’t a peer reviewed paper. But, to Phosita, it can be a rich source of clues on how to perform some particular expired art that may serve as the basis of a product or process.

Nernstian Sunrise in the Cryosphere

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WAWAwawa ..wawa..wawawa..waawaa..waaawaaa..wa..wa……wa……….wa.

The thermometer read -20 F this morning. It hasn’t been that cold for a few years.  As I sat in the Jeep listening to my battery die hard, my mind wandered fondly to the green meadows of P-Chem and the Nernst equation. This equation sets forth the relationship between temperature and cell potential.  The University of Arizona has this fantastic Nernst simulator (web version) that lets you dial in temperature and immediately see the effect on the voltage of the electrochemical cell.  It is plain to see that as the temperature drops, the EMF drops as well.

Knowing that nature wouldn’t let me summon sufficient wattage from my battery, I went back inside and switched on CNN.  After seeing multiple replays of an indignant journalist hurling a pair of shoes at our president, I was treated to an ad by the Central Intelligence Agency- the CIA. Yeah, the CIA is advertising on CNN!  Take a minute to get your arms around that.

Strangely, uncharacteristically perhaps, I experienced a synergistic swelling of sympathy after seeing the shots of Bush II being assaulted by Iraqi footwear followed by the patriotic CIA ad. For a moment- just a sparkle in time- a quorum of voices in my head agreed that somebody should kick that journalist’s ass. Bush II may be a buffoon, but he is OUR buffoon and nobody should treat him like that. There- I said it.

Receding Tide Strands All Boats

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Wow. Major dose of reality. For Th’ Gaussling, this economy fiasco just went from made-for-TV to in-your-face reality. Big chemical producers are pitching 10 % chunks of resourceful humanity overboard. They are burning down inventory levels, pushing back raw material purchases, and stopping capital projects. The reciprocal of the old saw about “a rising tide lifting all boats” is in effect.

Well, everywhere except government. Government seems to continue to build up debt obligations into the tens of terabucks range. Now is a good time to have defense related products- things that have MIL SPEC on them.

But now is when it really sucks to be in advertising, RV sales, and office supplies.  Advertising budgets are among the easiest to cut when the flancing of blubber begins. 

This is a great time to hire. Lots of job candidates out there with degrees. I’ve been getting Hail Mary resumes from people wildly disconnected from chemistry.

If you are a well paid 50-something, golly, you might as well put a target on your back. This is one of the ways companies can re-jigger their staff to be rid of those expensive, middle aged folk who burden the health insurance pool with those costly diseases. In a recession, a company can use the situation to reset the payroll and have a chance to restaff with cheaper worker bees when things pick back up. That is, if there is anybody left.

The Chemical Entrepreneur. Part 2.5.

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There are as many ways of starting a chemical business as there are people starting them. Entrepreneurs range in profile from smooth talking slicksters to sober, ROI-calculating engineers. Entrepreneurs can also be rather unruly folk. It is not automatically true that business founders are inherently talented at designing and running orgainzations. In fact, they are frequently poor at it.  But, successful founders are usually highly focused and are able to attract resources.

A common motivation for starting a business is that the founder is possessed with existential certainty that he/she can operate a business venture better than, say, a former boss or rival. A business founder may be a free spirit, refractory to sensible advice, or may be a solemn Harvard MBA operating by the book. It is not uncommon for a founder to have had several previous failed ventures prior to a successful one.

And make no mistake, the sense of power that a founder feels in the execution of a business plan can be as addictive as heroin or crack. Once a person has had the experience of successfully gathering resources and then allocating them to leverage progress to a goal, they are forever changed. Whether or not they continue the role of managing funds or personnel, their eyes have been opened to the real meaning of power.

Power is the ability to allocate resources.

No matter what kind of chemical business one wishes to start, it is crucial to understand that it will require the accumulation of some kind of resource that you can apply to a problem. That resource can range from your technical reputation, 30 days net of commercial credit, VC monies, or a chemical processing plant. It is all a form of leverage toward the greater goal converting streams of goods and services into streams of cash.

Try to get cash flowing from sales as early as possible. Choosing a Market-Pull activity is the best way to do this.

A chemist starting up a business is able to choose several kinds of general business activities.  If you want to be a consultant, you must determine the boundaries of your knowledge and then find demand for that expertise.  If you are truly an expert in a field, then more likely than not you know who might buy your services.

If you choose a Technology-Push approach, try to target customers who are willing to be early adopters.

A chemist may be well situated to start an operation offering analytical services. In that case, the enterprising analyst needs to know about underserved demand out in the marketplace. You need to offer a service that prompts people to send a purchase order to you.

If your startup is a one-act pony, it is critical that the pony actually be able to jump through the flaming hoop as advertised. Try to avoid one-act pony business plans.  Find Market-Pull products to pay the bills while your Technology-Push products are under development.

A chemist is in a great position to get into formulations.  While this might not be strictly a “chemistry’ activity, the walking-around-knowledge of chemicals that a chemist might have probably well exceeds the basic chemistry knowledge of many “experts” in the formulations business. However, a chemists general knowledge may not be applicable for direct application to formulations. A formulator must accumulate specialized knowledge and analytical methods for the materials they handle, including things like rheology, cloud and pour points, fungal contamination, and miscibilities. The level of infrastructure for doing formulations can be dramatically less stringent than chemicals manufacturing as well, requiring less startup capital. That said, formulations may be in demand at the large scale. Puttering around at only the less-than-drum scale may have no future.  Again, to be a formulator you need to know what is in demand.

Remember-Sometimes it is dumb to be too smart about things. Be customer oriented. Be honest about strengths and weaknesses.  Learn the difference between smart and cagey. Dick was a cagey businessman. Don’t be a Dick.

Fine chemicals manufacture has many success stories.  Alfred Bader started his Aldrich empire making what we now call Diazald. Bader was extremely customer service oriented and I believe this was the key to his success. He visited laboratories and asked workers what they needed. If the request was reasonable, he would put the material in the catalog collection. If the chemist-entrepreneur desires to start a catalog fine chemical company to sell reagent chemicals and widgets, then I would advise making a study of that business arena.

An understanding of the regulatory compliance world is critical as well, especially relating to the Toxic Substances Control Act, TSCA. A company may have to start out as being a provider of ‘R&D Only’ products. To freely sell commercial quantities of specialty and fine chemicals, a substance must be on the EPA’s public or confidential lists. If not, then permission must be granted by EPA. This will require a special filing which discloses its manufacturing and/or use process, Personal Protection Equipment (PPE), fugitive dust and corresponding controls on exposures to workers and the environment, vapor releases and method of control, a disclosure of how much of the New Chemical Substance (NCS) gets into the environment, any and all available toxicity data, a Safety Data Sheet, physicochemical data, waste NCS disposal, batch size and yearly production. For less than or equal to 10,000 kg per year a Low Volume Exemption (LVE) can be filed. This is an abbreviated version of a Pre-Manufacturing Notification (PMN) filing which will be examined in greater detail and will take much longer for EPA to complete. EPA has the right to require the submitter to collect certain kinds of toxicological data at the submitters expense. These tests are standardized and are performed by certified labs.

Most advisors to entrepreneurs will say that the prospective businessperson is well advised to put down a written plan. This is important on many levels. The act of writing a business plan is useful to the entrepreneur in several ways.  It causes the writer to focus his/her ideas and energy as well as to clarify the goal and how to track towards it. A well written business plan is critical if you need to attract funds to get the operation started. Investors and bankers need a document to study and to bring before others for analysis and buy-in. Just gotta have it.

Starting a drug company is going to be quite difficult for a few isolated chemists to do. It is a complex and insanely expensive and risky business that requires a wide diversity of players to be on board and committed. Somewhere you have to get an MD or MD/PhD, finance people, former pharma executives, regulatory affairs peoples, etc., on the board to add gravitas to your plan. A whole circus of expensive prima donnas. Sounds like a nightmare to me.

Melamine Spill on Isle Five!

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The reality of melamine in animal feeds and milk products has crossed the ocean and landed on the shores of North America. Trace levels of melamine have been detected in certain baby formula products in the US.

The National Milk Providers Federation (NMPF) has responded with a statement on their position on adulterants. Having been in the milk processing business as a quality control chemist, I can add that my experience with the industry is consistant with the statement by the NMPF.

To understand the true level of confusion and diverse practices relating to this problem, it is important to note that the analytical methods used by US milk processors are insensitive to the presence of melamine itself. Here is why: Raw milk arriving to a processing facility is tested for the presence of antibiotics, fat content, flavor, pH, and total solids. To my knowledge, there is no batch QC protein analysis anywhere in the US manufacturing flow. In Asia, apparently protein analysis is common. 

The practical consequence of this analytical protein blindness in the US is that there is no benefit to adding melamine to milk because pricing is not determined by protein content. Milk is sold by the pound and its premium value is determined by the butterfat content.

Milk has been subject to many kinds of fraudulent modifications in the past. Sour milk has been neutralized with caustic. Today all milk is taste-tested for off flavor. Milk has been diluted for higher profit. Today all raw milk is tested for % solids and % fat to detect dilution. It should be above a certain minimum on both accounts. Cows have been milked abusively into chronic mastitis and given antibiotics. All milk is now tested for antibiotic residues via chemical and microbial assays. Finally, milk that contains an excessive microbial loading is rejected.

If Chinese milk processors adopted a similar testing protocol, the benefit of direct adulteration of milk with melamine would disappear. The effects of melamine-laced cattle feed is another issue. I have not heard of studies that connect ingestion of melamine contaminated feedstocks to milk contamination. Perhaps this has already been done.

According to the Wall Street Journal–

Dr. [Stephen] Sundlof said the melamine traces stemmed from the products coming in contact with the chemical during processing. The FDA approved melamine as a “food contact substance” about four decades ago.

The article continues-

The FDA said last month that it’s safe for consumers to eat most food with melamine below 2.5 parts per million, but infant formula was the exception. “FDA is currently unable to establish any level of melamine and melamine-related compounds in infant formula that does not raise public health concerns,” it said.

I am heartened to see that the FDA is reluctant to establish a threshold for safe consumption by infants. But at the same time, the matter of a 2.5 ppm threshold for everyone else amounts to a sh*t sandwich for the public.

The levels detected by US companies and agencies seems rather low. Again, from WSJ-

A spokesman for Mead Johnson Nutritionals, owned by Bristol-Myers, said the company’s own tests haven’t turned up any melamine, and the FDA tests turned up melamine levels “lower than the 0.25 parts per million limit that can be measured by the published FDA test method.” Mead Johnson, he said, maintains “stringent standards at all our manufacturing sites to ensure the high quality and safety of our products that our customers have come to expect.”

Dr. Sundloff said the melamine detected was tiny. Out of 87 samples, it found one sample with 0.137 parts per million and 0.140 parts per million on a verification test.

While toxicological threat to US consumers at the sub-ppm level is unclear at the moment, what seems to be lacking at FDA is a discussion as to the need to allow any level of melamine in any consumable.

Here is what is clear to Th’ Gaussling:

There is no overlap in the material streams of melamine or melamine resin manufacture with any dairy product. No dairy operation should reasonably expect to require containers of melamine monomer in its warehouse, nor should any supplier to dairy product manufacture.

Melamine contamination by contact exposure to melamine resin components can be averted by the use of many other food grade materials of construction, i.e., stainless steel.

If melamine is detected in food articles, it is the duty of the manufacturer to promptly audit all suppliers and eliminate the source of contamination.

Rather than tolerate and regulate the presence of a material whose only purpose is to perpetrate fraud, the FDA should ban food products containing detectable amounts of melamine. If the FDA goes forward with acceptable levels of melamine in dairy products, suppliers would begin to game the system. In a short time, ppm levels of melamine will be considered “normal” and suppliers of melamine contaminated feedstocks will be legitimized up to the regulatory threshold. 

A firm stand by regulatory agencies will strengthen the motivation of manufacturers to maintain strong audit trails and take away the financial incentive to use this fraudulent additive.